Anellated Calix[4]arenes
Dissertation
for the Degree of
Doctor of Natural Sciences (Dr. rer. nat.)
by
Wiebke Hüggenberg
from Witten
Faculty of Chemistry and Biochemistry
Bochum 2011
Referent: Prof. Dr. Gerald Dyker
Koreferent: Prof. Dr. Martin Feigel
Tag der Abgabe: 16.5.2011
Tag der Disputation: 8.7.2011
Die vorliegende Arbeit wurde von Januar 2007 bis Mai 2011 am Lehrstuhl für
Organische Chemie II der Fakultät für Chemie und Biochemie der Ruhr-Universität
Bochum in dem Arbeitskreis Organische/Metallorganische Chemie von Herrn Prof. Dr.
Gerald Dyker angefertigt.
Herrn Prof. Dr. Gerald Dyker danke ich für die Überlassung des interessanten Themas,
die Diskussionsbereitschaft bei theoretischen und praktischen Problemen sowie den
gegebenen Freiraum zur Forschung.
Herrn Prof. Dr. Martin Feigel danke ich für die freundliche Übernahme des Koreferats.
Meinen Laborkollegen Marcus Pillekamp, Dr. Matthias Kanthak, Erik Schwake,
Stephan Schöler, Christian Dietz, Dr. Hebert Estevez Rivera, Dr. Lertnarong Sripanom
und Dr. Thomas Meyer-Gall danke ich für das angenehme Arbeitsklima, die zahlreichen
kleineren und größeren Gefallen und die Unterstützung während der gesamten Zeit.
Annamaria Seper und Christian Wagner danke ich für ihre Beiträge zu dieser Arbeit im
Rahmen von Vertiefungspraktika.
Den ehemaligen Masterstudenenten Sebastian Klimczyk, Simon Trosien und Saskia
Neukirchen möchte ich ebenfalls für ihre Unterstützung und das angenehme
Arbeitsklima danken.
Besonderer Dank gilt den Mitgliedern der analytischen Abteilungen der Fakultät: Herrn
Gregor Barchan und Herrn Martin Gartman möchte ich ganz besonders für die
Aufnahme zahlreicher NMR-Spektren danken. Frau Sabine Bendix und Frau Jutta
Schäfer danke ich für die Aufnahme zahlreicher Massenspektren. Frau Karin
Bartholomäus möchte ich für die Durchführung der Elementaranalysen danken.
Frau Prof. Dr. Iris M. Oppel danke ich für die Aufnahme und besonders die
Verfeinerung der Röntgenstrukturanalysen. Ebenfalls möchte ich Frau Manuela Winter
für die Aufnahme der Röntgenstukturanalysen danken.
Tobias Plöger danke ich für die Aufnahme der ATR-IR Spektren.
Dem Lehrstuhl für Organische Chemie I von Herrn Prof. Kiedrowski möchte ich für die
Nutzung der Feinwaage danken.
Allen Mitarbeiterinnen und Mitarbeitern des Lehrstuhls Organische Chemie II, Frau
Heidemarie Joppich, Frau Barbara Schröder, Frau Ulrike Steger und Herrn Torsten
Haenschke der Ruhr-Universität Bochum danke ich für die vielfältige Unterstützung
und die freundliche Aufnahme. Besonderer Dank gebührt Herrn Klaus Gomann für die
technische Unterstützung bei Problemen mit der HPLC-Anlage.
Meinen Eltern danke ich für die Unterstützung und Geduld während dieser Arbeit,
besonders in den letzten Monaten.
Meinen Freunden möchte ich ebenfalls für ihre Hilfsbereitschaft, Geduld und
Unterstützung danken.
Besonderen Dank möchte ich Stephan Schöler und Christian Dietz für das kurzfristige
Korrekturlesen dieser Arbeit aussprechen.
Für finanzielle Unterstützung möchte ich der Deutschen Forschungsgemeinschaft
(DFG) danken (Projekt Dy 12/9-2).
i
Table of contents
I. Theoretical Part 1
1 Introduction 1
1.1 General 1
1.1.1 Syntheses of calixarenes 7
1.1.2 Conformational Isomerism 8
1.1.3 Inherently chiral calixarenes 11
1.1.4 Nomenclature 12
1.2 Goal of Research 12
2 Multifold Photocyclizations of Styrylcalix[4]arenes 15
2.1 Calix[4]arenes with anellated subunits and [2+2] cycloaddition products 15
2.2 Synthesis and photocyclization of a proximal distyrylcalix[4]arene 18
2.3 Prevention of the [2+2] cycloaddition by steric hindrance 25
2.4 Conclusion 30
3 Anellated calixarenes by dehydrohalogenation 31
3.1 Introduction 31
3.2 Phenanthrene model compounds 36
3.3 Syntheses of calix[4]phenanthrene derivatives 41
3.4 Synthesis of a fluorenone model compound 50
3.5 Syntheses of calix[4]fluorenones 57
3.6 Previous studies on calix[4]triphenylenes 70
3.7 Synthesis of a triphenylene model compound 74
3.8 Syntheses of calix[4]triphenylenes 76
3.9 Conclusion 84
4 Syntheses of unsymmetrical tetrazines 89
4.1 Introduction 89
4.2 Syntheses of tetrazine model compounds 92
4.3 Synthesis of tetrazine moieties at calix[4]arenes 100
4.4 Conclusion 105
Table of Contents
ii
5 Conclusion and Outlook 109
II. Experimental Part 113
1 Methods and Materials 113
1.1 Reaction control and separation methods 113
1.2 Analytical chemistry: apparatus, instruments, acquisition methods and
comments on analytical data 114
1.3 Solvents and reagents 116
2 Syntheses 121
2.1 Syntheses of reagents and model compounds 121
2.1.1 Triphenyl(1-phenylethyl)phosphonium bromide (84) 121
2.1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118) 123
2.1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124) 126
2.1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethyl-
silane (125) 129
2.1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-
phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-
3,5-dimethylphenyl)methanone) (120b) 132
2.1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and
1-(4-hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128) 137
2.1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) 141
2.1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130) 144
2.1.9 (2-Bromophenylethynyl)trimethylsilane (144) 147
2.1.10 1-Bromo-2-ethynylbenzene (140) 149
2.1.11 2-Chlorobenzoyl chloride (148a), 2-Bromobenzoyl chloride (148b),
2-Iodobenzoyl chloride (148c) 151
2.1.12 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) 154
2.1.13 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) 157
2.1.14 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c) 160
2.1.15 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151) 163
2.1.16 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154) 166
2.1.17 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161) 169
Table of Contents
iii
2.1.18 4-Bromo-2,6-dimethylphenol (208) 172
2.1.19 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209) 174
2.1.20 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210) 177
2.1.21 1,3-Dimethyltriphenylen-2-yl acetate (211) 180
2.1.22 4-Methoxy-3,5-dimethylbenzaldehyde (250) 183
2.1.23 4-Methoxy-3,5-dimethylbenzoic acid (251) 185
2.1.24 4-Methoxy-3,5-dimethylbenzoyl chloride (245) 187
2.1.25 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246) 189
2.1.26 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydra-
zonoyl chloride (247) 192
2.1.27 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole
(253) 195
2.1.28 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine
(249) 198
2.1.29 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258) 201
2.1.30 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzohydrazonoyl
chloride (259) and 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-
oxadiazole (260) 203
2.1.31 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine
(261) 208
2.1.32 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262) 210
2.2 Syntheses at the upper rim of calixarenes 213
2.2.1 Transannular cyclization-product (cone) (60) 213
2.2.2 cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]arene (73) 216
2.2.3 cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene (74) 218
2.2.4 cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]arene (75) 220
2.2.5 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-
arene (65) 222
2.2.6 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c) 226
2.2.7 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (85) 233
2.2.8 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene
(86a and 86b) 236
Table of Contents
iv
2.2.9 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-
tetra-n-propoxycalix[4]arene (88) 240
2.2.10 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-
calix[4]arene (132) 243
2.2.11 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(133) and 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]arene (134) 245
2.2.12 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-
propoxycalixarene (136) 249
2.2.13 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a) 252
2.2.14 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b) 255
2.2.15 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(141a) 257
2.2.16 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxy-
calix[4]arene (141b) 260
2.2.17 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a)263
2.2.18 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(137b) 266
2.2.19 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and
5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166) 269
2.2.20 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and
5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172) 274
2.2.21 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) and
5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) 279
2.2.22 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),
5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and
paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180) 282
2.2.23 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),
paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (175) and
5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176) 289
2.2.24 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165) 296
2.2.25 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and
5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174) 297
Table of Contents
v
2.2.26 cone-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163),
5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181) and
paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182) 302
2.2.27 cone-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (166),
paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) and
5,17-Bis(2-chloro-benzoyl)-25,26,27-tri-n-propoxcalix[4]arene (178) 306
2.2.28 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184) 309
2.2.29 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene
(212) 314
2.2.30 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene
(214) 317
2.2.31 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218) 320
2.2.32 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]-
arene (220) 322
2.2.33 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes
(217a and 217b) 325
2.2.34 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b) 329
2.2.35 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263) 332
2.2.36 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-dicarbonyl chloride
(264) 334
III. Appendix 335
1 Cross-peak tables 335
1.1 General Remarks 335
1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118) 336
1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124) 337
1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)-trimethyl-
silane (125) 338
1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-
phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-3,5-
dimethylphenyl)methanone) (120b) 340
1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and 1-(4-
Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128) 342
Table of Contents
vi
1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) 344
1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130) 345
1.9 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) 346
1.10 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) 347
1.11 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c) 348
1.12 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151) 349
1.13 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154) 350
1.14 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161) 351
1.15 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209) 352
1.16 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210) 353
1.17 1,3-Dimethyltriphenylen-2-yl acetate (211) 354
1.18 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246) 355
1.19 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydra-
zonoyl chloride (247) 356
1.20 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole
(253) 357
1.21 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine
(249) 358
1.22 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258) 359
1.23 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzohydrazonoyl
chloride (259) and 2-(4-Methoxy-3,5-dimethyl-phenyl)-5-phenyl-1,3,4-
oxadiazole (260) 360
1.24 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine
(261) 362
1.25 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262) 363
1.26 Transannular cyclization product (cone) (60) 364
1.27 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene
(65) 366
1.28 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c) 369
1.28.1 proximal cone-Calix[4]diphenanthrene (81a) 369
1.28.2 proximal cone-Calix[4]diphenanthrene (81b) 373
1.28.3 proximal cone-Calix[4]diphenanthrene (81c) 375
1.29 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxy-
calix[4]arene (85) 377
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vii
1.30 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene
(86a and 86b) 380
1.31 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-
tetra-n-propoxycalix[4]arene (88) 383
1.32 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(133) 385
1.33 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-
propoxycalixarene (136) 387
1.34 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a) 389
1.35 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(141a) 391
1.36 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(141b) 393
1.37 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a) 395
1.38 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(137b) 397
1.39 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and
5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166) 399
1.40 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and
5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172) 403
1.41 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) 407
1.42 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),
5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and
paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180) 409
1.43 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),
paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (175) and
5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176) 415
1.44 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and
5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174) 421
1.45 paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182) 425
1.46 paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) 427
1.47 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184) 430
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viii
1.48 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene
(212) 435
1.49 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene
(214) 437
1.50 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(220) 439
1.51 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes
(217a and 217b) 441
1.52 29,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b) 444
1.53 Structure (157) 448
2 Crystal Structure Data 449
2.1 Transannular cyclization-product (cone) (60) 449
2.2 proximal cone-Calix[4]diphenanthrenes (81a) 463
2.3 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene
(86a) 475
3 Abbreviations 489
4 References 493
1
I. Theoretical Part
1 Introduction
1.1 General
Calixarenes are basket-shaped cyclic oligomers of phenol units, bridged by methylene
groups ortho to the hydroxyl groups.1 Their three-dimensional structure makes them
attractive building blocks for supramolecular chemistry2 and they are predestined to act
as host molecules because of their electron-rich, hydrophobic cavity. Moreover, they are
readily available and can easily be functionalized as required. Their ability to complex
cations3, anions4 or small neutral5 molecules makes them useful for separations and
applicable as sensors, selective receptors or extractants.6 Especially interesting is their
potential for enantioselective recognition and asymmetric catalysis utilizing inherently
chiral calixarenes (see Chapter 1.1.3 for inherent chirality).7 Furthermore, they can be
used as modifiers to improve selectivity in separations by HPLC or when bound to
silica gel they can serve as the stationary phase themselves.8
Calixarenes 1 and 2 are examples of fluorescent molecules able to detect toxic metals
(Figure 1.1). The 1,3-alternate calixarene 1, water-soluble due to the sulfonyl groups at
the upper rim, detects Cs+ selectively over other ions and could therefore find
application in extracting Cs+ from nuclear waste.9
Figure 1.1. Fluorescent sensors for Cs+ and Cd2+.
2 Theoretical Part
Functionalization of the calixarene scaffold with 1,2,3-triazole-containing systems, as
in calixarene 2, has been reported to be promising for the detection of Cd2+ and Zn2+
cations in organic solvents.10
Ion-selective electrodes based on calixarene 3, containing soft sulfur binding sites,
exhibit a high selectivity towards Ag+ over other ions, except Hg2+.11
Calixarene 4 contains pyrene units as chromphores, which are linked via amide
functionalities to the calixarene skeleton, and is an anionic receptor (Figure 1.2). It can
selectively detect fluoride, while no complex formation is observed with other halide
ions.12 The complex formation with F- ions causes a 54 nm red-shift of the UV
absorption band and a 12 nm blue-shift of the excimer emission as well as enhanced
fluorescence.
Figure 1.2. Fluorescent receptor for fluoride ions (4) and calixarene 5 , R = propyl, capable of
ion-pair recognition.
Calixcrown 5 is a ditopic receptor, which can complex a carboxylate ion by hydrogen
bonding with its upper rim hydroxytrifluoroethyl substituents and also bind a sodium
cation at the bridging polyether chain.13 Moreover, the presence of a sodium cation
enhances the ability to complex the anion at the upper rim. While the free ligand 5
adopts a flattened cone conformation with the trifluoroethanol groups sticking out and
the free phenolic units parallel to each other, the sodium complex has a more open
cavity. This probably enables the acetate ion to enter the cavity with the carboxylate
oxygen in proximity to the bound sodium cation, instead of forming hydrogen bonds to
the hydroxyl group.
Calixarenes also have a great potential in studying biomolecular functions like
recognition, catalysis and transport or acting as multivalent ligands for bio-
Introduction 3
macromolecules.14 One of the first examples was a vancomycin mimic based on the
calix[4]arene scaffold reported by Ungaro and et al.15
The transfer of chloride ions through lipid bilayer membranes has been studied using
calixarene like 6 bearing butylamide substituents at the lower rim.16 One molecule of 6
is, however, too small to span the membrane. Apparently, ion channels are formed by
HCl-mediated self-assembly to aggregates as observed for a comparable structure with
tetramethylamide chains. The proximally 1,5,9-triazacyclododecane substituted
calixarene 7 is a phospodiesterase mimic, efficiently catalyzing the cleavage of
phosphodiester bonds.17 Interestingly, it was observed that the metal centers act
cooperatively in the cleavage when they are on adjacent phenol units, while they act
independently from each other in the distally substituted analogue. The catalytic
efficiency was not further enhanced when three metal centers were placed at adjacent
positions.
HN
OO
OO
HN
O
NH
O
O ONH
6
OO OO
N N
N
N N
NH
H H
H
O O OO
Cu2+ Cu2+
7
Figure 1.3. Examples of calixarenes with the ability to mimic biological functions: ion
transporter 6 and the artificial phosphodiesterase 7.
Chiral recognition and asymmetric catalysis are important in biological systems.
Accordingly, chiral and especially inherently chiral calixarenes are of great interest
since artificial chiral receptors based on calixarenes could help in the study and
understanding of biological systems. Calixarene 8 contains a chiral side chain and
reveals enantioselective recognition towards N-Boc-protected alanine anion 9 (Figure
1.4).18 The (+)-enantiomer of calixarene 10 was reported by Shimizu et al. to show
recognition towards (R)- and (S)-mandelic acid and could be used to determine
enantiopurity of the acid by NMR.19
4 Theoretical Part
Figure 1.4. Enantioselective anionic receptor 8 for alanine anion 9 and inherently chiral
calixarene 10 that can distinguish between enantiomers of mandelic acid.
Moreover, 10 was the first inherently chiral calixarene to be used for asymmetric
catalysis. Although the observed enantioselectivy was poor, the asymmetric Michael-
type addition of thiophenol and cyclohexanone catalyzed by 10 showed chiral
induction.
The enantiomeric palladium complex 11 is the first example of a metal complex based
on an inherently chiral calixarene used in asymmetric catalysis (Figure 1.5).20,21 It
shows good activity as a catalyst for allylic alkylation and hydrogenation. The
alkylation of 1,3-diphenylprop-2-enyl acetate 12 with dimethyl malonate in the presence
of Me3SiOC(NSiMe3)CH3 proceeded with 100 % conversion. After three hours 67 % ee
were achieved with R = H, while R = SiMe3 afforded only 45 % ee.
Figure 1.5. First example of a metal complex based on an inherently chiral calixarene and its
application in the alkylation of 1,3-diphenylprop-2-enyl acetate 12.
When 11 was synthesized with two identical chiral side chains, and thus being not
inherently chiral, no chiral induction was observed. The complementary distally
Introduction 5
substituted ligand showed only poor enantioselectivity, giving 16 % ee. These findings
suggest that the selectivity is little influenced by introduction of asymmetric carbons
alone.
n n n n
Figure 1.6. Calixarenes and calixarene metal complexes used in catalysis.
Calixarenes like 14 can act as phase-transfer catalysts or be used for the extraction of
alkali-metal ions (Figure 1.6).22 While the lipophilic tert-octyl group enhanced the
catalytic activity as well as the extraction ability, the length of the polyether chain,
where the ions bind, has no significant effect.
Biscalix[4]arene-dirhodium complex 15 has been used for the cyclopropanation of
olefins. For example, employing 1 mol% at 20 °C in dichloromethane successfully
converted styrene (17) in 98 % (E/Z 72:28) in the presence of methyl diazoacetate
(MDA) (Scheme 1.1, example a)).23
Furthermore, calixarene 16, formed in situ from its chloromethyl precursor and
Pd(OAc)2, has been applied in the Suzuki cross-coupling of 4-chlorotoluene (19) with
phenylboronic acid (Scheme 1.1, example b)).24
Scheme 1.1. Applications of calixarene metal complexes 15 and 16: a) cyclopropenation of
olefins and b) Suzuki cross-coupling.
6 Theoretical Part
When 16 itself was used as ligand, 4-methylbiphenyl (20) was obtained in only 16 %
yield. Exchanging the isopropyl groups for mesityl groups improved the yield to 50 %,
which could be further increased to 60 % by introducing tert-butyl groups in para-
position of the other two phenol units.
Lately, the interest in hetera- and heterocalixarenes or mixtures of both as a new
generation of supramolecular host molecules has increased (Figure 1.7).25 In
heteracalixarenes phenol units are bridged by heteroatoms―such as oxygen, nitrogen or
sulfur―while in heterocalixarenes phenol units are substituted for hetero-
aromatics.25b,26,27
Figure 1.7. General structures of hetera- and heterocalixarenes.
Although oxa-,28 aza-29 and thiacalixarenes28c have been known for a while, the low
yields in which they were obtained prevented them from becoming more generally used.
Meanwhile, Miyano et al.30 introduced a one-pot procedure similar to conventional
calixarene synthesis to yield thiacalix[4]arene 21 in 54 % as well as a two-step
procedure yielding 21 in 83 % and the corresponding calix[6]- and calix[8]arenes as by-
products in significantly lower yields of about 5 % (Figure 1.8). Both lower and upper
rim derivatization have been successfully employed with this class of calix[4]arenes as
well as derivatization of the bridging sulfur atoms.31
Figure 1.8. Heteracalixarenes.
Several oxacalix[4]arenes27 were synthesized by Katz et al.32 in one step by
nucleophilic aromatic substitution (SNAr) of resorcinols with 1,5-difluoro-2,5-
Introduction 7
dinitrobenzene in yields between 80–90 %. Calixarene 22, for example, was obtained in
88 % yield and shown by X-ray diffraction analysis to adopt a distorted 1,3-alternate
conformation in the solid state.
Azacalixarenes, however, have been only obtained in low yields so far. Compound 23
was synthesized by Tsue et al.33 in a stepwise procedure yielding only 9 % overall,
while 24 was obtained in 19 % in one-step by Yamamoto et al.34,35
Figure 1.9. Heterocalixarenes.
Among heterocalixarenes (Figure 1.9), calixpyrroles like 25a, first synthesized by
Baeyer in 1886,36 have been studied extensively regarding their ability to act as
receptors for anions or neutral molecules and their transition metal coordination
chemistry.37,38
Calix[4]pyrroles have been converted to chlorocalix[4]pyridines 26, with chlorine in
one of the indicated positions, by reaction with dichlorocarbene.39 Jurczak et al.
reported the synthesis of calixfuran 25b in 71 % yield by condensation of furan with
acetone in the presence of concentrated sulfuric acid.40 Research by Wang et al. has
concentrated on stepwise fragment coupling to yield various heterocalixarenes with
mixed aromatic subunits bridged by heteroatoms. Examples are the oxacalix[2]-
arene[2]triazene 27 and azacalix[4]pyridines like 28, of which the azacalix[4]-
arene[4]pyridine shows high complexation ability towards C60 and C70.25d,41
1.1.1 Syntheses of calixarenes
Calixarenes are synthesized by base-catalyzed condensation of para-substituted
phenols, usually p-tert-butylphenol (29), with formaldehyde (30) (Scheme 1.2).
The ring size depends on the base used and its concentration as the cations have a
template effect.1a,42 Symmetrically substituted calixarenes with four, six or eight
8 Theoretical Part
subunits are available in good yields by one-pot procedures.43 Calix[5]arenes as well as
larger ring sizes have also been synthesized in low yields.44
Scheme 1.2. Synthesis of calix[4]arene 32.
Calixarenes consisting of nine to twenty phenol subunits, for example, were obtained
through acid-catalyzed condensation by Gutsche et al.44c Stepwise syntheses can yield
unsymmetrically substituted calixarenes, but are often tedious and give low overall
yields, which is improved by convergent multi-step syntheses.45,46
In para position unsubstituted calixarenes are obtained by lewis acid catalyzed
dealkylation47 of the corresponding p-alkylcalixarenes.48 A wide range of calix[4]arenes
is available by functionalization of calix[4]arene 32 at the hydroxyl groups49 (lower rim
or narrow rim) and the para position of the phenyl rings50 (upper rim or wide rim).
Although less common, meta-substituted calixarenes are also available either by the less
attractive fragment condensation51 or direct functionalization,52 usually assisted by
ortho-directing groups. Thus, not only tetrasubstituted calixarenes can be obtained, but
mono-, 1,2-di- or 1,3-di- and trisubstituted calixarenes, both at the upper as well as the
lower rim, can be also selectively synthesized.53
1.1.2 Conformational Isomerism
Calix[4]arenes can adopt the four different conformations depicted in Figure 1.10: cone,
partial-cone (paco), 1,2-alternate and 1,3-alternate.54 These conformations can
interchange through ring inversion, whereby either the hydroxyl groups or the
para-substituent passes through the ring. However, the latter only matters when
hydrogen is in para-position.
In most cases the cone conformation is favoured both in solution and in the solid state
for calixarenes with free hydroxyl groups. This is confirmed by crystal structure data as
well as the stretching vibrations of the hydroxyl groups, which appear at unusually low
frequencies, in IR spectra.5a-b,55 The reason is stabilization of the cone conformation by
intramolecular hydrogen bonding between the phenolic hydroxyl groups.
Introduction 9
Figure 1.10. Conformational isomerism of calix[4]arenes substituted at the upper rim.
Due to the ring inversion, 1H NMR spectra show only two broad singlets for the
bridging methylene groups at higher temperatures. At lower temperatures, when the ring
inversion is slow on the NMR time scale, these signals appear as two doublets.
Inversion barriers and coalescence temperatures were investigated in dependence from
various solvents by temperature-dependent 1H NMR spectroscopy.56
Alkylation of the hydroxyl groups can fix the calix[4]arene in one of the four
conformations when the alkyl groups are larger than ethyl.57 The conformation adopted
upon alkylation can be influenced by the choice of solvent and alkylating agent as well
as the base used for the deprotonation of the hydroxyl groups, since a metal template
effect of the cations plays a crucial role.57b,58
The different conformations can be distinguished by the characteristic signal pattern
of the methylene protons (Table 1.1). For symmetrical cone calixarenes a highfield
doublet at about 3.2–3.5 ppm and one at lower field around 4.2–4.5 ppm can be usually
observed. The first is assigned to the equatorial protons (in proximity to the aromatic
ring), while the latter belongs to the axial protons (closer to the hydroxyl group).
Figure 1.11. Phenol rings in syn and anti orientation.
10 Theoretical Part
Table 1.1. Characteristic NMR signals of the methylene groups in the different conformations.
signals for the methylene protons conformation
1H NMR
13C NMR
cone two doublets
(each 4 H, J ≈ 12 Hz) one signal: 30–32 ppm
partial-cone
four doublets
(each 2 H, J ≈ 12 Hz) or
two doublets (each 2 H,
J ≈ 12 Hz) and one singlet (4 H)
two signals: 31 ppm and 37 ppm
1,2-alternate two doublets (each 2 H,
J ≈ 12 Hz) and one singlet (4 H) two signals: 31 ppm and 37 ppm
1,3-alternate one singlet (8 H) one signal: 37–38 ppm
13C NMR spectra also give information about the conformation since the shift of the
methylene carbons is little influenced by functionalization in para position or at the
hydroxyl groups.59 Methylene carbons between phenol units with anti orientation are
shifted by about 6 ppm downfield compared to their syn equivalents (Figure 1.11).
Tetra-O-alkylated calix[4]arenes usually do not adopt C4v symmetry, as would be
expected from NMR data. Crystal structure analyses as well as temperature-dependent
NMR experiments in solution60 have shown that the C2v-symmetric conformation,
pinchend cone or flattened cone, is favoured (Figure 1.12). In the pinched cone
conformation two phenol units are coplanar to each other, while the other units are tilted
outwards. The meta and para aryl protons of the subunits that are parallel to each other,
experience an upfield shift caused by the ring current of the opposite phenol ring.61
Figure 1.12. Inversion of calix[4]arenes in cone conformation between C2v-C4v symmetries.
Computational studies confirm that the C2v-symmetric conformation is the
energetically more stable conformation.62 Thus, the C4v symmetry observed in NMR
Introduction 11
spectra is considered to be a transition state between the pinched cone conformers, the
rate of interconversion between these being faster than the NMR timescale.
1.1.3 Inherently chiral calixarenes
The easiest way to synthesize chiral calixarenes is functionalization with chiral
substituents.63 However, due to their three-dimensional structure calixarenes can be
chiral although consisting of achiral phenol units.64 This inherent chirality, first
mentioned by Böhmer,64a was defined by Schiaffino et al.65 as arising “from the
introduction of a curvature in an ideal planar structure that is devoid of symmetry axes
in its bidimensional representation”, or to be more exact “is devoid of perpendicular
symmetry planes in its bidimensional representation” as described by Szumna.66 The
first example of an inherently chiral calixarene was reported by Gutsche et al. (33,
Figure 1.13).46
OAcOAc AcOOAc
OO
O
33
OH
O
O O
OO OO
35
37
OHOH HOOH
O OEt
34
OOH HOO
Br Br
PO
OO
36
OO OO
EtO EtO OEt OEt
38
OO OO
EtO EtO OEt OEt
39
O
Br
HN O
Figure 1.13. Examples of inherently chiral calixarenes.
12 Theoretical Part
One way to introduce inherent chirality in calixarenes in the cone conformation is
asymmetric funtionalization at either the upper67 or lower rim68, or both.69 In addition
asymmetric functionalization can be combined with conformational variation of the
calixarene ring as in calixarene 37.70 Another approach is meta functionalization,
usually achieved by prior functionalization of the para position with an ortho-directing
group,52a as described for calixarene 38 by Reinhoudt et al., or involving intramolecular
ring closure, as reported by Shinkai for calixarene 39.71
1.1.4 Nomenclature
It is common to designate cyclic tetramers of phenol units like 31 and 32 as
calix[n]arenes, with the number in brackets describing the ring size.1a,55 When the
hydroxyl groups are not functionalized the name of the para-substituent is used as a
prefix. With more complex substitution patterns the numbering system according to
IUPAC (Figure 1.14) is used to specify the positions of substituents.
When necessary the conformation of the calixarene is added as a prefix to its name.
Regioisomers of disubstituted calixarenes can be distinguished by the terms proximal or
distal.53 The first means that adjacent phenol units are functionalized, while the latter
means that the substituents are at phenol units opposite each other.
22
21
25
1
24
23
13
12
11
10
9
2716 15
26
1918
17
7 6
5
43
28
20 2
814
OH
OH HOOH
A
B
C
D
Figure 1.14. Numbering of the parent calix[4]arene.
1.2 Goal of Research
This thesis deals with the synthesis and functionalization of calixarenes and can be
divided into two main topics.
Introduction 13
The first objective is the synthesis of inherently chiral calixarenes that consist of
phenol units being part of anellated ring systems. Extending and functionalizing the
electron-rich calixarene cavity should provide access to tailor-made hosts for molecular
recognition. The calix[4]monophenanthrene 40 has previously been synthesized in our
group by oxidative photocyclization of strylcalix[4]arenes (Figure 1.15).72 Preliminary
studies have shown that polysubstituted styrylcalix[4]arenes undergo transannular
[2+2] cycloaddition yielding the cyclobutane-bridged calix[4]diphenanthrene 41.73
Figure 1.15. Previously synthesized calix[4]monophenanthrene 40 and [2+2] cycloaddition
product 41.
This competing reaction has to be suppressed in order to synthesize higher
homologues of the calixphenanthrenes. Furthermore, it will be investigated if the first
cyclization influences the orientation of the successively formed phenanthrene units.
As an alternative approach to calixphenanthrenes and its derivatives as well as
calix[4]arenefluorenones, palladium-catalyzed cyclizations are going to be investigated
(Figure 1.16).
Additionally, calix[4]triphenylenes should be available from acid-catalyzed
rearrangement of spirocalixarenes 46 (Scheme 1.3). The latter as well as biphenylcalix-
arene 45 have been synthesized by our group with R being pyridyl substituents.72a,74
Figure 1.16. Envisaged anellated calixarenes.
14 Theoretical Part
Scheme 1.3. Acid-catalyzed rearrangement of spirocalixarene 46 to calix[4]triphenylene 47.
Preliminary studies have been made to replace the basic pyridyl with benzyl or benzoyl
groups, resulting in loss of the substituents upon Suzuki reaction to biphenylcalixarene
45.73 Therefore, the reaction conditions of the Suzuki reaction are to be adjusted and
suitable reaction conditions for the formation of the spiro-compound and its subsequent
rearrangement to the triphenylenes to be established.
The second objective is to enlarge the calixarene cavity at the upper rim with
N-heteroarenes. Sterically demanding substituents at the heteroarene should lead to the
orientation of the nitrogens towards the inside of the cavity, acting as endo-oriented
coordination sites in addition to the π-cavity. Molecules like that should be able to
complex transition metals in the cavity. The tetrazinecalix[4]arene 48 and its subsequent
Diels–Alder reaction to calixarene 49, containing eight endo-oriented nitrogens, is the
primary goal (Scheme 1.4).
Scheme 1.4. Synthesis of calixarene 49 with endo-oriented N-coordination sites.
15
2 Multifold Photocyclizations of Styrylcalix[4]arenes
2.1 Calix[4]arenes with anellated subunits and [2+2] cycloaddition
products
Calix[4]arenes containing anellated subunits are rare and often inherently chiral due to
their functionalization in meta position of the phenolic unit (Chapter 1.1.3).
Calix[4]naphthalenes are probably the best-known examples, which are usually
prepared by stepwise procedures from suitable fragments (Figure 2.1).51,75,76 The
indenol derivative 52 was also obtained via a stepwise synthesis by Böhmer et al., while
tetrahydronaphtol derivative 51 was isolated in 20 % yield by condensation of the
starting material with formaldehyde in alkaline solution.51 Gutsche et al. reported the
calixarenes 53-55, which were synthesized by 1,4-conjugate additions to
calix[4]monoquinones.52c
Figure 2.1. Examples of calix[4]arenes with anellated subunits.
Figure 2.2. Calix[4]arenes with anellated subunits obtained by intramolecular reactions.
16 Theoretical Part
Calix[4]naphthalene 56 and the cyclic ether 57 were obtained by intramolecular
reactions of para-substituted tetrapropoxycalixarenes (Figure 2.2).77
Our group successfully prepared the first calix[4]phenanthrene 40 by irradiation of
styrylcalix[4]arene 58 with iodine and potassium carbonate in benzene in 89 % yield
(Scheme 2.1).72 Studies of the mechanism have shown that basic reaction conditions are
crucial to prevent acid-catalyzed cleavage of an intermediary enol ether to the linear
tetramer 59 (39 %) in addition to the formation of 40 (22 %).
Scheme 2.1. Photocyclization of Monostyrylcalix[4]arene 58 in presence of base and without
(route a or b).
Photocyclization of distyryl- 60 and tetrastyrylcalix[4]arene 62 under the optimized
reaction conditions, however, did not yield the desired calixphenanthrenes but the
transannular [2+2] cycloaddition products 61 and 41 (Scheme 2.2).73,78 In fact,
syntheses of ladderanes from functionalized [2.2]paracyclophanes reported by Hopf et
al. are in accordance with these results.79 Mattay et al. also attempted the
photocyclization of 62, concluding from mass spectra that the reaction took place on
only two positions.77
The cyclobutane-bridged calixarene 61 was the only product obtained analytically
pure from the reaction mixture in 37 % yield. Additionally, two only poorly resolved
fractions were isolated by HPLC. The 1H NMR spectra of both compounds showed a
diagnostic signal for the bay-region proton of a phenanthrene unit at around 8.6 ppm.
Based on the integration of the respective NMR signals, the compounds are presumably
calixmonophenanthrene 63, which has a molecular ion peak at m/z = 794 in the FAB
mass spectrum, and the desired calixdiphenanthrene 64 (Figure 2.3).
Multifold Photocyclizations of Styrylcalix[4]arenes 17
Scheme 2.2. [2+2]-cycloaddition products 61 and 41 formed during photolysis of
styrylcalix[4]arenes 60 and 62.
Diphenanthrene 64 was unfortunately only obtained as a minor by-product in about
6 %, while approximately 25 % of the partially cyclized product 64 were formed. The
overall ratio of compounds 61, 63 and 64 was determined to be 6:4:1.
Figure 2.3. Minor products of the photolysis of styrylcalix[4]arene 60.
A crystal structure of calixarene 61 surprisingly showed a partial cone conformation
(Figure 2.4), which would be minimally favoured over the cone conformation by
0.8 kcal mol-1 according to semi-empirical PM3 calculations. However, since the inter-
conversion between these two conformations is prevented by the propoxy groups, the
obtained crystals presumably do not represent the bulk material, but a minor impurity
18 Theoretical Part
not detectable by NMR. Indeed, the 13C NMR spectrum before the crystallization shows
no signals at about 37 ppm, which would indicate an anti orientation of the adjacent
phenol units (Chapter 1.1.2). The 1H NMR spectrum reveals that calixarene 61 is fixed
in a pinched cone conformation due to the bridging cyclobutane. This results in an
extraordinary upfield shift of the m-aryl protons of the substituted phenyl units to
δ = 5.50 and 5.86 ppm.
Figure 2.4. Crystal structure of cyclobutane-bridged calixarene 61 in the partial cone
conformation.
2.2 Synthesis and photocyclization of a proximal distyrylcalix[4]-
arene
Since [2+2] cycloaddition between two adjacent styryl units should not be possible, the
proximal distyrylcalix[4]arene 65 was synthesized (Scheme 2.4). Introducing
functionalities at the lower rim of just two phenyl units of a calixarene, usually to
reduce the reactivity of these rings in order to make substitution at the upper rim of the
unsubstituted units more favourable, is a commonly used method.49a,80
While selective 1,3-functionalization is often easily achieved in good yields, direct
1,2-functionalization at calixarenes is more difficult and often results only in moderate
yields. Several methods for 1,2-functionalization at the lower rim were described in
literature (Scheme 2.3). Reinhoudt et al.,81 for example, observed that the proximal
substituted product is an intermediate in tetrapropylation of calixarenes with sodium
Multifold Photocyclizations of Styrylcalix[4]arenes 19
hydride and propyl iodide in DMF. Based on this, Harvey et al.80c reported direct
propylation under the same conditions to result in 45 % of dipropoxycalixarene 66 after
2 h. However, attempts to reproduce this reaction under varying reaction conditions
gave only tetrapropoxycalixarene or no reaction at all.78a
Scheme 2.3. Proximal difunctionalizations at the lower rim known from literature.
Other known lower rim 1,2-functionalized calixarenes are the 25,27-di(3,5-
dinitrobenzoyl)-26,28-dihydroxy-calix[4]arene (70) in the partial cone conformation
and the 25,26-dibenzoylcalixarene 69, both of which were synthesized by
transesterification of the corresponding 1,3-substituted compounds in good yields―81
% and 90%.80c Although first distal substitution is necessary, which adds a reaction
step, especially the benzoylcalixarene proved to be interesting. Indeed the benzoyl
group is easily removable and thus used as protecting group in the synthesis of mono-80b
and dibromated78a,80c calixarenes, respectively. However, the transesterification is
sensitive to the amount of base used, and Harvey et al. reported that it does not occur
when more than one equivalent sodium hydride is used. Accordingly, attempts using
sodium hydride as dispersion in mineral oil (60 %) failed to yield the desired 1,2-
dibenzoylcalixarene 69.
Shimizu et al.82 reported the synthesis of 25,26-dipropoxycalixarene via hydrogenation
of the corresponding allyl ether in 99 % yield as well as the direct preparation of the
25,26-dibenzylcalixarene 71 in 60 %. As reported yields for the 1,2-functionalized allyl
20 Theoretical Part
ether are moderate,81,83 the dibenzylcalixarene was prepared (Scheme 2.4). However,
stirring parent calixarene 32 with sodium hydride and benzyl bromide in acetonitrile
yielded only up to 47 % of the required calixarene 71. Tetrabenzylcalix[4]arene and
monobenzylcalix[4]arene were isolated in varying yields up to 32 % and 6 % along with
traces of the distal substituted calixarene and starting material. The best and fastest
method to isolate the desired proximal dibenzylcalixarene 71 from larger experiments
was found to be dry-column chromatography. Starting with petroleum ether/toluene 1:1
and increasing the ratio of toluene in 10 % steps, pure toluene finally elutes the pure
product. The by-products were usually not completely separated from one another and
have to be purified further.
Scheme 2.4. Synthesis of 5,11-distyrylcalix[4]arene 65.
The dibenzylcalixarene 71 was submitted to bromination with N-bromosuccinimide in
2-butanone as described in literature to yield 86 % of compound 72.82 Subsequent
removal of the benzyl groups was easily achieved by treatment of 72 with aluminium
Multifold Photocyclizations of Styrylcalix[4]arenes 21
chloride in toluene at 0 °C to afford 85 % of 5,11-dibromotetrahydroxycalixarene 73.
The 1H NMR spectrum shows two broad signals for the methylene protons at δ = 3.49
and 4.18 ppm, characteristically for calixarenes with free hydroxyl groups (spectrum,
see p. 216).80c
Propyl groups at the lower rim were introduced under standard reaction
conditions81,49b,84 and gave the proximal dibromotetrapropoyxcalixarene 74 in an
excellent 94 % yield. Transformation to the diformylcalixarene 75 in 45 % yield was
achieved by lithiation of the 5,11-dibromo compound and subsequent treatment with
DMF in analogy to the method used for preparation of the 1,3-functionalized
diformylcalixarene.85 Alternatively, synthesis of the proximally substituted
diformylcalixarene was described by Casnati et al.86 using Gross formylation (Scheme
2.5). In that case tetrapropoxycalixarene 76 is treated with SnCl4 and Cl2CHOCH3.
However, the reaction yields a mixture of proximal and distal diformylcalixarenes 75
and 78 from which the 1,2-functionalized compound can be isolated by reduction to the
alcohol, separation of the same and subsequent reoxidization. The detour over the
alcohol is necessary since the diformylated isomers are inseparable by chromatography.
Consequently, this method was not considered to provide a superior route.
Scheme 2.5. Alternative synthesis of proximal diformylcalixarene 75 by Gross formylation.86
Wittig reaction of the diformylated compound with benzyltriphenylphosphonium
chloride yielded 95 % of the distyrylcalixarene 65. Due to the mixture of possible E/Z
isomers the signal pattern for the bridging methylene protons in the 1H NMR spectrum
22 Theoretical Part
Figure 2.5. Partial 1H NMR spectra of 5,11-distyrylcalixarene 65, recorded at 200 MHz in
CDCl3. Top: mixture of E/Z isomers, bottom: sample isomerized with iodine.
is rather complex with six superimposed signals for the equatorial and seven for the
axial protons (Figure 2.5). Isomerization of a NMR sample with iodine in the heat87 led
to a simpler spectrum, especially in the aliphatic region, showing only three doublets for
equatorial protons and one at δ = 4.46 ppm for the axial ones. In the unisomerized 13C NMR spectrum eight different peaks appear between δ = 156.18 and 157.18 ppm for
the tertiary aromatic carbon atoms substituted by propoxy groups, indicating that all
possible isomers were formed. A signal at m/z = 796 in the FAB mass spectrum
unambiguously identified styrylcalixarene 65.
The proximal disubstituted distyrylcalixarene was irradiated according to the standard
photolysis conditions with iodine and potassium carbonate in benzene. Purification by
flash chromatography yielded 67 % of cyclization products. From 235 mg material
subjected to HPLC three different compounds were isolated, which is consistent with
the number of expected diasteroisomers (Scheme 2.6). The molecular ion peak at
Scheme 2.6. Photocyclization of proximal distyrylcalix[4]arene 65.
Multifold Photocyclizations of Styrylcalix[4]arenes 23
m/z = 792 present in the FAB mass spectra of all three compounds, confirms that the
calixphenanthrenes have been formed. Semiempirical PM3 calculations revealed that
the diastereoisomer 81c should be favoured compared to structures 81b and 81a with
about 3.4 and 10.6 kcal mol-1, respectively. However, 81a was clearly identified as the
main product by one- and two-dimensional NMR experiments as well as a crystal
structure analysis (Figure 2.6).
Figure 2.6. Crystal structure of proximal calix[4]diphenanthrene 81a.
These findings suggest that attracting π-π interactions predominate steric repulsion in
the first cyclization. Although 81a is a meso compound by its configuration, the steric
demands of the phenanthrene units pointing towards each other result in an asymmetric
conformation of the molecule. Accordingly, the 1H and 13C NMR spectra show a large
number of signals and there are four different sets for each of the propyl groups,
bridging methylene groups and the aryl units. The existence of four different subunits
and the crystal structure confirm the chirality of 81a.
The diagnostic signals for the Phen-5-H appear at δ = 8.70 and 7.61 ppm, respectively
(Figure 2.7). The phenanthrene, tilted towards the cavity, experiences anisotropic
effects from the other phenanthrene unit and exhibits a 1.03 ppm upfield shift for its
Phen-5-H as well as an even stronger paratropic shift for the corresponding Phen-6-H,
which is found as a triplet at δ = 5.71 ppm. Its Phen-1-H is assigned to a singlet at
δ = 6.00 ppm. The upfield shift of this signal and those of an unsubstituted aryl unit
prove that these units are tilted towards each other (rings B and D) and the molecule is
fixed in a pinched cone conformation. The meta proton facing the phenanthrene unit
exhibits the strongest paratropic shift of about 1.3 ppm to δ = 5.30 ppm. Accordingly,
the protons of the adjacent methylene bridge also experience an upfield shift of about
24 Theoretical Part
5.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.6ppm
5.30
5.71
5.76
5.80
6.00
6.16
6.23
8.00
8.70
HmH5
H8
H1'
Hp
HaxHeq
H6'Hm'
Figure 2.7. Partial 1H NMR spectrum of 81a, recorded at 600 MHz in CDCl3.
0.3 ppm to 3.04 and 4.26 ppm. Notably, the two methylene protons at the bridge
between the phenanthrene units exhibit an extremely large downfield shift of about
2 ppm, especially in the case of the equatorial proton, and appear at δ = 5.76 and
5.81 ppm. In addition, they exhibit a somewhat enlarged geminal coupling constant of
J = 15.9 Hz compared to the normal 13.5 Hz.
The number of signals in the NMR spectra exhibited by the second compound isolated
by HPLC indicates a plane of symmetry, which would be only in agreement with
structure 81b. Indeed, there are only two sets of signals each for the propoxy carbons
and the phenyl carbons attached to the oxygen atoms in the 13C NMR spectrum,
confirming two different aryl units. In addition, the three signals for the bridging
methylene carbons at δ = 30.54, 30.89 and 31.33 ppm as well as the three sets of
doublets, identified by coupling in the two-dimensional NMR spectra, are in accord
with the proximal difunctionalization of the calixarene. The diagnostic phenanthrene
signal at δ = 8.78 ppm in the 1H NMR spectrum integrates to two protons, further
evidence that both phenanthrene units have been formed. The relative upfield shift of
the m-aryl protons, δ = 5.84 and 6.26 ppm (∆ ≈ 0.8 and 0.3 ppm), indicates a pinched
cone conformation. Furthermore, these signals as well as the Phen-1-H protons at
δ = 7.06 ppm are broadened, suggesting an equilibrium of the two conformations with
coalescence at room temperature. Again the meta aryl proton and the protons of the
methylene group opposite the phenanthrene unit exhibit the strongest upfield shift to
δ = 5.84 (∆ 0.8) or δ = 2.90 (∆ 0.6) and 4.28 (∆ 0.2) ppm, respectively.
The NMR spectra of the third compound obtained by HPLC shows rather complicated
Multifold Photocyclizations of Styrylcalix[4]arenes 25
NMR spectra and the large number of signals again implies high asymmetry. Since the
third expected stereoisomer 81c should exist in a racemic mixture with its enantiomer
this is no surprise. The molecular ion at m/z = 792 and the diagnostic signal for the
phenanthrene-5-H at δ = 8.73 ppm with an integral of two protons, strongly suggest that
it is compound 81c with both phenanthrene units pointing in the same direction. For the
bridging methylene units four sets of doublets appear in the 1H NMR spectrum. The
signals at δ = 4.52 and 4.66 ppm exhibit the large 1.1 ppm downfield shift expected for
the equatorial methylene protons in the bay-region of the phenanthrene units, while their
axial partners appear at δ = 4.94 and 5.31 ppm, ∆ = 0.4 and 0.8 ppm, respectively. The
relative upfield shift of a third set, δ = 3.04 and 4.38 ppm, indicates that this bridge is
opposite one of the phenanthrene units. The fourth set shows no remarkable shift with
peaks at 3.41 and 4.73 ppm. The 13C NMR spectrum shows signals for four different
propyl groups and three signals for the aryl carbons attached to the oxygen, one of
which consists of two superimposed peaks for the PhenC–O. Broad signals at δ = 6.39
and 7.49 ppm again indicate a dynamic process of the different pinched cone
conformations. Due to this as well as the asymmetry of the molecule a complete
assignment of the NMR signals was not possible.
2.3 Prevention of the [2+2] cycloaddition by steric hindrance
In order to suppress the transannular [2+2] cycloaddition of opposite styryl units by
steric hindrance, an additional methyl group at the stilbene moiety was introduced.
First, the modified benzyltriphenylphosphonium bromide 84 had to be prepared as
depicted in Scheme 2.7. The first step involved hydrobromination of styrene (82)
according to a literature method,88 affording (1-bromoethyl)benzene 83 in 88–99 %
yield after distillation in vacuo. Subsequent conversion to compound 84 involving
procedures described in literature89,90 resulted in yields lower than 50 % (Table 2.1).
Scheme 2.7. Synthesis of benzyltriphenylphosphonium bromide 84.
26 Theoretical Part
Table 2.1. Reaction conditions for the synthesis of 1-phenethyltriphenylphosphonium
bromide 84.
Entry Solvent Time Yield
1 benzene 24 h 44 %a
2 ethyl acetate 24 h 45 %b
3 toluene 24 h 62 %
4 toluene 3 d 88 % a yield according to literature 80 %89, b yield according to literature 78 %90
After optimizing the reaction conditions, benzyltriphenylphosphonium bromide 84 was
finally obtained in 88 % yield by refluxing 83 with triphenylphosphane in toluene for
three days in a screw-cap flask.
Diformylcalixarene 7885 was subsequently transformed to the corresponding
distyrylcalixarene 85 in 41 % yield under Wittig conditions (Scheme 2.8). Compound
85 seems to be formed almost exclusively as the E/E isomer. The 1H NMR spectrum is
in fact much less complicated compared to the corresponding distyrylcalixarene 60
without the additional methyl groups at the styryl moiety. Signals of the bridging
methylene protons of the minor isomers exhibit an upfield shift compared to the E/E
isomer, which shows the respective signals at δ = 3.19 and 4.50 ppm. A 1:10 ratio was
determined from the proton NMR. The newly introduced methyl groups give slightly
broadened singlets at δ = 1.89 and 2.12 ppm. Another broad singlet at 6.53 ppm,
assigned to the alkene-H, shows coupling to the singlet of the meta aryl protons of the
substituted subunit at 6.69 ppm. The protons of the unsubstituted ring give a triplet at
δ = 6.64 ppm with J = 7.5 Hz and a doublet at 7.67 ppm with J = 7.4 Hz. A molecular
ion peak at m/z = 824 in the FAB mass spectrum also identifies the product.
Consequently distyrylcalixarene 85 was submitted to photolysis and gave an
inseparable mixture of calix[4]bisphenanthrenes 86a and 86b in 20 % yield after HPLC
(Scheme 2.8). The FAB mass spectrum shows a peak at m/z = 820 which is in
accordance with the molecular ion. The diagnostic signals for the Phen-5-H appear as
doublets at δ = 8.57 and 8.60 ppm in the 1H NMR spectrum. Although the proton NMR
of the mixture is rather complicated, some signals could be assigned to either of the
diastereomers with the help of HMQC and HMBC correlations (Figure 2.8).
Multifold Photocyclizations of Styrylcalix[4]arenes 27
OO OO
O O
(E/Z)(E/Z)
OO OO
OO OO OO OO
+
78
86a and 86b(20 %; 1:1.1)
84, -78 °C -> rt, 16 h
nBuLi, THF,45 min, -78 °C;30 min, rt
85 (42 %)
I2, K2CO3,benzene, Ar,hv, 18 h
Scheme 2.8. Synthesis and irradiation of distyrylcalix[4]arene 85.
1.12
1.00
0.54
1.00
1.00
1.68
Figure 2.8. Partial 1H NMR spectrum of a mixture of 86a and 86b in a ratio of 1:1.1, recorded at
400 MHz in CDCl3.
28 Theoretical Part
Isomer 86a has two different subunits while its diastereomer 86b has three.
Accordingly, two different phenanthrene units (A’, A) and three different unsubstituted
units (B’, B and C) are to be expected for the mixture. The 13C NMR spectrum indeed
shows five different peaks each for the carbon atoms of the propoxy groups as well as
the aryl carbons attached to the oxygen. The latter give two different signals at 159.55
and 159.69 ppm assigned to the phenanthrene subunits of the different isomers.
Furthermore, there are three peaks for the corresponding atoms of the unsubstituted aryl
units at δ = 154.57, 154.88 and 155.32 ppm in a 1:2:1 ratio. Therefore, the middle signal
must belong to the two equivalent aryl units (B’) of 86a and the HMBC spectrum shows
coupling to the meta aryl protons of this ring. They appear as doublets at δ = 5.33 and
6.03 ppm with the p-ArH triplet at δ = 5.94 ppm. The signal at 5.33 ppm exhibits the
expected anisotropic upfield shift of about 1.3 ppm caused by the adjacent phenanthrene
unit. The corresponding m-ArH of the diastereomer 86b appear at δ = 5.12 ppm as a
doublet, exhibiting an even larger shift, indicating that both phenanthrene units point
towards one aryl ring. The proton in para position of the aryl unit gives a signal at
δ = 5.64 ppm, while the protons of the opposite aryl ring appear as a multiplet at lower
field between 6.26-6.31 ppm, obviously not influenced by the phenanthrenes.
Integration of the two different sets of signals reveals a ratio of the two diastereomers
86a: 86b of roughly 1:1.1. Crystals of 86a, with both enantiomers in the unit cell, were
obtained from ααα-trifluorotoluene/methanol, confirming the pinched cone
conformation of the molecules (Figure 2.9).
Figure 2.9. Crystal structure of calix[4]diphenanthrene 86a with both enantiomers in the unit
cell.
Multifold Photocyclizations of Styrylcalix[4]arenes 29
Scheme 2.9. Synthesis of tetrastyrylcalix[4]arene 88.
Encouraged by the successful suppression of the [2+2] cycloaddition
tetrastyrylcalixarene 88 was prepared by Wittig reaction of the tetraformylcalixarene 87
with benzyltriphenylphosphonium bromide 84 in 64 % yield (Scheme 2.9). A molecular
ion peak at m/z = 1056 in the FAB mass spectrum identifies compound 88. Again one
conformation of the stilbene units is preferred and relatively simple NMR spectra are
obtained. The methyl group of the main isomer appears at 1.96 ppm in the 1H NMR and
17.3 ppm in the 13C NMR spectrum.
Irradiation of tetrastyrylcalixarene 88 resulted in a complex mixture of products. The
crude product was submitted to flash chromatography repeatedly, but no pure
compound was isolated. Diagnostic phenanthrene signals above 8 ppm were observed in
several of the obtained 1H NMR spectra.
3.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.06.26.46.66.87.07.27.47.67.88.08.28.48.68.89.0ppm
Figure 2.10. Top: Calixdiphenanthrenes 86, bottom: One fraction obtained from the photolysis
of tetastyrylcalixarene 88. Spectra recorded at 200 MHz in CDCl3.
30 Theoretical Part
The spectrum depicted in (Figure 2.10) resembles the calix[4]diphenanthrenes 86.
Another fraction, however, showed a peak at m/z = 1052 in a FAB mass spectrum
indicating that a maximum of two phenanthrene units has been formed. The mass would
also be in accord with a cyclobutane-bridged diphenanthrene like 41. Indeed, several
spectra show peaks between 5.5 and 6.0 ppm as well as around 50 ppm in the 13C NMR
spectrum, similar to the cycloaddition products.
2.4 Conclusion
Introducing steric hindrance at the styryl moiety successfully suppressed the
transannular [2+2] cycloaddition, giving a mixture of the calix[4]diphenanthrene
stereoisomers 86a and 86b. Since the stereoisomers were formed approximately in a 1:1
ratio, apparently no regioselectivity is induced by the first cyclization.
In the case of proximal disubstitution the photocyclization proceeded smoothly,
yielding all possible diastereoisomeric calixdiphenanthrenes, but favouring the sterically
overcrowded and thermodynamically disfavoured isomer. According to NMR as well as
X-ray crystal structure data the calixphenanthrenes prefer a pinched cone conformation
with the sterically demanding phenanthrene units pushed outwards.
However, the yields are only low to moderate and photolysis of a modified
tetrastyrylcalix[4]arene 88 resulted in a complex mixture of steroisomers. The
separation of these mixtures is already difficult in the case of the lower homologues.
Moreover, steric crowding seems to prevent complete cyclization of the tetrasubstituted
starting material. Cycloaddition might be favoured over the ring closure even for the
modified tetrastyrylcalixarene, as remaining styryl units get close to each other due to
the pinched cone conformation the calixdiphenanthrene adopts. Calixtetraphenanthrenes
do not seem to be accessible by this route, especially without a method to control the
regioselectivity of the reaction.
31
3 Anellated calixarenes by dehydrohalogenation
3.1 Introduction
Since the multiple oxidative photocyclization of calixarenes resulted in only moderate
yields and the purification of products proved to be difficult and time-consuming, an
alternative route to anellated rings at the calixarene framework was sought. The central
problem in any other synthesis is the intramolecular C–C bond formation in the meta
position of a phenol unit.
Scheme 3.1. Different routes to C–C bond formation depicted as intramolecular reaction.
The classical approach to link two aryl units would be by traditional transition-metal
catalyzed cross-coupling reactions like Suzuki,91 Stille,92 Negishi93 or Kumada94
(route a), Scheme 3.1).95 All these methods require prefunctionalization of both
coupling partners or reaction sites as usually aryl halides and an organometallic species
are employed. The latter can be difficult to prepare and are often problematic in terms of
stability and compatibility with functional groups. Besides, the necessary
prefunctionalization steps generate additional waste to the stoichiometric amount of
metal waste created in the coupling step. Moreover, in the case of calixarenes
functionalization of the position meta to the alkoxy group is not possible, thus excluding
this approach for the intramolecular C–C bond formation.
32 Theoretical Part
Route b) as depicted in Scheme 3.1 would provide the best way, economically and
ecologically, to synthesize biaryls as both coupling partners are simple arenes.
However, oxidative coupling processes like these are thermodynamically unfavoured
and problematic concerning regioselectivity as the substrates usually have several C–H
bonds which might react. Nevertheless, some examples are known in literature, for
instance the synthesis of Mukonine 90 (Scheme 3.2) or the intermolecular coupling of
indoles with benzene, both reported by Fagnou et al.96,97
Scheme 3.2. Pd(II)-catalyzed intramolecular oxidative coupling to Mukonine 90.
In recent years, investigations have focused on direct arylation reactions (route c),
Scheme 3.1), in which only one coupling partner needs prefunctionalization.98 The
organometallic species is usually substituted for a simple arene which is coupled with
an aryl halide under transition metal catalysis. Since functionalization of the meta
position in a calixarene is thus unnecessary, this method was chosen for the calixarenes.
As catalysts for direct arylation reactions palladium, ruthenium or rhodium species
are commonly used and a broad range of ligands has been employed. The nature of the
ligand, however, greatly varies depends on the scope of the reactions. Usually the
coupling reactions are carried out in polar aprotic solvents such as DMA, DMF or NMP
under addition of an inorganic base. As the prefunctionalized species aryl bromides,
chlorides, iodides and tosylates can be used respectively, though metal salt additives are
often necessary in reactions with aryl iodides.99
Figure 3.1. Intermediates for the electrophilic aromatic substitution pathway (left) and for the
concerted metalation-deprotonation pathway (right).
Anellated calixarenes by dehydrohalogenation 33
In the first step of the mechanism an oxidative addition of the transition metal into the
aryl halide occurs. For the C–C bond forming step, however, various models have been
proposed. An electrophilic aromatic substitution pathway (SEAr) has been favored
especially for electron-rich heteroarenes.102 Experimental and computational studies by
Echavarren et al. and Fagnou et al. provided evidence that simple and electron-deficient
arenes are more likely to react by a concerted metalation-deprotonation pathway
(CMD), where the ligated base abstracts the proton (Figure 3.1.).100,101,104b The exact
mechanism may highly depend on the respective substrates and reaction conditions
used.
One of the early examples of direct arylations was reported by Ames and Opalko with
the intramolecular reaction to dibenzofurans like 92 as depicted in Scheme 3.3.
Scheme 3.3. Synthesis of dibenzofuran 92 employing 10 mol% Pd(OAc)2 and 1.2 eq base.
Electron-rich heteroarenes have been successfully employed in inter- and
intramolecular direct arylations (Scheme 3.4).102
Scheme 3.4. Reaction of an indole with iodobenzene.
Simple arenes are less nucleophilic and ortho-directing groups are often used to
facilitate the reaction as aryl-transition metal interactions are weak (a, Scheme 3.5).103
The use of a palladium-pivalic acid co-catalyst system, where the pivalate ion acts as
“proton-shuttle”, has also been proved to be useful for the direct arylation of simple
arenes or heteroarenes (b, Scheme 3.5).104
34 Theoretical Part
Scheme 3.5. a) Direct arylation with an amide directing group. b) Use of palladium-pivalic acid
co-catalyst system in the direct arylation of benzene.
Examples where one catalyst is employed to perform different types of catalytic
reactions in a one-pot procedure are also known. Fagnou et al., for example, reported
the tandem catalysis reaction depicted in Scheme 3.6, where a Heck reaction is followed
by direct arylation and subsequent hydrogenation.105
Scheme 3.6. Tandem catalysis comprising Heck reaction, direct arylation and hydrogenation.
Direct arylations have been also applied to the synthesis of bowl-shaped PAHs like
the corannulene depicted in Scheme 3.7. 106,107
Scheme 3.7. Double direct arylation to 1,2-Dihydrocyclopenta[b,c]dibenzo[g,m]-corannulene
106.106
Anellated calixarenes by dehydrohalogenation 35
Scheme 3.8. Inter- and intramolecular decarboxylative coupling.109a,c
Carboxylic acids provide an interesting alternative to aryl halides as the carboxy group
acts as a leaving group in decarboxylative biaryl synthesis (Scheme 3.8).108,109
Mattay et al.77,110 were the first to report successful intramolecular direct arylation at a
calixarene (Scheme 3.9), using reaction conditions optimized by Fagnou et al.99
Scheme 3.9. Intramolecular direct arylation at a calixarene.
An alternative to transition metal-catalyzed couplings are photoinduced ring closures.
Moorthy et al.111 reported the synthesis of diversely substituted fluorenones by
photolysis (Scheme 3.10).
Scheme 3.10.Synthesis of fluorenone 114 by photoinduced ring closure.
36 Theoretical Part
Several promising reaction conditions for the intramolecular direct arylation were to
be evaluated at model compounds before applying them to the synthesis of anellated
calixphenanthrenes and -fluorenones.
3.2 Phenanthrene model compounds
In order to find suitable reaction conditions for the intramolecular direct arylation at
calixarenes, the easily accessible model compound 118 was synthesized (Scheme 3.11).
2-Bromophenylacetic acid (115) was converted to the corresponding acid chloride
116 according to a literature method112 in quantitative yield and used in the subsequent
Friedel–Crafts acetylation of 2,6-dimethylanisole (117) without further purification.
Ethanone 118 was obtained in 94 % yield by using reaction conditions reported by
SanMartin et al.113 for the corresponding compound without methyl groups. Substitution
in para position to the methoxy group is verified by a 2 H singlet at δ = 7.73 ppm in the 1H NMR spectrum. The carbonyl group shows a peak at δ = 195.8 ppm in the 13C spectrum as well as a peak at 1684 cm-1 in the IR spectrum. Furthermore, the mass
peak at m/z = 333 in the FAB spectrum also confirms the formation of 118.
Scheme 3.11. Synthesis of ethanone model compound 118.
First, cyclization of 118 (Scheme 3.12) was attempted using Pd(OAc)2 (5 mol%),
tetrabutylammonium bromide (2 eq) and potassium carbonate (8 eq) in DMF, similar to
conditions described in literature.114 Neither heating to 70 °C for 5 days nor to 100 °C
for 2 days in a screw-capped flask produced the desired compound 119. Only traces of
the dimeric phenanthrene 120b were detected in the 1H NMR spectra.
Anellated calixarenes by dehydrohalogenation 37
Scheme 3.12. Attempted palladium-catalyzed cyclization of 118; a: 24 h, 145 °C b: 3 d, 170 °C.
Only starting material was recovered when the reaction conditions were changed to
PdCl2 (5 mol%), PCy3·HBF4 (2 eq per Pd) in DMA with DBU (2 eq) as base for 24 h at
145 °C,106 as described for the synthesis of PAHs (Scheme 3.7). Likewise conditions
reported by Ames et al. for cyclization of 2-bromobenzophenone―employing
Pd(OAc)2 (10 mol%), sodium carbonate in DMA and heating to 170 °C overnight―
failed to produce the product.115
Very promising seemed the reaction conditions optimized by Fagnou et al.,99 which
employed Pd(OAc)2 (5 mol%), PCy3·HBF4 (2 eq per Pd), potassium carbonate (2 eq) in
DMA, usually at 130 °C for 24 h (hereafter referred to as the ‘usual conditions’). These
conditions were applied to a wide range of substrates and are compatible with aryl
bromides as well as chlorides and iodides (Scheme 3.13). However, reaction of 1 mmol
of ethanone 118 employing these conditions resulted in dimerization after 24 h at 145
°C. Dihydrophenanthren 120a was isolated in 19 % yield, whereas phenanthrene 120b
was produced in 38 % yield. Both compounds were identified by their mass peaks at
m/z = 505 [M+H]+ for 120a and m/z = 503 [M+H]+ for 120b, leading to the conclusion
that dimers had been formed. In the 1H NMR spectrum of dihydrophenanthrene 120a
the additional protons appear as a 2 H singlet at δ = 5.47 ppm with the corresponding
carbon at δ = 48.9 ppm.
38 Theoretical Part
Scheme 3.13. Reaction conditions established by Fagnou et al. and examples of the compounds
synthesized.99
When the reaction was heated to 170 °C for 3 d, phenanthrene 120b was obtained in
8 % yield as well as 23 % of an unidentified compound. The latter shows peaks at
m/z = 511 [M+Na]+ and 488 [M+H]+ in the FAB mass spectrum. Interestingly, the NMR
spectra are almost identical to those of phenanthrene 120b (Figure 3.2). However, both
the 1H as well as the 13C NMR spectrum show two different methyl groups at δ = 2.12
and 2.18 ppm with the respective carbons at δ = 15.9 and 16.3 ppm. The singlet of 120b
at 7.44 ppm splits into two signals for the other compound 120a, resulting in an
additional peak at 7.46 ppm. Noteworthy is also a peak at 157.7 ppm in the 13C NMR
spectrum, indicating an aromatic carbon with a free hydroxyl group. Thin-layer
chromatography of the different substances in PE/EtOAc 2:1 shows a spot with
Rf = 0.58 for 120b and one with Rf = 0.41 ppm for the other phenanthrene, which shows
the latter is more polar than 120b. These findings suggest that 120c has been formed by
partial dealkylation of 120b (Scheme 3.12), which would also be consistent with the
observed mass and integration of the 1H NMR spectrum (Figure 3.2).
For the formation of phenanthrene derivatives 120a-c two molecules of 118 obviously
undergo Ullman-type coupling followed by coupling of enolates and reductive
elimination.
In an attempt to suppress dimerization, the reaction was carried out in dilute solution,
c = 0.07 M instead of 0.2 M, at 130 °C for 24 h. According to the 1H NMR of the crude
product again the two dimers 120a and 120b had been formed approximately in a 1:1
ratio and were therefore not further purified.
Anellated calixarenes by dehydrohalogenation 39
Figure 3.2. Partial 1H NMR spectra of phenanthrendimer 120b (top) and an unidentified
compound, presumably 120c, recorded at 200 MHz in CDCl3.
Even if the Ullman-type dimerization could be successfully suppressed, it is still
questionable if the envisaged cyclization would take place. Miura et al.116 report that
ketone 121, formed by previous α-arylation, does not undergo ortho-arylative coupling
to the cyclic ketone 122 (Scheme 3.14). Instead arylation takes place at an intermediary
enolate oxygen leading to benzufuran 123. Accordingly, 119 would probably undergo
α-arylation as well as oxygen arylation yielding a benzofuran.
Scheme 3.14. Oxygen arylation leading to 2,3-diphenyl-2,3-dihydrobenzofuran 123 as reported
by Miura et al.116
40 Theoretical Part
Scheme 3.15. Reduction of ethanone 118 and subsequent protection of the alcohol 124.
To decrease the acidity of the methylene protons, ketone 118 was reduced to the
corresponding alcohol 124 with sodium borohydride in THF, yielding 87 % alcohol
after 24 h reflux (Scheme 3.15). A 1 H doublet of doublet assigned to the proton at the
carbon bearing the hydroxyl group at δ = 4.92 ppm and the corresponding carbon at δ =
73.3 ppm in the 13C NMR spectrum confirm the formation of the alcohol. The alcohol
was protected with trimethylsilyl chloride to yield 74 % of 125.117 The methyl groups at
the silane appear at δ = −0.19 ppm in the 1H NMR spectrum and δ = −0.24 ppm in the
carbon NMR. Cyclization using again the usual conditions for 3 days at 170 °C did not
give the desired product 126. Instead, the desilylated dehalogenation products 127 and
128 were obtained in 56 % and 28 % yield, respectively (Scheme 3.16).
Scheme 3.16. Attempted cyclization of Silane 125: 5 mol% Pd(OAc)2, PCy3·HBF4 (2 eq per
Pd), 2 eq potassium carbonate, DMA, 170 °C, 3 d.
Removal of the carbonyl group by Wolff–Kishner reduction118 yielded 5-(2-Bromo-
phenethyl)-2-methoxy-1,3-dimethylbenzol (129) in 71 % (Scheme 3.17). The NMR
spectra verify the reduction as the methylene groups appear as two 2 H multiplets,
which are ‘roof effect’, at δ = 2.80 and 3.00 ppm with the carbons at δ = 35.8 and
38.7 ppm. Applying standard cyclization conditions successfully gave 69 % of
Anellated calixarenes by dehydrohalogenation 41
dihydrophenanthrene 130. The 1H NMR shows only a 1 H singlet at δ = 6.95 ppm for
the proton meta to the methoxy group as well as two different signals for the methyl
groups at δ = 2.32 ans 2.55 ppm. The molecular ion at m/z = 238 in the EI mass
spectrum also confirms the formation of 130.
Scheme 3.17. Wolff–Kishner reduction of ethanone 118 and subsequent intramolecular direct
arylation to dihydrophenanthrene 130.
3.3 Syntheses of calix[4]phenanthrene derivatives
Friedel–Crafts acetylation at calixarenes has been reported to yield tetrasubstituted
calixarenes. Usually dichloromethane or nitrobenzene are employed as solvents and
aluminium chloride as the Lewis acid to yield the para-substituted products in moderate
to good yields.119
Selective monofunctionalization by Friedel–Crafts reactions at calixarenes is
problematic.120,121 Matt et al. prepared the monoacetyl- and diacetylcalixarene by
Friedel–Crafts acetylation by presequent introduction of two propoxy groups at the
lower rim.121 Thus only the free phenol units, which are more reactive, were acetylated
in nitrobenzene at room temperature using one and two equivalents of aluminium
chloride and acetylchloride, respectively.
Dipropoxycalixarene 131 was reacted accordingly with acetyl chloride 116 for 2 h at
room temperature in dichloromethane (Scheme 3.18). After flash chromatography using
PE/EtOAc and subsequent recrystallization from DCM/MeOH about 13 % of the
desired product 132 were isolated, still slightly impure. The 1H NMR spectrum shows a
characteristic singlet for the methylene protons adjacent to the carbonyl group at
42 Theoretical Part
Scheme 3.18. Friedel–Crafts acetylation of dipropoxycalix[4]arene 131.
6.44
3.92
3.74
4.42
3.27
2.26
3.37
6.09
2.08
4.00
1.52
1.32
1.99
2.16
3.46
3.99
4.28
4.38
6.76
6.92
7.04
7.23
7.61
7.80
9.16
Figure 3.3. 1H NMR spectrum of Bisethanonecalix[4]arene 132, recorded at 200 MHz in CDCl3.
δ = 4.38 ppm (Figure 3.3). Integration of the NMR and a [M+H]+ peak at m/z = 903 in
the FAB spectrum confirm disubstitution.
Modelled on the protocol by Matt et al., monosubstitution of tetrapropoxycalixarene
76 was attempted (Scheme 3.19). Subsequent cyclization of 133 would only lead to a
racemic mixture of enantiomers. This would circumvent the difficult separation of
stereoisomers which would be obtained from polysubstituted derivatives. One
equivalent each of aluminium chloride and the benzoyl chloride 116 in dichloromethane
were employed. A solution of the acetyl chloride was added dropwise to a suspension of
aluminium chloride and calixarene in dichloromethane over a period of two hours at
room temperature. However, only 25 % of the desired product 133 were obtained under
these reaction conditions while 22 % tripropoxycalixarene 134 were formed (Scheme
3.19).
Anellated calixarenes by dehydrohalogenation 43
Scheme 3.19. Synthesis of calixarene 133.
Bromophenylacetylcalixarene 133 was identified by one- and two-dimensional NMR
spectroscopy. The 1H NMR spectrum shows the methylene group next to carbonyl as a
2 H singlet at 4.14 ppm. In addition, the proton next to the bromo substituent appears as
a doublet of doublets at 7.57 ppm. Monosubstitution is verified by a 2 H singlet at 7.21
ppm assigned to the aryl protons of the substituted phenol unit. The signal pattern
observed for the propoxy groups as well as the bridging methylene groups in both the
proton and carbon NMR spectra also confirms monosubstitution. The carbonyl group
appears at 195.6 ppm and the adjacent methylene carbon at 45.3 ppm in the 13C NMR
spectrum. Moreover, the FAB mass spectrum shows the [M+H]+ peak at m/z = 789,
which is consistent with compound 133.
Adding a suspension of aluminium chloride to a solution of the other starting
materials, again over a period of two hours, resulted in the formation of 15 % of 133
and increased 29 % tripropoxycalixarene. Additionally, about 32 % of the starting
material was recovered. When the same reaction was carried out in nitrobenzene 16 %
133 and 24 % 134 were obtained, respectively. The yields being about the same as in
the reaction performed in dichloromethane, nitrobenzene showed no advantage besides
completely dissolving the aluminium chloride.120 Dichloromethane might be preferred
because it can be easier removed.
Various attempts to synthesize 133 by lithiation of monobromocalixarene80b 135 with
n-butyllithium and different reactions times did not yield any product (Scheme 3.20).
When warmed to room temperature overnight after addition of acetyl chloride 116 only
starting material was recovered quantitatively, suggesting the lithiation failed. Further
attempts yielded only tetrapropoxycalixarene 76 after reaction at room temperature for
two or three hours, respectively.
44 Theoretical Part
Scheme 3.20. Attempted synthesis of 133 by lithiation: 1. THF, nBuLi, –78°C, 45 min; 2. acetyl
chloride 116, –78 °C to rt overnight or room temperature for 2 h and 3 h,
respectively.
Similar to the synthesis of model compound 118, tetrapropoxycalixarene 76 was
reacted with 1.6 eq AlCl3 and 2.7 eq acetyl chloride 116 per position under reflux. Only
the tetrasubstituted calixarene 136 was isolated in a very low 8 % yield (Scheme 3.21).
The NMR spectra confirm the symmetry of the molecule with a singlet at 4.10 ppm
assigned to the methylene protons adjacent to the carbonyl group and the corresponding
carbon at 45.4 ppm in the 13C NMR. The carbonyl groups cause a signal at
δ = 195.5 ppm, as well as a strong carbonyl band at 1682 cm-1 in the infrared spectrum.
Scheme 3.21. Synthesis of tetrasubstituted calixarene 136.
In analogy to the Wolff–Kishner reduction of model compound 118, the same reaction
conditions were applied to calixarene 133 (Scheme 3.22). After running the reaction for
1 h 20 min and subsequent purification by multiple flash chromatography about 12 % of
a solid, exhibiting signals of the desired product 137a in the NMR spectra, were
isolated.
An alternative route to calixarene 137a is the reduction of the corresponding
acetylene, which can be prepared by Sonogashira coupling (Scheme 3.23).
Anellated calixarenes by dehydrohalogenation 45
Scheme 3.22. Attempted Wolff–Kishner reduction of calixarene 133.
Therefore, monoiodocalixarene 139a was synthesized by transhalogenation of the
corresponding bromide 135 in 36 % yield, modelled on a protocol for
resorcin[4]arenes.122 Monosubstitution is confirmed by the expected molecular ion at
m/z = 718 in the FAB mass spectrum as well as NMR analyses. The iodo-substituted
carbon appears at δ = 86.0 ppm in the 13C NMR spectrum.
OO
n 4-n
Br 1. nBuLi, THF, -78 °C,15 min
2. I2/THF, overnight, rt
OO
n 4-n
I
OO
n 4-n
Br
OOn 4-n
Br
135 (n=1) 139a (36 %)139b (69 %)
141a (75 %)141b (70 %)
137a (84 %)137b (85 %)
Br
Pd(PPh3)2Cl2, CuI,NEt3, 3 d , 80 °C
140
1. p-toluenesulfonylhydrazide, DME, 8 h,85 °C, NaOAc/H2O, with a: n = 1
b: n = 2
138 (n = 2)
2. 6 h, 85 °C
Scheme 3.23. Alternative route to 2-bromophenethyl calixarenes 137.
The acetylene 141a was obtained by subsequent Sonogashira coupling84,123 with 1-
bromo-2-ethynylbenzene (140) in 75 % yield. The Pd-catalyst was generated in situ
from PdCl2 and triphenylphosphine, using 5 mol% Pd-catalyst and 10 mol% CuI per
iodo group according to reaction conditions described previously by our group.123a
46 Theoretical Part
Scheme 3.24. Preparation of 1-bromo-2-ethynylbenzene (140).
Diagnostic are the acetylene carbons at δ = 86.5 and 95.3 ppm in the 13C NMR
spectrum as well as the signal of the C≡C valence vibration at 2010 cm-1 in the IR
spectrum. The FAB mass spectrum shows the molecular ion at m/z = 772.
1-Bromo-2-ethynylbenzene (140) was synthesized from o-dibromobenzene (142) by
Sonogashira coupling with either trimethylsilylacetylene or 2-methyl-3-butyn-2-ol and
subsequent deprotection (Scheme 3.24). Following a literature procedure124 coupling
with the butynol gave product 143 in 86 % yield as brown oil after column
chromatography. In contrast to the literature the catalyst was generated in situ and the
mixture was stirred overnight instead of only 5 h. Deprotection was problematic,
yielding acetylene 140 in only 33 % when refluxed with sodium hydride and distilled at
a water separator to remove acetone.125 In contrast, the silylacetylene 144 was obtained
in 78 % yield, employing the same reaction conditions used to prepare 143, and
deprotected to give very good 85 % of 1-bromo-2-ethynylbenzene (140) following a
literature procedure.126
Calixarene 141a was finally reduced to 137a by treatment with p-toluenesulfonyl
hydrazide.99,127 Under the reaction conditions diimide is generated in situ and
hydrogenates the multiple bond by cis-addition of hydrogen.128 Calixarene 137a was
obtained in a very good 84 % yield. Characteristically the 1H NMR spectrum shows the
methylene protons at δ = 2.60 and 2.79 ppm with the corresponding carbon atoms at
δ = 35.5 and 38.6 ppm in the 13C NMR spectrum. Both the proton and the carbon NMR
show a great number of additional small peaks, indicating either impurities or a
conformational flexibility on the NMR time scale. In fact, elemental analysis is
unexeptionally close to the calculated values with 77.33 % carbon (∆C = 0.02) and
7.10 % hydrogen (∆H = 0.05). Moreover, both the spectra of the substance obtained by
Wolff–Kishner reduction or reduction of the alkine as well as those of the disubstituted
Anellated calixarenes by dehydrohalogenation 47
compound 137b show these smaller signals. This strengthens the previous assumption
of conformational flexibility.
The disubstituted calixarene 137b was synthesized accordingly. Hennrich et al.84 and
similarly Friedrichsen et al.129 reported a procedure, which employs
benzyltrimethylammonium dichloroiodate130 and calcium carbonate in a mixture of
dichloromethane/methanol to iodinate the dipropoxycalixarene. Subsequent alkylation
of the free hydroxyl groups would lead to diiodotetrapropoxycalixarene 139b. However,
the first step only gave inseparable mixtures of mono- and diiodinated products as well
as unreacted starting material, even with prolonged reaction times or heating. A
procedure by Dondoni et al.,131 employing NaHCO3 instead of CaCO3 in the iodination
step, was not tested. When the crude product was submitted to the alkylation step, only
about 25 % of compound 139b were obtained. The 1H NMR spectrum still shows
contamination, presumably with the monosubstituted compound. An attempt to
synthesize 139b like the corresponding dibromocalixarene85 by lithiation of the
tetraiodocalixarene and subsequent reaction with methanol, gave only traces of product
according to NMR spectra. Finally, transhalogenation of the bromocalixarene gave the
desired product in 69 % yield (Scheme 3.23).
Sonogashira coupling of the diiodocalixarene 139b gave 141b in 70 % yield. The
product was identified unambiguously by its diagnostic acetylene carbons at δ = 87.0
and 95.0 ppm in the 13C NMR spectrum and the C≡C valence vibration at 2010 cm-1 in
the IR spectrum. Subsequent reduction lead to 137b in 85 % yield. NMR spectra show
the methylene protons at δ = 2.71 and 2.93 ppm with the corresponding carbons at 35.5
and 38.7 ppm.
Both, the mono- and the disubstituted phenethylcalixarene 137a and 137b, were
subjected to the Pd-catalyzed intramolecular direct arylation (Scheme 3.25). Variations
of the usual already used for the preparation of model compound 130 (Scheme 3.17)
were employed.
For the conversion of bromophenethylcalixarene 137a 5 mol% catalyst were used.
Purification by flash-chromatography failed to yield completely pure material, but about
20 % seemed sufficiently pure to obtain a FAB mass spectrum and NMR data. The
mass spectrum shows only the peak at m/z = 694, consistent with the molecular ion. The
NMR spectra confirm that the material is not completely pure as there are clearly more
carbon signals than expected for the racemic mixture of 145.
48 Theoretical Part
Scheme 3.25. Attempted intramolecular direct arylation of calixarenes 137 to calix[4]-
dihydrophenanthrenes.
Figure 3.4. Partial 1H NMR spectra of calix[4]dihydrophenanthrene 145 (top) and calix[4]bis-
dihydrophenanthrenes 146a and 146b (bottom), recorded at 400 MHz in CD2Cl2.
Anellated calixarenes by dehydrohalogenation 49
Moreover, two spots are observed in thin-layer chromatography with PE/EtOAC 30:1.
The 1H NMR shows peaks at δ = 2.63 and 2.82 ppm, presumably the hydrogens at the
central ring of the dihydrophenanthrene moiety (Figure 3.4). Coupling to the signals at
around 31 ppm in the HMQC spectrum confirms this assumption, supported by the fact
that the corresponding carbons of the model compound also appear at 30 ppm.
The disubstituted compound 137b was reacted 3 d at 170 °C using 10 mol% catalyst
per group (20 % overall). After flash column chromatography and subsequent
recrystallization from DCM/EtOH, 32 mg (~ 18 %) of material were isolated. The FAB
spectrum shows the base peak at m/z = 796 which is in accord with molecular ion of
compound 146. Moreover, the 13C NMR spectrum shows 4 different peaks for the
propyl groups with signal patterns that strongly resemble the mixture of
calixdiphenanthrenes 86a and 86b (Figure 3.5). Thus the peaks at δ = 10.3 and
23.3 ppm are assigned to the propoxy groups attached to the dihydrophenanthrene units.
The signals at around δ = 11 and 24 ppm in an approximately 1:2:1 ratio belong to the
propoxy groups at the unsubstituted aryl units. Furthermore, the aryl carbons substituted
by the propoxy groups are also in accordance with a mixture of steroisomers 146a and
146b, in ratio presumably about 1:1. Accordingly, there are three signals for the aryl
units at around 155 ppm, in an approximate 1:2:1 ratio, and two signals at 150 ppm for
the dihydrophenanthrene subunits. The hydrogens at the positions nine and ten of the
dihydrophenanthrene ring give multiplets at δ = 2.69 and 2.87 ppm, very similar to the
mono compound 145.
Figure 3.5. Details from the 13C NMR spectrum of bisdihydrophenanthrene 146. Spectrum
recorded at 100 MHz in CD2Cl2.
Interestingly, both the mono- and the disubstituted compound show a 2 ppm upfield
shift of one bridging methylene group to 28.3 and 28.6 ppm, respectively. The
50 Theoretical Part
corresponding protons appear at around δ = 4.10 and 4.45 ppm for both substances,
revealing a strong downfield shift of around 1 ppm for the equatorial hydrogens. These
are presumably the bridging methylene groups in the bay-region of the
dihydrophenanthrene rings. The model compound 130 also exhibited an upfield shift for
the corresponding carbon and a downfield shift for the respective hydrogens compared
to those on the opposite site. Moreover, the upfield shift of signals assigned to the aryl
protons of the unsubstituted units to 5-6 ppm indicates that both 145 and 146 adopt a
pinched cone conformation as already observed for the calixdiphenanthrenes 86. It is
also noteworthy that the 13C NMR spectra of both compounds show small peaks at 35.9
and 39.0 ppm (145) as well as 37.7 and 38.7 ppm (146). These indicate that the reaction
did not go to completion and the isolated material is contaminated with starting material
or, in case if 146, partially cyclized product.
3.4 Synthesis of a fluorenone model compound
Since the palladium-catalyzed cyclization of 2-(2-bromophenyl)-1-(4-methoxy-3,5-
dimethylphenyl)ethanone (118) and its derivatives was unsuccessful (Chapter 3.2), the
corresponding methanones 149 were chosen as a new precursor.
One method to prepare the acid chlorides 148 is by stirring the respective benzoic acid
147 with oxalyl chloride in dichloromethane at room temperature.112b Thus, the
chlorobenzoyl chloride 148a was obtained in 99 % yield and the bromobenzoyl chloride
148b in nearly quantitative yield according to NMR (Scheme 3.26). Alternatively,
reaction with thionyl chloride and DMF in dichloromethane at reflux for three hours led
to 148a in 86–94 %, 148b in 92–98 % and 148c in 81 % yield.
Scheme 3.26. Synthesis of acid chlorides 148 and subsequent Friedel–Crafts acetylation: a)
oxalyl chloride, drop DMF, CH2Cl2, 3.5 h, rt; b) SOCl2 (2.2 eq), DMF, CH2Cl2, 3 h,
reflux.
Anellated calixarenes by dehydrohalogenation 51
All acid chlorides were used without further purification in the subsequent Friedel–
Crafts acetylation of 2,6-dimethylanisole (117).113 Chlorophenylmethanone 149a was
obtained in 88 % yield, whereas the corresponding bromide gave slightly better 91 % of
149b. The iodide 149c was isolated in a good 83 % yield. The three compounds were
identified by mass spectrometry and their respective NMR spectra. The
chlorophenylmethanone 149a was identified by its molecular ion at m/z = 274 in the EI
mass spectrum. In addition, the IR spectrum shows the carbonyl band at 1665 cm-1 with
the corresponding NMR signal at 194.7 ppm in the 13C NMR spectrum. For
bromophenylmethanone 149b a [M+H]+ peak at m/z = 319 in the FAB mass spectrum is
observed and the 13C NMR spectrum shows the carbonyl carbon at 195.3 ppm. Another
characteristic signal is the bromo-substituted carbon at 119.6 ppm. The iodo compound
149c shows the corresponding iodo-substituted carbon at 94.4 ppm and the molecular
ion causes a signal at m/z = 366 in the EI mass spectrum.
Table 3.1 summarizes the different conditions that were tested with methanone 149
for the intramolecular direct arylation to fluorenone 151 (Scheme 3.27). Reaction of the
bromide 149b with 10 mol% palladium acetate and potassium carbonate as base
(entry 1) yielded about 34 % of the fluorenone, not completely pure after flash
chromatography. No product was obtained using only 5 mol% Pd(OAc)2 and tri-o-
tolylphosphine as ligand (entry 2). By employing Pd(OAc)2 and tetrabutylammonium
bromide only starting material was recovered (entry 3). Good results were achieved
with 5 mol% Pd(OAc)2 as catalyst, two equivalents tricyclohexylphosphine
tetrafluoroborate per palladium as ligand and potassium carbonate as base in DMA at
170 °C (entries 4–7). The reaction was carried out for 3 days or 24 hours, respectively.
The yields did not increase significantly when the reaction time was prolonged,
indicating that the reaction is completed after 24 hours. Aryl chloride 149a produced
better yields than the corresponding bromide compound 149b, yielding good 74 %
(entry 5). The best yield was obtained when the Bedford catalyst132 150 depicted in
Figure 3.6 was used instead of palladium(II) acetate (entry 8). The reaction was carried
out in DMA/toluene (2:1) with 3 mol% of the catalyst, pivalic acid as co-catalyst and
potassium carbonate as base to yield 90 % of the pure fluorenone 151. Further attempts
following the literature procedures described by Ames and Opalko115 for cyclization of
bromo- or iodobenzophenones (entries 9-11) were only in one case successful. The
fluorenone was obtained in 38 % yield according to NMR, when the bromide 149b was
52 Theoretical Part
Table 3.1. Conditions tested for the intramolecular direct arylation of 149.a,b
Entry starting
material catalyst ligand base yield
1 bromide 149b Pd(OAc)2
(10 mol%) - K2CO3
(1.2 eq) 34 %e
2 bromide 149b Pd(OAc)2 (5 mol%)
o-tolyl phosphine (2 eq per Pd)
K2CO3 (2 eq)
0 %
3 bromide 149b Pd(OAc)2 (5 mol%)
nBu4Br (2 eq)
K2CO3 (8eq)
0 %
4 bromide 149b Pd(OAc)2 (5 mol%)
PCy3·HBF4 (2 eq per Pd)
K2CO3 (2 eq)
66 %
5 chloride 149a Pd(OAc)2 (5 mol%)
PCy3·HBF4 (2 eq per Pd)
K2CO3 (2 eq)
74 %
6 bromide 149b Pd(OAc)2 (5 mol%)
PCy3·HBF4 (2 eq per Pd)
K2CO3 (2 eq)
64 %c
7 chloride 149a Pd(OAc)2 (5 mol%)
PCy3·HBF4 (2 eq per Pd)
K2CO3 (2 eq)
73 %c
8 bromide 149b 150
(3 mol%) PivOH as co-catalyst
K2CO3 (6 eq)
90 %d
9 bromide 149b Pd(OAc)2 (10 mol%)
- Na2CO3
(1.2 eq) 38 %c,e
10 bromide 149b Pd(OAc)2 (10 mol%)
PPh3 (2 eq per Pd)
NaOAc (2.5 eq)
0 %c
11 iodide 149c Pd(OAc)2 (10 mol%)
- NMI 0 %c,f
12 bromide 149b photolysis 18 %c,e,g
a Generally all the reactions were carried out only once; b Reactions were carried out in DMA at
170 °C for 3 d if not stated otherwise; c 24 h reaction time; d Bedford catalyst, 1 eq PivOH per
149b, DMA/toluene (2:1), 10 h, 120 °C; e purity estimated from NMR; f NMI is the solvent,
reaction at 190 °C; g in CH3CN
PO O
O
tButBu
tBu
tBu
tBu
tBu
Pd Cl
2
150
Scheme 3.27. Intramolecular direct arylation to fluorenone. Figure 3.6. Bedford catalyst.
Anellated calixarenes by dehydrohalogenation 53
reacted with palladium(II) acetate and sodium carbonate for 24 h. Only 18 %
fluorenone, estimated from the NMR spectra, were obtained by photolysis according to
Moorthy (entry 12).111
Sannicolo prepared the yellow fluorenone 151 by intramolecular Friedel–Crafts
acetylation from the corresponding dimethylanisole bearing a phenyl group meta, and
an acid chloride functionalization para to the methoxy substituent (Scheme 3.28).133
Scheme 3.28. Preparation of fluorenone 151 according to Sannicolo.133
1H NMR data of the fluorenone obtained by Pd-catalyzed cyclization are in accord
with those reported in the literature. Additionally, the 13C NMR spectrum shows the
peak assigned to the carbonyl group at 193.7 ppm, which also causes a strong
absorbance at 1707 cm-1 in the infrared spectrum. The successful cyclization is
confirmed by two different signals for the methyl groups, δ = 2.50 and 2.29 ppm as well
as 12.8 and 16.6 ppm. The molecular ion appears at m/z = 238 in the EI mass spectrum.
The UV spectrum shows a strong absorbance at 255 nm and smaller ones at 289, 301,
323 and 336 nm.
With regard to further reaction conditions that might lead to fluorenone 151,
methanones 154 and 156 were synthesized, bearing carboxy groups instead of halogens
(Scheme 3.29).
Scheme 3.29. Syntheses of benzoic acids 154 and 156 by Friedel–Crafts acetylation with
phthalic anhydride (153).
54 Theoretical Part
The synthesis of 154 was initially based on a protocol by Yamato et al.134 in which the
substructure was synthesized at a cyclophane, but starting with a tert-butyl group in
para position of the methoxy group. Only starting material was recovered when the
exact protocol―adding the aluminium chloride solution at 0 °C and stirring at room
temperature for one hour―was applied to 117. The reaction conditions were changed to
refluxing the mixture for one hour after addition of the aluminium chloride solution at
room temperature. Beside unreacted starting material, the benzoic acid 154 was isolated
in 9 % yield. The 13C NMR spectrum shows the carbonyl carbons at δ = 196.6 and
169.7 ppm, the strong bands appear at 1603 and 1669 cm-1 in the IR spectrum.
Using 2,6-Dimethylphenol (155) and applying the same reaction conditions used for
the Friedel–Crafts acetylation with the 2-halobenzoyl chlorides, yielded 49 % of an
unidentified compound. At first sight the 1H NMR seems to be in accordance with the
expected benzoic acid 156 (Figure 3.7). The aromatic signals at 7.66, 7.89 and 8.06 ppm
integrate to a 2:1:1 ratio as expected for the aryl ring bearing the carboxy group.
Moreover, there is only one kind of methyl group and a singlet at δ = 7.10 ppm, which
is assigned to the protons meta to the hydroxyl group. Integration, however, reveals that
this singlet equals only three protons instead of the expected two. Furthermore, the 13C NMR spectrum does only show 12 instead of the expected 13 carbon atoms.
Notably, there is no signal for a keto carbonyl group and the HMBC spectrum does not
show coupling from an expected carbonyl group either. However, a 13C NMR spectrum
obtained in DMSO-d6 exhibited 13 carbon atoms, but also no carbonyl group of a
ketone. The three signals with the largest downfield shift appear at δ = 172.5, 164.9 and
148.3 ppm. The latter is assigned to the carbon bearing the hydroxyl group of a 2,6-
dimethylphenol substructure as the HMBC shows coupling to the methyl groups as well
as the meta aryl protons (Figure 3.8). The other two signals, which could well be
carbons of carboxyl groups, show coupling to a substructure of the phthalic anhydride.
It is also noteworthy that the singlet at 7.10 ppm shows coupling to two different
carbons at δ = 126.3 and 128.9 ppm in the HMQC spectrum (Figure 3.8). The FAB
mass spectrum shows peaks at m/z (%) = 563 (12), 293 (56) and 271 (100). The latter
two are in accordance with the [M+H]+ and [M+Na]+ peaks of the expected carboxylic
acid. The first signal would indicate a dimer of 156 complexing an additional sodium
ion, possible for a carboxylic acid. No plausible empirical formula could be deduced
from the mass spectrum in combination with the elemental analysis, which is consistent
with structure 156, assuming this was the molecular ion. Therefore, it was concluded
Anellated calixarenes by dehydrohalogenation 55
that the molecular mass is indeed 270. Since other findings are also in accord with the
carboxylic acid, with the one crucial exception of the missing carbonyl carbon, it is
assumed that the acid 156 is in an equilibrium with its tautomer 157 (Scheme 3.30).
6.38
3.10
2.03
1.01
1.00
2.27
7.10
7.65
7.68
7.88
7.91
8.05
8.07
2.03
1.01
1.00
7.65
7.68
7.88
7.91
8.05
8.07
16.6
126.3
128.9
129.7
130.0
130.7
131.4
131.9
132.0
148.3
164.9
172.5
126.3
128.9
129.7
130.0
130.7
131.4
131.9
132.0
Figure 3.7. Partial NMR spectra of an unidentified compound obtained by Friedel–Crafts
reaction of 2,6-dimethylphenol (155) and Phthalic anhydride (153). Spectra
recorded at 400 and 100 MHz, respectively, in CDCl3. Residual solvent signals are
marked with an asterisk.
56 Theoretical Part
Figure 3.8. Details from the HMBC (left) and the HMQC (right) spectrum of the unidentified
compound (for full cross-peak table see Appendix).
Such ring-chain tautomerism has been reported to occur for 2-benzoylbenzoic acids like
156 and related structures. The position of the equilibrium strongly depends on the kind
and position of substituents at either of the phenyl rings. The complexation of one
molecule of water by 157 is assumed since an 1H NMR spectrum in CDCl3 interestingly
shows a broad peak at about 5 ppm that integrates to 3 H. Further experiments have to
be conducted in order to confirm this assumption.
Another attempt was made to synthesize the anthracene-9,10-dione 159 directly by a
double Friedel–Crafts acetylation from 2,6-dimethylsanisole (117) and phthaloyl
chloride (158) (Scheme 3.31).
Scheme 3.30. Assumed ring-chain tautomerism of carboxylic acid 156 and the pseudo-ester
157.
The FAB mass spectrum shows a base peak at m/z = 403 and it was initially assumed
that the phthaloyl chloride (158) reacted twice with the anisole to give 160. The 13C NMR spectrum, however, does not show a keto carbonyl carbon. Moreover, 14
different signals instead of the 10 expected for 160 appear in the carbon NMR, one of
Anellated calixarenes by dehydrohalogenation 57
these unexpectedly at δ = 91.8 ppm. The IR spectrum exhibits a carbonyl band at
1769 cm-1 and a signal at 170.1 ppm in the 13C NMR spectrum is also in accord with a
carbonyl carbon in an ester. Based on these findings structure 161 was assigned to the
compound obtained in 67 % yield. The structure was confirmed by HMQC and HMBC
spectra and is also consistent with the [M+H]+ peak at m/z = 403.
Scheme 3.31. Attempted double Friedel–Crafts acetylation to anthracene-9,10-dione 159.
3.5 Syntheses of calix[4]fluorenones
Intramolecular direct arylation of benzoylcalixarenes 162, substituted by either bromine
or chlorine, under the reaction conditions established for the model compound, should
lead to the corresponding calixfluorenone.
First Friedel–Crafts acetylation of tetrapropoxycalixarene 76 with the benzoyl
chlorides 148 was attempted to synthesize the precursor (Scheme 3.32). Addition of a
suspension of aluminium chloride in dichloromethane to a solution of calixarene and
bromobenzoyl bromide 148b at room temperature over a period of 2 h yielded mostly
unreacted starting material and little tripropoxycalixarene 134 (10 %). Only traces (2 %)
of calixarene 162 were isolated and identified by its [M+H]+ at m/z = 775 and 1H NMR
spectra.
58 Theoretical Part
Scheme 3.32. Friedel–Crafts acetylation at calixarene 76.
Chlorobenzoyl chloride 148a was employed under the same reaction conditions, but
the aluminium chloride was added at an inner temperature of 0 °C. According to NMR
16 % of monocarbonyl 163 were obtained alongside tripropoxycalixarene and recovered
starting material. All isolated compounds were insufficiently pure after flash
chromatography. Repeating the reaction at room temperature produced about 7 % of
163 estimated by NMR. Again starting material and tripropoxycalixarene were obtained
as well.
Prompted by the very low yield, the reluctance to react at all and the occurrence of
ether hydrolysis as a side-reaction, alternative routes to produce the precursor were
investigated.
Scheme 3.33. Attempted synthesis of benzoylcalixarenes 165 and 166 by lithiation of
dibromocalixarene 138 and reaction with bezonitriles 164.
After lithiation of dibromocalixarene 138 with n-butyllithium for an hour at –78 °C
and reaction with 2-bromobenzonitrile (164a) overnight, surprisingly starting material
138 was recovered (Scheme 3.33). This indicated that the lithiation had failed.
Exchanging n-butyllithium for t-butyllithium and warming the mixture to –20 °C during
the lithiation produced the same result. Both times the solution of calixarene 138 in
Anellated calixarenes by dehydrohalogenation 59
THF turned yellow upon addition of butyllithium, indicating that the lithiation actually
took place. Furthermore, all the reaction mixtures were dark green the next day, also
when 2-chlorobenzonitrile (164b) was employed. In the latter case a complex mixture
was obtained. The crude product showed at least six spots in thin-layer chromatography
with PE/EtOAc 2:1. Tetrapropoxycalixarene 76 and chlorobenzonitrile were the only
compounds isolated in sufficient purity. Further fractions showed calixarene signals, but
purification was unsuccessful even after multiple flash chromatography. However,
NMR and mass spectra indicated partially hydrolyzed compounds. It is interesting that a
reaction took place with the chlorobenzonitrile, while the dibromocalixarene 138 was
recovered unchanged in reactions with bromobenzonitrile. Moreover, a reference
reaction run parallel to a lithiation where the bromobenzonitrile was used, gave
diformylcalixarene 78 in the usual yield. This suggests that instead of acetylation a
lithium-bromine exchange might take place when the bromo compound 164a is
employed.
Scheme 3.34. Lithiation of dibromocalixarene 138 and reaction with aldehydes 167 or benzoyl
chloride 148a.
Replacing benzonitrile with benzaldehydes 167 (Scheme 3.34) yielded a complex
mixture when bromine was the substituent in ortho position of the aldehyde. Several
fractions obtained after multiple flash chromatography showed signals characteristic for
calixarenes. Interestingly, 6 % of the monosubstituted carbonyl calixarene 162 were
60 Theoretical Part
identified in one fraction and about 9 % of the corresponding disubstituted 165 in
another. Three other fractions seemed to contain some of the desired alcohol 168a or at
least the corresponding monosubstituted compound, as they show signals between 5.5–
6.0 ppm consistent with the proton at the carbon bearing the hydroxyl group. Since this
carbon is chiral, a mixture of stereoisomers would be obtained in the case of the
disubstituted calixarene 168. None of the supposed alcohols, however, could be purified
enough for identification. From the analogous reaction with the chlorobenzaldehyde
167b about 4 % of pure 166 were isolated after crystallization from DCM/MeOH.
Furthermore, about 7 % of the corresponding monosubstituted compound were detected
by 1H NMR spectrometry in a second fraction. Another fraction showed a signal at
δ = 5.83 ppm in the 1H NMR spectrum, indicating that alcohol 168b has also been
formed as a mixture of stereoismers, but further attempts at purification failed.
More of compound 166, about 13 % according to NMR, was obtained when
chlorobenzoyl chloride 148a was employed in the reaction. Another fraction contained
about 20 % of the corresponding monosubstituted calixarene 163 according to the 1H NMR spectrum.
A last attempt, employing a Weinreb amide,135 finally turned out more successful.
Amide 169b was obtained by reaction of chlorobenzoyl chloride 148a with N,O-
dimethylhydroxylamine hydrochloride in 93 % yield after distillation (Scheme 3.35).136
Scheme 3.35. Synthesis of Weinreb amides 169.
Lithiation of dibromocalixarene 138 and subsequent reaction of six equivalents amide
169b gave monochlorobenzoylcalixarene 163 in 33 % and the disubstituted compound
166 in 28 % yield (Scheme 3.36). Just warming the reaction mixture to room
temperature overnight instead of heating to 60 °C slightly decreased the yield. This
route turned out to be quite economical despite the moderate yield. In fact, the crude
product consists only of the two products, which can be easily separated by flash
chromatography, and unreacted amide can be also recovered. The 1H NMR spectrum of
163 shows four partly superimposed doublets for the bridging methylene units at
Anellated calixarenes by dehydrohalogenation 61
δ = 3.17 and 4.46 ppm. These as well as a 2 H singlet at 7.01 ppm, assigned to the meta
aryl protons of the substituted phenol units, confirm monosubstitution. The 13C NMR
also clearly shows three different types of phenol units as well as the carbonyl carbon at
194.2 ppm. The FAB mass spectrum exhibits peaks for [M+H]+ and [M+Na]+ at
m/z = 731 and 753, respectively. In comparison, 166 has a peak at m/z = 869 [M+H]+ in
the FAB mass spectrum and NMR spectra indicate symmetry as there are only two
different phenol units. The carbonyl carbon exhibits a signal at 194.3 ppm in the 13C NMR spectrum as well as a strong absorbance at 1666 cm-1 in the infrared
spectrum.
Scheme 3.36. Lithiation of 138 and reaction with Weinreb amide 169b.
Preparation of the Weinreb amide with a bromine in ortho position in analogy to 169b
yielded 169a in 95 % yield (Scheme 3.35). However, only unreacted starting material
was recovered using four equivalents of 169a under the same reaction conditions that
had yielded the chloro compounds 163 and 166. This further supports the hypothesis of
a lithium-bromine exchange when bromo-substituted arenes are employed as
nucleophiles in the lithiation reaction.
Since the bromo compounds were not available by lithiation reactions, once again
Friedel–Crafts acetylation was attempted. This time dipropoxycalixarene 131 was
employed as starting material to induce a difference in reactivity between the phenol
subunits of the calixarene (Scheme 3.37).121
Dipropoxycalixarene 131 was initially reacted with 3.95 equivalents 2-bromobenzoyl
chloride (148b) and 4.8 eq aluminium chloride at room temperature for 25 min. The
disubstituted bromobenzoylcalixarene 171 was obtained in 15 % yield along with 27 %
of the trisubstituted calixarene 172. Consequently, the amount of bromobenzoyl
chloride was reduced to 2.2 equivalents and the reaction was carried out at different
temperatures and with different reaction times to improve the selectivity.
62 Theoretical Part
Scheme 3.37. Friedel–Crafts acetylation of dipropoxycalixarene 131 with bromobenzoyl
chloride 148b.
No clear optimum was observed as the reaction seems to be also sensitive to the
amount of starting material employed (entries 1 and 4, Table 3.2). After 10 min at room
temperature 57 % of the disubstituted 171 and only 3 % of trisubstituted 172 were
obtained, while a smaller experiment yielded 13 % of the monosubstituted 170 and
80 % of 171, but no 172. As might be expected the same reaction time at 0 °C gave
considerably more mono compound 170 (43 %), but also 52 % of 171. When the
reaction was prolonged to 35 min at 0 °C, 25 % monocarbonyl calixarene 170 and 58 %
of the disubstituted 171 were isolated. In addition, traces of 172 were detected in the
NMR spectra.
Table 3.2. Tested reaction conditions for the Friedel–Crafts acetylation of 131 with 2-
bromobenzoyl chloride (148b) (2.1 eq) and aluminium chloride (4.5 eq).
Entry 131
(mmol)
time
(min)
T
(°C) 170 171 172
1 0.69 10 rt 13 % 80 % -
2 1.97 35 0 25 % 58 % traces
3 2.36 10 0 43 % 52 % -
4 4.11 10 rt - 57 % 3 %
An attempt to synthesize 170 selectively by employing only 1.1 equivalents of the
bromobenzoyl chloride 148b for 10 min at room temperature resulted in 22 % of 170
and 41 % 171 beside unreacted starting material. This experiment indicates that the
mono compound cannot be obtained just by reducing the amount of benzoyl chloride
since the monosubstituted compound reacts readily at the second free phenol unit.
Bis(bromobenzoyl)calixarene 171 shows a [M+H]+ peak at m/z = 875 as well as a base
peak at m/z = 183. The latter is the mass of the bromobenzoyl fragment and is also
Anellated calixarenes by dehydrohalogenation 63
detected in the FAB mass spectra of 170 and 172. The NMR spectra of 171 confirm its
symmetry, showing a characteristic signal at 9.25 ppm for the free hydroxyl groups and
the carbonyl carbon at 194.6 ppm. Tris(bromobenzoyl)calixarene 172 shows three
different phenol subunits and the signal of the hydroxyl groups experiences an upfield
shift to δ = 8.77 ppm in the 1H NMR spectrum. The mono compound 170 shows two
different peaks for its hydroxyl groups at δ = 8.26 ppm and 9.28 ppm. All three 13C NMR spectra show the brominated carbon at about 119 ppm.
Dipropoxycalixarene 131 was also reacted with 2.1 equivalents 2-chlorobenzoyl
chloride (148a) at 0 °C for 35 min. Thus chlorobenzoyldipropoxycalixarene 173 and
bis(chlorobenzoyl)dipropoxycalixarene 174 were obtained in 35 % and 53 % yield,
respectively (Scheme 3.38). NMR spectra clearly show three different phenol subunits
for 173. Characteristic are again the two signals for the hydroxyl groups at δ = 8.26 and
9.27 ppm as well as the carbonyl carbon at 194.0 ppm. The FAB mass spectrum shows
the [M+H]+ peak at m/z = 647 and the base peak at m/z = 139, which is the chlorbenzoyl
fragment. The disubstituted 174 also shows the fragment at m/z = 139 as well as a
[M+H]+ peak at m/z = 785. NMR spectra confirm the symmetrical substitution of the
molecule with a peak at 9.23 ppm for the hydroxyl groups in the 1H NMR spectrum.
Scheme 3.38. Friedel–Crafts acetylation of dipropoxycalixarene 131.
Standard reactions conditions,72a using sodium hydride and propyl iodide in DMF at
60 °C–70 °C for 2 h, were initially used to achieve tetralkylation of the disubstituted
calixarene 171 (Scheme 3.39). From the reaction mixture cone product 165 (21 %) and
paco product 175 (37 %) were isolated. Besides the only partially alkylated 176 was
formed in about 12 % yield according to 1H NMR spectra (entry 1, Table 3.3). When
reacted overnight at 80 °C with more sodium hydride and 19 equivalents of propyl
iodide per hydroxyl group, the alkylation went to completion to yield 34 % of 165 and
33 % of 175 (entry 2).
64 Theoretical Part
Scheme 3.39. Alkylation of dipropoxycalixarenes 174 and 171.
Table 3.3. Reaction conditions tested for the alkylation of 171.
Entry base RX reaction
time
T
( °C)
cone
165
paco
175 176
1a 5.0 eq
NaH 7.6 eq PrI
2 h 70-80 21 % 37 % 12 %c
2a 6.6 eq
NaH 19 eq PrI
14 h 80 34 % 33 % -
3a
13 eq Na2CO3
14 eq PrI
3 d reflux 77 % - -
4b
13 eq Na2CO3
14 eq PrBr
3 d reflux 39 % - 58 % a DMF as solvent; b CH3CN as solvent; c calculated from NMR spectra.
However, to suppress the undesired change of the calixarene confirmation, reaction
conditions were modelled on a protocol by Bonini et al.137 for the alkylation of
diformyldipropoxycalixarene. Using sodium carbonate in acetonitrile for three days
under reflux and propyl iodide as alkylating agent gave a good 77 % yield of the cone
conformer 165 (entry 3).
Since 165 is the sole product of this reaction, workup is easily achieved by either
treating the crude product with methanol in an ultrasonic bath or recrystallization from
DCM/MeOH.
The original protocol employed propyl bromide under otherwise unchanged
conditions. Following this procedure, however, the alkylation did not go to completion,
yielding 39 % of the tetraalkylated 171 as well as 58 % of the trialkylated 176 (entry 4).
Anellated calixarenes by dehydrohalogenation 65
Integration of the signals caused by the hydrogens of the propoxy group for 176 clearly
shows trialkylation, as well as a peak at δ = 6.07 ppm from the free hydroxyl group. The
FAB mass spectra of 165 and 175 confirm that the products are tetraalkylated.
Furthermore, the NMR spectra do not show free hydroxyl groups and integration of the
signals belonging to the propoxy groups also confirms tetraalkylation. Crystals of 165
were obtained from DCM/EtOH and the crystal structure reveals that the substituted
units are coplanar to each other, while the aryl rings are pushed outwards (Figure 3.9).
Figure 3.9. Crystal structure of Bis(bromobenzoyl)tetrapropoxycalixarene 165 in a pinched cone
conformation (disorder of the propyl groups is not sufficiently refined).
The partial cone conformation of 175 is verified by two signals for the bridging
methylene groups at δ = 30.7 and 36.0 ppm in the 13C NMR spectrum. The
corresponding protons exhibit the characteristic pattern of two doublets and a singlet in
a 1:2:1 ratio at δ = 3.10, 3.67 and 4.10 ppm. There are three different sets of signals for
the propoxy groups and thus three different aryl subunits. Two aryl units are substituted
and show different carbonyl carbons at δ = 195.1 and 195.5 ppm. The meta aryl protons
give two 2 H singlets at 7.57 and 7.75 ppm, while the unsubstituted subunits are
identical. The meta aryl protons of the latter appear at 6.28 and 6.94 ppm with the para
proton at 6.47 ppm.
The corresponding chloro compounds were obtained when disubstituted
chlorobenzoylcalixarene 174 was reacted with NaH and propyl iodide at 80 °C
overnight according to entry 2. Cone 166 was isolated in 40 % yield beside 29 % of the
paco calixarene 177b. Traces of 178b were detected in the NMR spectra, but the
66 Theoretical Part
compound was not isolated in its pure form. NMR data of these three compounds show
the same characteristics as their bromo counterparts.
Alkylation of the monosubstituted dipropoxycalixarenes 170 and 173 was also carried
out with sodium hydride and propyl iodide in DMF at 80 °C overnight (Scheme 3.40).
In the case of the bromo compound 33 % of the monosubstituted 162 along with 6 %
partial cone 180 and 27 % trialkylated 179 were isolated.
Bromobenzoyltetrapropoxycalixarene 162 exhibits a [M+H]+ peak at m/z = 775 in the
FAB mass spectrum and NMR spectra clearly show three different phenol subunits. The
complementary partial cone calixarene 180 shows the same mass peak, but the 13C NMR spectrum shows peaks at δ = 30.7 and 36.2 ppm, indicating that a subunit is
trans to the others. That this is the unit bearing the bromobenzoyl substituent was
determined from two-dimensional NMR spectra. The third compound, 179, has a signal
assigned to the free hydroxyl group at 5.99 ppm and integration as well as a [M+H]+
peak at m/z = 733 in the FAB mass spectrum verify trialkylation.
Scheme 3.40. Alkylation of Monocarbonyldipropoxycalixarenes 170 and 173.
Slightly lower yields were obtained from the reaction of the corresponding chlorides.
Cone chlorobenzoylcalixarene 163 was isolated in 24 % yield as well as 2 % of its
partial cone counterpart 182. According to 1H NMR spectra about 16 % of the
trialkylated 181 were also formed. The compound was not characterized further, but
identified by comparison with the corresponding bromo compound 179. Integration of
the proton NMR as well as a peak at 5.99 ppm, caused by the free hydroxyl groups, are
characteristic. Partial cone compound 182 exhibits the characteristic pattern for the
bridging methylene groups with doublets at δ = 3.05 and 4.07 as well as a singlet at
3.68 ppm in the 1H NMR spectrum. The 13C NMR shows the corresponding carbon
atoms at 30.7 and 36.2 ppm, respectively.
Anellated calixarenes by dehydrohalogenation 67
Scheme 3.41. Intramolecular direct arylations to calix[4]fluorenones.
Intramolecular direct arylation was attempted with reactions conditions used for the
corresponding model compound 149 (Scheme 3.41). First, cyclization of
chlorobenzoylcalixarene 163 was attempted employing 5 mol% catalyst for 3 d at
170 °C. Mainly unreacted starting material was recovered, which was again submitted
to the reaction, using 10 mol% of the catalyst. NMR spectra indicated that little of
calixmonofluorenone 183 had been formed. When 163 was reacted with 20 mol%
catalyst at 130 °C for 3 days no reaction took place and the crude product was again
reacted under the same conditions, but at 170 °C for a further 3 days. Again traces of
183 were detected in NMR, but could not be obtained in sufficient purity for
characterization. The same applies to an attempt carried out with the corresponding
bromo compound 162 under the exact reaction conditions reported by Mattay et al. The
crude product obtained by photolysis of 162 clearly exhibited product signals in the 1H NMR. Two fractions of the first flash chromatography (silica gel, PE/EtOAc 8:1 to
2:1) were submitted to a second column. A large excess silica gel along with an unpolar
eluent mixture (PE/EtOAc 100:1 to 50:1) was employed. Under these conditions it was
possible to isolate 25 mg (20 %) of the pure calixfluorenone 183. In addition, a further
9 % of the product were detected in NMR spectra, resulting in an overall yield of 29 %.
The material isolated exhibits a [M+H]+ peak at m/z = 695. NMR spectra reveal the
existence of four different phenol units as expected for the cyclized compound (Figure
3.10).
68 Theoretical Part
6.66
6.48
8.67
3.23
4.27
4.15
1.04
4.14
6.00
1.15
1.92
1.03
1.02
0.97
1.00
1.00
0.92
0.95
1.12
1.14
1.85
1.96
1.98
2.12
3.16
3.18
3.25
3.65
3.79
3.98
4.09
4.26
4.33
4.45
4.47
4.53
6.11
6.23
6.92
7.13
7.28
7.45
7.51
7.65
7.88
10.19
10.24
11.26
23.58
23.89
24.16
25.97
31.43
31.58
77.12
77.70
77.77
122.50
122.68
122.71
123.21
124.26
125.74
127.27
127.74
128.29
128.44
128.77
129.46
129.57
132.26
132.75
134.09
134.18
134.94
134.98
137.74
137.76
137.91
155.77
156.07
158.52
165.80
193.73
Figure 3.10. NMR spectra of calixfluorenone 183, recorded at 400 and 100 MHz in CD2Cl2,
respectively.
The carbonyl carbon appears at 193.7 ppm in the 13C NMR spectrum. This carbon
(C6) shows coupling to a doublet at 7.65 (H8) and a 1 H singlet (H4) at 7.51 ppm in the
HMBC spectrum. The latter is assigned to the proton meta to the propoxy substituent at
the fluorenone unit. The bridging methylene carbon (C15) experiences anisotropic
effects from the fluorenone moiety and exhibits a strong upfield shift of 5 ppm to
26.0 ppm. Weak characteristic absorbances at 328 nm and 274 nm as well as a strong
absorbance at 263 nm are observed in the UV spectrum of the yellow fluorenone.
35 14
4
15
OOO O
6
11
10
98
O
Anellated calixarenes by dehydrohalogenation 69
When the disubstituted chlorobenzoylcalixarene 166 was reacted with 10 mol%
catalyst for 24 h at 130 °C, 29 % of 184 were obtained as a mixture of both
stereoisomers. However, 7 % of the overall yield were pure isomer 184a, isolated by
column chromatography. The solid shows the characteristic yellow of the fluorenones.
From the other reaction conditions tested with the bromo compound 165 (Table 3.4),
only mixtures of the stereoisomers were obtained. Generally flash chromatography was
insufficient to yield pure material and recrystallization from DCM/EtOH was necessary.
Table 3.4. Tested reaction conditions for the cyclization to calixdifluorenones 184.
Entry starting
material catalyst
a T in °C time yield
1 166 10 mol% 130 °C 24 h 29 %
2 165 10 mol% 130 °C 3 d 23 %b
3 165 10 mol% 150 °C 3 d 31 %b
4 165 10 mol% 170 °C 3 d 12 %b
5 165 5 mol% 130 °C 24 h 46 %b
17 %c
6 165 photolysis 24 h 78 %b
55 % c
7d 165 3 mol% 120 °C 10 h 37 %b
8d 165 3 mol% 120 °C 10 h
76 %b
57 %c
All reactions were carried out only once; a Pd(OAc)2 except for entries 7 and 8 where a Bedford
catalyst 150 was used; b estimated from NMR spectra; c isolated after recrystallization; d PivOH,
K2CO3 in DMA/toluene (entry 7) or DMA (entry 8).
However, when the reaction was carried out in a DMA/toluene mixture (entry 7, Table
3.4), a mixture of the desired fluorenones and starting material was obtained. Separation
by flash chromatography was unsuccessful. According to NMR spectra, the mixture
contained 37 % of the calixdifluorenones and 40 % starting material. The yield
improved to 76 %, estimated from NMR, when DMA was the sole solvent (entry 8).
Satisfying 57 % 184 were isolated after a single flash chromatography and subsequent
recrystallization from DCM/EtOH.
70 Theoretical Part
Photolysis of bis(bromobenzoyl)calixarene 165 in acetonitrile for 24 h (entry 6), was
the only reaction with comparable yields, but the material thus obtained was less pure
even after recrystallization.
The FAB mass spectrum of the isomer mixture of 184 shows the [M+H]+ as base peak
at m/z = 797. NMR data are very similar to those of the calixmonofluorenone 183.
Structure 184a was assigned to the single isolated isomer based on the symmetry
observed in the spectra. Only two different subunits are observed in the NMR spectra;
the signals obtained for the carbons substituted by the propoxy groups are diagnostic.
Isomer 184a shows one peak at 165.1 ppm for the fluorenone unit and a second signal at
155.3 ppm for the unsubstituted ring. As would be expected the steroisomeric mixture
exhibits three different unsubstituted aryl units at 155.0, 155.3 and 155.6 ppm.
In contrast to the calixphenanthrenes and calixdihydrophenanthrenes, the
calixfluorenones 184 do not seem to be fixed in a pinched cone conformation. The
protons of the unsubstituted aryl unit appear as a multiplet at about 6.2 ppm comparable
to the shift observed for the tetrapropoxycalixarene 76.
3.6 Previous studies on calix[4]triphenylenes
As previously reported by our group, dehydration of Bisbiphenylcalix[4]arene 185
yielded 68 % of spiro-calixarene 186 (Scheme 3.42).72a,74 Due to the lack of hydrogen-
bonding that could stabilize the cone conformation, 186 shows fast ring inversion at
room temperature. Time-dependent NMR studies established that 186 prefers a partial
cone structure. Acid-catalyzed rearrangement of spiro-compounds like this should make
calix[4]triphenylenes like 187 available. Plieninger et al.138 reported an analogous
reaction to fluorenonylcyclohexadienones.
Since the basicity of the pyridyl groups might be unfavourable for the acidic
conversion, replacement of these substituents by benzyl or benzoyl groups was
attempted in preliminary studies.78 However, in both cases the new substituents were
lost, or partially lost, during the Suzuki coupling to the corresponding
biphenylcalixarenes (Scheme 3.43).
Therefore, conditions of the Suzuki coupling have to be readjusted to prevent loss of
the lower rim substituents. Besides, the corresponding dipropoxycalixarene is to be
synthesized and submitted to Suzuki coupling. Furthermore, problems occurred in
Anellated calixarenes by dehydrohalogenation 71
reproducing spiro-calixarene 186, necessitating investigations into alternative methods
to produce the spiro compound.
Scheme 3.42. Synthesized spiro-calixarene 186 and planned acid-catalyzed rearrangement to
calix[4]triphenylene 187.
188 or 189
OHOH OO
R R
Br Br
OHOH HOOH
191 (42 %)
OHO HOOH
193 (22 %)
O
OHOH HOOH
+
191 (29 %)
OHOH HOOO
192 (6 %)
+
B(OH)2+
190
R = Bn
R = Bz
Scheme 3.43. Suzuki coupling of dibromodibenzylcalixarene 188 or dibromodibenzoyl-
calixarene 189 resulting in loss of R. 10 mol% Pd(PPh3)4, 2 N K2CO3, THF, 20 h,
120 °C.
72 Theoretical Part
Hypervalent iodine(III) reagents139 like (diacetoxyiodo)benzene (PIDA)139 or
[bis(trifluoroacetoxy)iodo]benzene (PIFA)140,141 seem to provide a promising alternative
(Figure 3.11). They are easy to handle, readily available and have low toxicity, while
their reactivity is similar to heavy metal reagents or aniodic oxidations.142
Figure 3.11. The hypervalent iodine reagents PIDA and PIFA.
Oxidation of p-substituted phenols with hypervalent iodine(III) reagents in the
presence of nucleophiles, yields 4,4-disubstituted cyclohexa-2,5-dienones (Scheme
3.44).143 In the intramolecular reaction, spiro-annulated cyclohexadienones comparable
to calixarene 186 are obtained (Scheme 3.45).144
Scheme 3.44. Oxidation of p-substituted phenol 196 and trapping with nucleophile.143a
Kita et al. reported that the reactions proceed with better yields in poorly nucleophilic
protic solvents like the fluorinated alcohols 2,2,2-trifluoroethanol (TFE) and 1,1,1,3,3,3-
hexafluoro-2-propanol (HFIP).144c With phenol ethers nucleophilic substitution occurs
in these solvents, leading to biaryl compounds and yields can be improved by addition
of BF3·Et2O (Scheme 3.46). Phenols react with the iodine center in the hypervalent
iodine compound via intermediate 206, while in reactions with phenol ethers a cation
radical intermediate like 207 is generated (Scheme 3.47).145,146
Anellated calixarenes by dehydrohalogenation 73
OH O
PIDA, CH3CN,reflux, 4 h
198 199 (30 %)
OH O
PIDA, MeOH, rt
200 201 (50 %)
a)
b)
OH O
PIFA,TFE,-40 °C
202 203 (61 %)
N NCOCF3 COCF3
c)
OMe
Scheme 3.45. Spiro-annulated cyclohexadienones.
Scheme 3.46. p-substituted phenol ether reacting under nucleophilic substitution.
Scheme 3.47. Mechanistic pathways for hypervalent iodine oxidations.
74 Theoretical Part
3.7 Synthesis of a triphenylene model compound
In order to find suitable reaction conditions for the synthesis of the spiro compound,
2,6-dimethylphenol (155) was chosen as precursor for the model compound 209
(Scheme 3.48).
Scheme 3.48. Synthesis of Triphenylene 211.
Winzler et al. reported that bromination of 155 with bromine in glacial acetic acid at
10 °C yielded the brominated compound 208 in 88 % after recrystallization.147 The
initial attempt to reproduce this protocol gave only a 41 % yield after recrystallization.
Using bromine in chloroform the yield was increased to 69 %.148 The EI mass spectrum
showed the molecular ion at m/z = 199 and 1H NMR data were in accord with those
reported by Fischer et al.149 Subsequent Suzuki coupling with 2-biphenylboronic acid
(190) yielded 66 % of phenol 209, using reaction conditions previously established for
the calixarenes.150 NMR data as well as the peak at m/z = 274 from the molecular ion
verify the formation of 209.
Conversion to the spiro compound 210 was attempted using PIFA in various solvents
(Table 3.5). When the reaction was carried out in acetonitrile for 15 min, modelled on a
protocol by Swenton et al.,142a about 28 % product were obtained according to NMR
(entry 1). Only traces of product were detected in the 1H NMR spectra of the reaction in
Anellated calixarenes by dehydrohalogenation 75
chloroform (entry 2). When 2,2,2-trifluoroethanol was used as solvent as described by
Kita et al.,144c,151 spiro compound 210 was formed in about 53 % according to NMR
(entry 3). With regard to the poor solubility of most calixarenes in alcohols, different
solvent mixtures were investigated (entries 4 to 6) since also the biphenylphenol 209
exhibited only moderate solubility. Good yields of 210 around 70 % were obtained from
1:3 and 1:1 mixtures of CH2Cl2/CF3CH2OH, respectively. The reaction conditions
originally employed in the synthesis of spirocalixarene 186 failed to yield any product
at all (entry 7).74
Table 3.5. Reaction conditions for the synthesis of spiro compound 210 with PIFA at room
temperature.
Entry reaction time solvent yield
1 15 min MeCN 28 %a
2 20 min CHCl3 tracesb
3 15 min CF3CH2OH 53 %a
4 15 min 1:3 MeCN/CF3CH2OH 28 %a
5 15 min 1:3 CH2Cl2/CF3CH2OH 70 %
6 15 min 1:1 CH2Cl2/CF3CH2OH 73 %a
7b c CH2Cl2, MeNO2 -
a purity estimated from NMR spectra; b detected in 1H NMR spectrum; c 1. CH2Cl2, 15 min, Ar,
2. FeCl3, MeNO2, 40 min, rt.
Spiro compound 210 shows the [M+H]+ base peak at m/z = 273. The diagnostic signal
for the quaternary carbon atom appears at δ = 56.9 ppm in the 13C NMR spectrum and
the carbonyl carbon is observed at 187.9 ppm. The carbons meta to the carbonyl group
give a peak at 144.6 ppm, while the corresponding protons exhibit a singlet at 6.30 ppm
in the 1H NMR spectrum.
Rearrangement of the spiro compound 210 to triphenylene 211 was achieved applying
the protocol by Plieninger et al.,138 whereby concentrated sulfuric acid catalyzes the
reaction at 100 °C in acetic anhydride. Triphenylene 211 was obtained in a very good
92 % yield with a molecular ion at m/z = 314 in the FAB mass spectrum. The 1H NMR
spectrum confirms the asymmetry of the rearranged molecule, exhibiting two 3 H
singlets at δ = 2.42 and 2.76 ppm, as well as a 1 H singlet at 8.37 ppm for the proton
76 Theoretical Part
meta to the ester group. The 13C NMR spectrum shows the carbonyl peak at 169.1 ppm
and a strong carbonyl band also appears at 1749 cm-1 in the IR spectrum.
3.8 Syntheses of calix[4]triphenylenes
To prevent removal of the benzyl groups in the Suzuki coupling, the reaction conditions
were changed from potassium carbonate in THF to sodium carbonate in
toluene/methanol. In addition, the reaction time was reduced to 4 h at only 100 °C
(Scheme 3.49).131,152 Thus, the biphenylcalixarene 212 was synthesized once in 34 %
yield after multiple flash chromatography. The FAB mass spectrum of 212 shows the
molecular ion at m/z = 908. In the 1H NMR spectrum the free hydroxyl groups give a
2 H singlet at 7.56 ppm and the meta aryl protons another 4 H singlet at 6.87 ppm.
Employing the dibromodipropoxycalixarene 213 under the same reaction conditions
resulted in a considerably better 77 % yield of biphenylcalixarene 214. The free
hydroxyl groups appear as a singlet at 8.04 ppm and the protons meta to the hydroxyl
groups give a 4 H singlet at 6.87 ppm.
B(OH)2
213190 214 (77 %)
OO HOOH
Br Br
OO HOOH
Pd(PPh3)4, 2 M Na2CO3,toluene, MeOH, 4 h, 100 °C
OO HOOH
Pd(PPh3)4, 2 M Na2CO3,toluene, MeOH, 4 h, 100 °C
OO HOOH
Br Br
188 212 (34 %)
B(OH)2
190
Scheme 3.49. Synthesis of biphenyldibenzylcalixarene 212 and biphenyldipropoxy-calixarene
214 by Suzuki coupling.
Anellated calixarenes by dehydrohalogenation 77
Several attempts to oxidize compound 214 with PIFA, using acetonitrile or
dichloromethane as solvents, showed signs that a reaction had taken place, but only
starting material was recovered and identified. The same applies to reactions carried out
in the solvent mixtures also used in the synthesis of model compound 211.
Identification is complicated by the supposed conformational flexibility of spiro
calixarene 215 also observed for the corresponding dipyridylcalixarene 186.
Scheme 3.50. Attempted oxidation and rearrangement of biphenylcalixarene 214 followed ester
hydrolysis to 217. Only one steroisomer of the calix-triphenylenes is depicted.
Rearrangement to the calixtriphenylene may reduce the flexibility since the free
hydroxyl groups are available for hydrogen bonding. Accordingly, no further attempts
at isolating the spiro compound 215 were made. Biphenylcalixarene 214 was reacted
with PIFA in a 1:1 mixture of dichloromethane and trifluoroethanol at room
temperature for 15 min. After removal of the solvent the crude product was directly
submitted to the rearrangement in acetic anhydride with sulfuric acid (Scheme 3.50).
One fraction obtained after purification by flash chromatography with PE/toluene 1:1
was considered relatively pure. The FAB mass spectrum gives evidence that it is indeed
calixtriphenylene 216, exhibiting a peak at m/z = 915 consistent with [M+Na]+. An
additional peak at m/z = 850 is in accord with the loss of one ester group. The 1H NMR
spectrum clearly differs from the starting material and shows signals around 8.5 ppm
78 Theoretical Part
characteristic for the bay-region protons of the triphenylene moiety (Figure 3.12). The
methyl groups of the acetyl groups give two singlets at δ = 2.36 and 2.38 ppm,
respectively. Other calixarene signals like the bridging methylene groups, however, are
superimposed by a large number of additional signals between 3.0–4.5 ppm. The mass
of signals observed is not surprising considering that a mixture of steroisomers is
formed in the reaction and the product itself is asymmetric. The upfield shift of signals
to the region between 5 and 6.5 ppm, indicate that the compound adopts a pinched cone
conformation since these signals are assigned to the aryl protons of the unsubstituted
rings.
Figure 3.12. 1H NMRs of the assumed calixtriphenylene 216 (top) and the deprotected 217
(bottom), recorded at 200 MHz in CDCl3.
Compound 216 was not further purified and analysed, but submitted to ester cleavage.
After subsequent purification by flash chromatography and recrystallization from
DCM/MeOH, 18 mg (40 %) of a colorless solid were obtained. The molecular ion
observed in the FAB mass spectrum at m/z = 808 is in accord with triphenylene 217.
NMR spectra confirmed that the material is quite pure and approximately a 1:1 mixture
of the steroisomers (Figure 3.12). Again characteristic triphenylene signals are observed
as multiplets at about 8.32, 8.57 ppm and a third at 7.50–7.66 ppm. Coupling in the
HMBC shows that the 1 H singlets of the protons meta to the hydroxyl groups are
superimposed by the 8.32 multiplet and appear at 8.32 and 8.38 ppm. The two singlets
at higher field, δ = 6.68 and 6.78 ppm, do not show cross-peaks in the HMQC and were
Anellated calixarenes by dehydrohalogenation 79
assigned to the hydroxyl groups. This was confirmed by the HMBC spectrum as
coupling to the aryl carbons bearing the hydroxyl groups at δ = 154.90 and 154.94 ppm
was observed. The corresponding carbons of the unsubstituted aryl units appear at
δ = 152.8, 153.2 and 153.6 ppm. Three different types of these units are expected for a
stereoisomeric mixture of 217. Consequently, the number of signals as well as their
approximate 1:2:1 ratio confirms that both stereoisomers have been formed. Identical
signal patterns can be observed for the propoxy substituents at these units. It is
noteworthy that two methylene signals experience an upfield shift of about 1–2 ppm to
29.0 and 29.2 ppm due to anisotropic effects from the triphenylene moiety. Comparable
shifting has already been observed in the case of the calixfluorenones (Chapter 3.5).
Furthermore, these two signals exhibit coupling only to a multiplet at 4.75–4.90 ppm,
which consists of several superimposed doublets. These are assigned to the protons of
the bridging methylene groups, indicating that the equatorial protons influenced by the
triphenylene moiety experience a large downfield shift of more than one ppm. For
comparison, the equatorial protons of the other methylene bridges appear at 3.64 and
3.68 ppm, their axial counterparts at 4.46 and 4.49 ppm.
Signals of the unsubstituted aryl units exhibit an upfield shift and it was possible to
distinguish three sets of signals in the H,H-Cosy spectrum (Figure 3.13). In accordance
with the shifts observed for the methyl substituted diphenanthrene 86, the protons of the
aryl ring towards which both triphenylene units are directed (ring B) should experience
the largest shift due to anisotropic effects. Therefore, the signals at 5.69 and about
5.87 ppm were assigned to the meta and para protons of this ring in isomer 217b. In
fact, the muliplets at 5.86–5.89 as well as 6.62–6.68 ppm each consist of a doublet and a
triplet. The latter are the para aryl protons of isomer 217b, the first the meta aryl
protons of 217a. A triplet at 6.24 ppm is assigned to the para protons in isomer 217a.
Practically no shift is observed for the meta aryl protons of ring C in 217b, from
which both triphenylene units are directed away. These exhibit a doublet at 6.91 ppm.
A 1:1 ratio of the stereoisomers 217a and 217b was determined from the 1H NMR
spectrum by integration of the aryl protons.
Since Pd-catalyzed dehydrohalogenation was successfully employed in the synthesis
of the fluorenone model compound an alternative approach to calixtriphenylenes was
developed (Scheme 3.51). Consequently, the bromosubstituted biphenylcalixarene 220
80 Theoretical Part
5.75.96.16.36.56.76.97.0(ppm)
5.6
5.7
5.8
5.9
6.0
6.1
6.2
6.3
6.4
6.5
6.6
6.7
6.8
6.9
7.0
(ppm)
Ha
HbH
c
Hd
He
Hf
Hg
Hf
Hg
He
Ha
Hc
Hb
Hd
OH
OPr
OPr
HOA'
B'
Hc
Hb
Ha
Ha
OH
OPr
OPr
HOA
B
A
C
Hf
Hg
Hf
Hd
Hb
Hc
He
Hd
A'
B'
Figure 3.13. Detail of the H,H-Cosy spectrum of the stereoisomeric mixture 217, recorded at
400 MHz in CDCl3.
had to be prepared by using reverse starting materials in the Suzuki coupling, reacting
the calixareneboronic acid 218 with 2,2'-dibromobiphenyl (219).
The latter was easily prepared according to a literature procedure by Gilman et al.
from two equivalents 1,2-dibromobenzene and one equivalent n-butyllithium at low
temperature.153 2,2'-Dibromobiphenyl (219) was obtained in 88 % yield as colorless
crystals with a melting point of 78-79 °C (lit. 80-81°C) and the molecular ion at
m/z = 312 in the EI mass spectrum.
Synthesis of the calixareneboronic acid in 42 % yield was reported by Larsen et al. by
lithiation of the dibromocalixarene and reaction with trimethyl borate.85 Purification
was achieved by conversion of the crude product into the 1,3-propanediol ester as it was
problematic to purify the crude boronic acid directly. The pure ester was then
hydrolyzed to give pure 218 (Scheme 3.52).
First attempts to reproduce this procedure gave about 50 % of the boronic acid ester, but
with 42 % after hydrolization considerably less than the 71 % reported for this step in
the literature. Furthermore, a pure 1H NMR, which unambiguously verified the
deprotection and purity of the obtained compound, could neither be obtained in
DMSO-d6 nor in chloroform-d1. Since this method was time-consuming and did not
yield satisfying amounts of pure material, another procedure reported by Atwood et al.
was adopted.154 The crude product was sonificated with hexane and filtered to yield
Anellated calixarenes by dehydrohalogenation 81
Scheme 3.51. Alternative approach to calixtriphenylenes.
OO OO
(HO)2B B(OH)2
OO OO
Br Br
OO OO
B B
OO OO
(HO)2B B(OH)2O
O OO
1. nBuLi, THF,-78 °C, 15 min
2. 4 eq B(OMe)3,2 h, -78°C to rt
propanediol,benzene
THF/H2O (8:3),0.1 N HCl, reflux, 1h
1. nBuLi, -78 °C,THF, 15 min
2. 19 eq B(OMe)3,overnight,-78°C to rt
3. 4 N HCl, 90 min
218
218 222 (~ 50%)
138
~ 42%
53 %
Scheme 3.52. Synthesis of calixareneboronic acid 218 (left) in comparison to a method
described in the literature (right).
82 Theoretical Part
53 % of supposed 218. The isolated compound was used without further purification in
the Suzuki coupling.
Initially the same reaction conditions used for the corresponding unbrominated
compound were applied―Tetrakis(triphenylphosphine)palladium(0) with 2 N
potassium carbonate in THF for 20 h at 120 °C.72a,150 No product at all was isolated and
the reaction time was prolonged to 3 d. However, the desired biphenylcalixarene 220
was still obtained in only about 11 % yield. Once again the reaction conditions were
changed, using sodium carbonate in toluene/methanol at 100 °C for 5 h.152 After
subsequent flash chromatography and recrystallization from DCM/MeOH 25 % of
220 were isolated. The formation of 220 confirms that the calixareneboronic acid 218
has been obtained in the previous step. However, the low yield might be due to
insufficient purity of the material. Otherwise it should be possible to increase the yield
by further optimization of the reaction conditions.
The FAB mass spectrum depicts a molecular ion at m/z = 1054 in accord with
calixarene 220. In the 1H NMR spectrum slight impurities can be detected and it was
not possible to obtain analytically pure material for elemental analysis. However, a 2 H
doublet assigned to the protons next to the bromo substituent appears at 7.65 ppm. The
existence of two different aryl subunits is also confirmed. The signal pattern of the
peaks for the bridging methylene groups suggests that the molecule adopts an
asymmetric conformation. In accordance with this assumption is the splitting of signals
observed for the protons at the aryl units. The meta aryl hydrogens of the biphenyl
substituted ring appear at δ = 6.88 and 6.97 ppm. Contrary to the expected singlets for
each one, a more complex pattern is observed. Moreover, the HMBC shows coupling
between the two signals. This indicates that the calixarene prefers a structure with the
biphenyl substituent directed to one side of the aryl subunit comparable to the structure
of the triphenylene (Figure 3.14). It would have also been conceivable that one of the
biphenyl moieties is directed into the cavity and the other pointing away from it. There
has been evidence that the monobiphenyltetrapropoxycalixarene without bromo
substituents prefers a comparable structure with its biphenylmoiety inside the calixaren
cavity.72a
However, only two types of subunits can be distinguished. This suggests that the
structure shows conformational flexibility, which might also explain the splitting of the
respective signals. The aryl protons of the unsubstituted phenol units also exhibit
splitting, resulting in more complex signals than the expected doublet and triplet.
Anellated calixarenes by dehydrohalogenation 83
Figure 3.14. Possible conformations the bisbiphenylcalixarene 220 might adopt.
The observed upfield shift to δ = 5.50–5.55 for the meta aryl protons and to δ = 5.97–
6.26 for the ones in para position is a sign for a pinched cone conformation of
calixarene 220.
Biphenylcalixarene 220 was subsequently submitted to reaction conditions described
by Müllen et al. (Scheme 3.51).107c The molecular ion at m/z = 892 in the FAB mass
spectrum is in accordance with the triphenylene 221. The 13C NMR spectrum exhibits
signals for five types of subunits, which is the number of subunits expected for the
mixture of stereoisomers The 1H NMR shows the signals characteristic for the
triphenylene moieties as multiplets δ = 7.60, 8.33 and 8.63 ppm. Additionally, two
singlets for the protons in meta position to the propoxy groups appear at δ = 8.36 and
8.42 ppm, respectively. Moreover, the NMR spectra show that indeed a mixture of both
isomers has been formed. The 1H NMR is in fact very similar to that obtained for the
calix[4]diphenanthrene with additional methyl groups 86 (Chapter 2.3). The protons of
the unsubstituted aryl units exhibit distinct signals between δ = 5.0 and 6.5 ppm, which
can be assigned to the three different types of aryl rings (Figure 3.15). The aryl unit of
isomer 221a has two different meta aryl protons, which appear at δ = 5.28 and 6.06 ppm
with the para protons as a triplet at 5.91 ppm. Isomer 221b on the other hand has two
different aryl subunits, each with identical meta protons. Both triphenylene moieties
point towards one of these units, which causes a large upfield shift to 5.04 ppm for the
meta and 5.57 ppm for the para protons. The corresponding signals of the opposite unit,
from which the triphenylene moieties are directed away, give a doublet at 6.38 and a
triplet at 6.27 ppm. Integration of the aryl signals reveals that stereoisomers 221a and
221b have been formed in a ratio of about 1:1.4. The observed upfield shifts are larger
than those for the corresponding dialkylated compound 217. This suggests that
calixarenes 221 prefer a pinched cone conformation with the bulky triphenylene
moieties pushes outwards. In that case, shielding of the aryl protons caused by the ring
84 Theoretical Part
current of the opposite aryl unit results adds to the observed upfield shift. The
calixphenanthrenes have also been shown to adopt a pinched cone conformation and
exhibit similar shifts (Chapter 2.3).
1.44
1.25
0.77
1.01
1.00
0.92
1.46
5.04
5.28
5.57
5.91
6.06
6.27
6.38
Figure 3.15. Aromatic region of the 1H NMR spectrum of the mixture of steroisomers 221a and
221b, recorded at 400 MHz in CDCl3.
3.9 Conclusion
A number of 2-bromobenzoyl- and 2-chlorobenzoylcalixarenes have been prepared by
Friedel–Crafts acetylation after initial attempts failed to yield the desired products. In
order to succeed, it was crucial to employ the dipropoxycalixarene and thus introduce a
difference in reactivity between the different aryl units. Low temperatures and short
reaction times as well as equimolar amounts of the reagents gave good results, albeit
mixtures of mainly mono- and disubstituted compounds. Further optimization of the
reaction conditions might improve the yields and the selectivity of this reaction.
Moreover, the bromophenylacetylcalixarene 132, already obtained in low yield by
Friedel–Crafts acetylation after two hours, and the corresponding disubstituted
compound should also be accessible by employing the optimized conditions with
Anellated calixarenes by dehydrohalogenation 85
shorter reaction times. Direct Pd-catalyzed cyclization of 223 to calix[4]-
phenanthrenones 227 seems not be possible due to the α-acidic hydrogens.
The alternative route depicted in Scheme 3.53 could circumvent this problem. First
reduction of 223 to the corresponding alcohol and subsequent protection to 225 with
chloromethylmethyl ether would be necessary. Parisien et al. reported the successful
Pd-catalyzed cyclization of a similar MOM ether.155 However, considering the number
of steps, the overall yield would probably be very low and the product is formed as a
mixture of different steroisomers.
The separation of the stereoisomers obtained in the successful cyclizations to
calix[4]dihydrophenanthrenes 146, calix[4]fluorenones 184 and calix[4]triphenylenes
221 proves to be a crucial problem. Since the stereoisomeric mixtures are inseparable
by normal flash chromatography, it is necessary to employ HPLC. The low solubility of
the calixarenes in eluents usually used for the flash chromatographic separations might
pose a problem. Chiral HPLC columns might be useful as the anellated calixarenes are
inherently chiral.
Both possible isomers seem to be formed in a ratio of about 1:1. This indicates that the
first cyclization does not influence the regioselectivity of the second ring closure.
Similar observations were also made by Barton et al. for the intramolecular direct
arylation to a calixarene containing benzochromene units 57.77
Although several calix[4]arenes containing anellated subunits have been isolated, the
reaction conditions have to be further improved as yields so far have been low. Very
promising seems to be the use of a Bedford catalyst 150 in combination with pivalic
acid co-catalyst. The model compound 151 was obtained in a very good 90 % yield
under these conditions and a first attempt with bis(bromobenzoyl)calixarene 165
yielded the calix[4]difluorenone 184 in a good 60 % yield.
The calix[4]triphenylenes 217 and 221 have been synthesized by two different routes.
In the case of the oxidation of biphenylcalixarenes with PIFA and subsequent acid-
catalyzed rearrangement to 216, it could not be determined what the yields of the
intermediate spirocalixarene 215 are. Its purification and identification was
unsuccessful, probably due to the assumed conformational flexibility of this compound
Alternatively, the intramolecular biaryl coupling of phenol ethers leads directly to
calixtriphenylenes. Kita et al. reported that using PIFA in DCM at low temperatures in
combination with BF3·Et2O yielded the anellated compound 205 (Scheme 3.54).156
86 Theoretical Part
OO HOOH OO HOOH
O O
131 116 132
BrBr
OO OO
O O
223
BrBr
OO OO
OH HO
224
BrBr
OO OO
OMOM MOMO
225
BrBr
OO OO
OMOM MOMO
OO OO
O O
226 227
Br
O
Cl+
Scheme 3.53. Alternative route to calix[4]phenanthrenones 227.
Scheme 3.54. Intramolecular biaryl coupling of phenol ethers with PIFA.
Anellated calixarenes by dehydrohalogenation 87
Furthermore, they report that employing heteropoly acids in combination with PIFA
also leads either to biaryl coupling (230) or selectively to spirodienone formation
(228).157 Direct intramolecular biaryl coupling would make the rearrangement and
subsequent ester cleavage unnecessary and save two steps in the synthesis of
calix[4]triphenylenes.
The second route, employing Pd-catalyzed cyclization of the bromobiphenyl-
calixarene 220, also suffers from low yields. One problem is the formation of the
boronic acid at the calixarene, which gave low yields and might also lack sufficient
purity. The reaction conditions of the subsequent cyclization require further
optimization. Similar reaction conditions to those already employed were reported by
Scott et al. and Rabideau et al. for the synthesis of dibenzocorannulenes.106,107a
Nevertheless, the Bedford catalyst/pivalic acid system should be also tested for the
synthesis of calix[4]triphenylenes.
89
4 Syntheses of unsymmetrical tetrazines
4.1 Introduction
1,2,4,5-Tetrazines are six-membered aromatic rings containing four nitrogen atoms.158
Their deep purple color is attributed to an n–π* transition in the visible with a maximum
usually between 510 and 530 nm. Its position is only weakly dependent on the
substituents in 3- and 6-position, contrary to the strong absorption in the UV region
corresponding to a π–π* transition.
Tetrazines exhibit interesting electrochemical as well as optical properties and their
potential applications include energetic materials, active molecules for nonlinear optics
and inclusion in conducting polymers.158b Attempts to include them in supramolecular
structures by synthesis of tetrazine-containing cyclophanes or coupling of tetrazines to
the hydroxyl function of cyclodextrins have also been reported recently.158b,159 The
basicity and coordination ability of the tetrazine nitrogens is low, but esters of 3,6-
dicarboxylic acids and 3,6-bis(pyridyl)-substituted derivatives (bptz or dptz) have
become popular in coordination chemistry (Figure 4.1).160 The 3,3’- and 4,4’-analogues
of bis(2-pyridyl)-1,2,4,5-tetrazine (bptz) have been reported to form complexes with
trimesic acid, which exhibit interesting two-dimensional structures.161
Symmetrically substituted tetrazines can be obtained by the reaction of aromatic nitriles
with hydrazine via imidoethers as reported by Pinner.162 A modified procedure employs
aromatic nitriles, hydrazine and sulfur.163 Both methods yield 1,2- or 1,4-
dihydrotetrazines (Scheme 4.1), which are subsequently oxidized to the 1,2,4,5-
Figure 4.1. Examples of 3,6-disubstituted tetrazines used as ligands.
90 Theoretical Part
Scheme 4.1. Synthesis of dihydrotetrazines from aromatic nitriles according to Pinner162(left)
and a modified procedure (right).
tetrazines, usually by employing nitrous gases or sodium nitrite in combination with
acetic acid.
Synthesis of unsymmetrically substituted tetrazines is more problematic. One method
is the functionalization of certain precursors, e.g., 3,6-dichlorotetrazine, by nucleophilic
aromatic substitution. Thereby, one chlorine is usually readily replaced at room
temperature whereas disubstitution requires harsher conditions.158b Another useful way
to unsymmetrically substituted tetrazines is a stepwise synthesis starting with an acid
chloride 231 and an aryl hydrazide 232 (Scheme 4.2). These react to a diacylhydrazide
233, which can be converted into the corresponding hydrozonoyl chloride 234. From
here, 1,2,4,5-dihydrotetrazines164,165,166 235 as well as 1,2,4-triazoles167 236 are
accessible by reaction with hydrazine or ammonia, respectively.
Scheme 4.2. Stepwise method to synthesize unsymmetrically substituted 1,2,4,5-
dihydrotetrazines or 1,2,4-triazoles.
Functionalization of a calixarene with tetrazine moieties might in itself give
supramolecular structures with interesting optical and electrochemical properties.
However, fixing the nitrogens in an orientation in which they are directed towards the
Syntheses of unsymmetrical tetrazines 91
inside of the calixarene cavity would probably be more effective for the formation of
complexes inside of it.
The electron-deficient tetrazines are well-known diene compounds in inverse electron
demand Diels–Alder reactions.165,168,169,164 Electron-rich dienophiles already react with
tetrazines at room temperature while other dienophiles require higher temperatures. The
first example of the formation of pyridazines by Diels–Alder reaction of tetrazines is the
reaction of 3,6-diphenyl-1,2,4,5-tetrazine with acetylenes to give, for example, 238
(Scheme 4.3), reported by Carboni et al.170
Scheme 4.3. Examples of tetrazines in the inverse electron demand Diels–Alder reaction: 238170,
239169b, 241
169f, 242169a.
Cycloaddition of diphenylacetylene, or other sterically demanding olefins and
acetylenes, to the tetrazine ring would yield tetrapyridazinecalixarenes like 243, in
which the nitrogens should be oriented towards the cavity with the phenyl rings pointing
outwards due to steric reasons (Scheme 4.4). This preoriented, the substituent is
predestined to act as a bis-chelating ligand with the pyridyl nitrogen as additional
coordination site.
92 Theoretical Part
Scheme 4.4. Envisaged Diels–Alder reaction of bistetrazinecalixarene 48 with
diphenylacetylene.
4.2 Syntheses of tetrazine model compounds
Construction of the asymmetric tetrazine moiety was first tested at the 2,6-dimethyl
anisole to find suitable reaction conditions. A method described by Tsefrikas et al.164
seemed promising and the initial synthesis was planned following the reported protocols
(Scheme 4.5).
N
O
NHNH2O
HN
NH
O N
O
Cl
NN
Cl N
ONN
HN NH
N
O
NN
N N
N
O
PCl5, CHCl3,ref lux, 20 h
NH2NH2·H2O,K2CO3, CH3CN,reflux, 25 h
NOx, CH2Cl2, rt
O
OCl
pyridine, 48 h, rt+
244 245 246
247 248(or 1,4-dihydrotetrazine)
249
Scheme 4.5. Initially planned route to asymmetric tetrazine 249.164
Syntheses of unsymmetrical tetrazines 93
The route starts with picolinohydrazide (244) and acyl chloride 245. Acetylation of
the hydrazine gives diacylhydrazide 246, which is then transformed to hydrazonoyl
chloride 247. Subsequent reaction with hydrazine hydrate yields the 1,2- or 1,4-
dihydrotetrazine 248, which is then oxidized with nitrous gases to the desired tetrazine
249.
First, precursors 245 and 244 had to be prepared. For the synthesis of acyl chloride
245, as outlined in Scheme 4.6, methods also described for calix[4]arenes were chosen.
Starting from 2-methoxy-1,3-dimethylbenzene (117) the aldehyde function was
introduced by a Duff–reaction. Aldehyde 250171a,172
was obtained in 85 % yield
employing modified literature procedures.171 Oxidation to the corresponding carboxylic
acid 251173 in excellent 97 % yield was achieved by treatment with sodium chlorite and
sulfamic acid174 upon which the product precipitated from the reaction mixture. The
acid 251 was converted into the acid chloride 245175 with thionyl chloride in
dichloromethane under reflux conditions in a very good 90 % yield.
Scheme 4.6. Synthesis of acid chloride 245.
The picolinohydrazide 244 was obtained as colorless solid with mp 99–101 °C (lit.: 176
100–102 °C) in an excellent 95 % yield by reaction of the ethyl picolinate (252) with
hydrazine hydrate (Scheme 4.7). The yield was even better than the 83 % reported in the
literature.176
Dicarbonylhydrazide 246 was prepared in a good 82 % yield according to a protocol
described by Wang et al.177 for 1,2-dibenzoylhydrazide (Scheme 4.8). The use of
Scheme 4.7. Preparation of picolinohydrazide 244.
94 Theoretical Part
Scheme 4.8. Synthesis of Dicarbonylhydrazide 246.
THF/water and sodium carbonate for 3 h is preferable over the use of pyridine and
longer reactions times as depicted in the original route. Upon addition of hydrazide 244
and sodium carbonate in THF/water to a solution of acid chloride 245 in THF, 246
precipitated from the solution. Extraction with dichloromethane and subsequent
recrystallization of the crude product from ethanol/methanol 4:1 was found to give
better results than collecting the product by filtration. The IR shows bands at 3230 cm-1
and 1643 cm-1 for the NH stretching vibrations and the carbonyl group, respectively.
The NH protons give two 1 H doublets at δ = 9.18 and 10.52 ppm.
Employing the method described by Tsefrikas et al., using PCl5, hydrazonoyl chloride
247 was synthesized.164,165 Initial experiments yielded about 40 % of a yellowish oil,
indicating impurity of the product as 247 was expected to be a solid. All attempts to
crystallize the compound failed. Finally, hydrazonoyl chloride 247 was isolated as a
yellow oil, which solidified upon standing, in 61 % yield.
Tsefrikas et al. also reported a low yield of the hydrazonoyl chloride (36 %) in this
step and observed the formation of the corresponding 1,3,4-oxadiazole in 30 % yield.
However, except for one experiment, when 253 and 247 were isolated in about 35 %
each, only traces of oxadiazole 253 could be detected in the NMR spectra when 246
was employed. Since except for that experiment dry chloroform had been used, the
presence of water might favour the formation of the oxadiazole.178
On the first look, oxadiazole 253 and hydrazonoyl chloride 247 can be hardly
distinguished by their respective 1H NMR spectra (Figure 4.2). However, elemental
Scheme 4.9. Synthesis of hydrazonoyl chloride 247 and oxadiazole 253.
Syntheses of unsymmetrical tetrazines 95
Figure 4.2. Partial 1H NMR spectra of hydrazonoyl chloride 247 (top) and oxadiazole 253
(bottom). Spectra recorded at 400 MHz in CDCl3.
analyses as well as mass spectra with a [M+H]+ peak at m/z = 336 in the FAB mass
spectrum of 247 and a molecular ion at m/z = 281 in the EI mass spectrum of 253
unambiguously identified the different compounds. Moreover, Rf values in PE/EtOAc
2:1 are 0.46 for 247 and 0.18 for 253, the latter appearing blue under UV light. For
hydrazonoyl chloride 247 the carbons bearing the chlorines appear at δ = 143.9 and
144.2 ppm in the 13C NMR spectrum. The corresponding carbons being part of the
oxadiazole ring in 253 show resonances at 163.8 and 165.8 ppm.
Prompted by the low yields of the initial experiments an alternative method was
sought. Taylor et al. reported the conversion of aroylhydrazones 254 into chloroazines
Scheme 4.10. Formation of benzylidenebenzohydrazonoyl chloride 255 as reported by
Taylor.179
96 Theoretical Part
255 utilizing thionyl chloride in toluene (Scheme 4.10).179 However, treatment of 246
with thionyl chloride in dry toluene yielded 88 % of oxadiazole 253 as the sole product.
Indeed, the reaction of hydrazonoyl chlorides with thionyl chloride is one method to
provide 1,3,4-oxadiazoles.178a
Oxadiazole 253 was also formed in about 20 % when reaction conditions, used by
Tsefrikas et al.164 for the conversion of the hydrazonoyl chloride to the dihydrotetrazine,
were applied to hydrozonyl chloride 247 (Scheme 4.11).
Changing the conditions and refluxing 247 with hydrazine hydrate in ethanol for 1 h,
as reported by Hu et al.180 and Sauer et al.,166 followed by oxidation of the crude product
using sodium nitrite in acetic acid161,180a,181 failed to produce the tetrazine. This result
indicates that the dihydrotetrazine was not formed. A mass spectrum obtained from the
crude product further supports this conclusion, showing a peak at m/z = 281, which
hints again at the formation of the oxadiazole 253. Using hydrazine dihydrochloride in
pyridine,182 dihydrotetrazine 248 was obtained in around 40 % after column
chromatography (Scheme 4.11).
Scheme 4.11. Synthesis of dihydrotetrazine 248 and subsequent oxidation to tetrazine 249.
However, fractions obtained by chromatography and identified as product already
exhibited a red colour. This indicates oxidation of 248 to tetrazine 249 in air, yielding a
mixture of both compounds (Figure 4.3). Because of this 248 was submitted to
oxidation without further attempts at purification and characterization.
Tetrazine 249 was finally obtained by oxidation of the dihydrotetrazine 248
employing aqueous sodium nitrite and acetic acid in up to 47 % yield as purple solid.
Syntheses of unsymmetrical tetrazines 97
Addition of diethylether was necessary since the product is formed as a purple solid
upon addition of sodium nitrite and the reaction mixture could not be stirred properly.
The FAB mass spectrum shows the base peak at m/z = 294 for [M+H]+. The tetrazine
carbons give peaks at δ = 163.3 and 164.4 ppm in the 13C NMR spectrum, respectively.
The UV/Vis spectrum shows the absorbance at 528 nm, characteristic for tetrazines.
Attempts to substitute the pyridine used in the synthesis of dihydrotetrazine 248 as
well as conversion of the crude product without complete purification failed. With
acetonitrile instead of pyridine unreacted starting material was recovered. Only trace
amounts of product could be detected by NMR, when small quantities of pyridine in
acetonitrile as the main solvent were employed. Likewise, using the crude product from
the reaction in pyridine directly in the next step after removal of the solvent gave only
traces of the product.
2.53.03.54.04.55.05.56.06.57.07.58.08.59.0ppm
Figure 4.3. 1H NMR spectrum of dihydrotetrazine 248 (bottom) showing traces of tetrazine 249
(top), recorded at 200 MHz in CDCl3.
Since only oxadiazole 253 was formed in the initial attempts to synthesize
dihydrotetrazine 248, the pyridyl substituent was replaced by a phenyl group to examine
if the same problems would occur (Scheme 4.12).
Benzohydrazide (257) was prepared in analogy to picolinohydrazide (244) in almost
quantitative yield as colorless solid with mp 112 °C (lit.176 111–113 °C). Reaction with
98 Theoretical Part
acid chloride 245 yielded 89 % of the dicarbonylhydrazide 258. The product
precipitated from the reaction mixture and was collected by filtration as it exhibited
very low solubility in contrast to the corresponding pyridyl-substituted compound 246a.
The [M+H]+ and [M+Na]+ peaks in the FAB mass spectrum at m/z = 299 and 321,
respectively, confirm formation of the product. The IR band at 3226 cm-1 is attributed to
NH stretching vibrations and the hydrogens attached to the nitrogens give a broad
singlet at δ = 10.38 ppm. Furthermore, the 13C NMR spectrum shows two different
carbonyl groups at 165.0 and 165.3 ppm.
O
HN
NH
O
O
Cl
NN
Cl
O
NN
HN NHO
NN
N NO
PCl5, CHCl3,ref lux, 20 h
258 (89 %)
260 (17 %)
261262 (51 %)
O
OMe
O
NHNH2
NH2NH2·H2O,ref lux, 18 h
257 (99 %)256
245, Na2CO3, THF,H2O, 3 h, 0 °C
O
259 (65 %)
O
NN
+
NH2NH2·H2O,EtOH, ref lux,30 min
SOCl2, toluene,ref lux, overnight
NaNO2 (10 %),CH3COOH, Et2O,0 °C, 15 min
Scheme 4.12. Synthesis of tetrazine 262.
When the carbonyl compound 258 was reacted with phosphorus pentachloride in
chloroform, a mixture of the desired hydrazonoyl chloride 259 and the oxadiazole 260
was obtained in 65 % and 17 % yield, respectively. However, a larger experiment gave
reverse yields with only about 18 % of the chloride, but 65 % oxadiazole. The reaction
could either be sensitive to scale-up or this again indicates sensitivity to water.
Syntheses of unsymmetrical tetrazines 99
Chloroform was dried over aluminium oxide, which might have been insufficient for the
larger reaction.
The compounds were identified by their respective [M+H]+ peaks at m/z = 335 for the
hydrazonoyl chloride 259 and 281 for the oxadiazole 260 in the FAB mass spectra. The 13C NMR spectrum of 259 showed peaks at δ = 144.1 and 144.3 ppm for the carbons
bearing chlorine, while the oxadiazole carbons give signals at δ = 164.5 and 164.7 ppm.
Additionally, in TLC the oxadiazole gave a spot which appeared blue under UV light,
which was also observed for the corresponding pyridyl compound 253.
By employing thionyl chloride in toluene again only oxadiazole 260 was formed in
about 70 % yield as shown by the 1H NMR spectrum. According to literature reports,
the oxadiazole can be converted to the dihydrotetrazine under the same conditions that
would be used for the hydrazonoyl chloride.183 However, only starting material was
recovered unreacted when 260 was refluxed with hydrazine hydrate in ethanol for
30 min,180 or heated to 40–50 °C for three hours in acetonitrile183 (Scheme 4.12).
Figure 4.4. 1H NMR spectra of Phenyldihydrotetrazine 261 (bottom) and the
pyridyldihydrotetrazine 248a (top), recorded at 200 MHz in CDCl3.
100 Theoretical Part
Upon treating 259 with hydrazine hydrate in ethanol the solution turned red,
indicating formation of dihydrotetrazine 261 and subsequent oxidation to tetrazine 262.
The precipitate was collected by filtration and washed to yield 52 % of almost colorless
material. The 1H NMR was not contaminated with the corresponding tetrazine and
shows strong similarities to the impure material obtained of the corresponding
pyridyldihydrotetrazine 248a (Figure 4.4). Furthermore, the UV/Vis spectrum shows
only one absorbance at 251 nm. The molecular ion appears in the FAB mass spectrum
at m/z = 294 as the base peak. The hydrogens attached to the nitrogen atoms give a
broad 2 H singlet at 7.12 ppm and the NH stretching vibrations cause a peak at
3268 cm-1 in the infrared spectrum.
When 261 was reacted with sodium nitrite in acetic acid and diethyl ether at 0 °C a
purple precipitate was formed immediately and 41 % of tetrazine 262 were isolated. The
[M+H]+ peak at m/z = 293 in the FAB mass spectrum as well as the characteristic
absorbance at 514 nm in the UV/Vis spectrum confirm the identity of 262. The 13C NMR spectrum shows the carbons of the tetrazine ring at δ = 163.8 and 163.9 ppm,
respectively.
4.3 Synthesis of tetrazine moieties at calix[4]arenes
The first steps of the synthesis have been described for calixarenes in literature. The
diformylcalix[4]arene 78 has been converted to the corresponding carboxylic acid85,184
263 (Scheme 4.13) in 90 % yield by Ungaro et al.184, using chloroform/acetone (1:1).
Various other formylcalixarenes have been transformed by similar procedures.60c,185,186
Since the calixarene would not be soluble in water or water/acetone, as used for the
model compound, the reactions are carried out in chloroform/acetone, usually in 1:1 or
1:3 ratios. The procedures generally employ more sodium chlorite and sulfamic acid as
well as longer reaction times and give yields about 80 % or higher.
However, when the protocol by Ungaro et al. was applied to the diformylcalix[4]arene
only about 30 % of dicarboxycalixarene 263 were obtained. The yield did not improve
on running the reaction for two days and consequently the reaction conditions were
modified. The same amounts or reagents used for the model compound, 1.2 equivalents
sodium chlorite and 1.7 equivalents sulfamic acid, were employed and the concentration
was increased to c = 0.06 mol/l from c = 0.03 mol/l in accord to Ungaro. Indeed, 263
was obtained in a considerably better 74 % yield (Scheme 4.13). It could not be
Syntheses of unsymmetrical tetrazines 101
determined why the literature procedure failed to give the expected yield. The outcome
of the reaction might be further improved by employing CHCl3/acetone in a 1:3 ratio or
increasing the amounts of reagents used.
Conversions of carboxycalixarenes to the corresponding acid chlorides have also been
described in the literature. Ungaro et al. reported the reaction of the tetracarboxy-
25,26,27,28-tetrapropoxycalix[4]arene with oxalyl chloride in dichloromethane184 or in
thionyl chloride/dichloromethane4c (1:1). The synthesis of the disubstituted 264 was
achieved by Jørgensen et al.187 in thionyl chloride in 62 % yield. Since thionyl chloride
is the less expensive reagent, a mixture of thionyl chloride/dichloromethane (1:3) was
employed to give about 73 % of the acid chloride 264, which was approximately 90 %
pure according to NMR and therefore used without further purification in the
subsequent transformation.
Scheme 4.13. Synthesis of dicarboxycalixarene 263 and subsequent conversion to acid chloride
264.
The phenylsubstituted tetrazine model compound exhibited low solubility and the
pyridyl unit offers an additional coordination site. Therefore, calixarene 264 was reacted
with the picolinohydrazide 244 under the same reaction conditions used for the model
compounds (Scheme 4.14). The 1H NMR spectrum obtained from the crude product
differs significantly from the starting materials. Especially the aromatic region (Figure
4.5) shows strong similarities to model compound 246, exhibiting a signal at about δ =
10.3 ppm assigned to NH, suggesting 265 has been formed.
102 Theoretical Part
OO OO
O OCl Cl
264
OO OO
O ONH HN
NH HN OO
N N
OO OO
Cl ClN N
N NClCl
N N
OO OO
HN NHN N
N NNHHN
N N
OO OO
N NN N
N NNN
N N
Na2CO3, THF,H2O, 3 h, 0 °C-rt
PCl5, CHCl3,ref lux, overnight
265
266
267 268
HOAc,NaNO2,Et2O, 0 °C
pyridine,NH2NH2·2 HCl,1.5 h, ref lux
Scheme 4.14. Envisaged synthesis of tetrazinecalixarene 268.
The 13C NMR spectrum gives clear evidence of two different phenol units and shows
20 of the expected 22 carbon peaks (Figure 4.6). The missing signals are those of the
methylene group next to the phenolic oxygen, which are superimposed by the
chloroform signal. Furthermore, carbonyl resonances at 165.1 and 162.0 ppm, similar to
those of the model compound, can be observed. The signals at 148 ppm are
characteristic of the pyridyl ring and a peak in the FAB mass spectrum at m/z = 941
[M+Na]+ gives further evidence for the successful coupling.
However, no eluent suitable for flash chromatography was found and crystallization
from DCM/MeOH failed. Therefore, the material was submitted to the next reaction
step, again using the reaction conditions tested with the model compounds. The NMR
Syntheses of unsymmetrical tetrazines 103
spectra give evidence for the formation of the hydrazonoyl chloride 266. The aromatic
region of the 1H NMR spectrum shows signals similar to those of the model
hydrazonoyl chloride 247 but also the oxadiazole 253 (Figure 4.8). The proton shifts
show closer resemblance to the hydrazonoyl chloride and the 13C NMR spectrum gives
further evidence of the formation of corresponding calixarene 265 (Figure 4.6). In fact,
the peaks at 144.4 and 144.9 ppm are consistent with the carbons
6.66.87.07.27.47.67.88.08.28.48.68.89.09.29.49.69.810.010.210.410.610.8ppm
Figure 4.5. Partial 1H NMR of model compound 246 (top) and the crude product obtained from
the reaction to 265 (bottom), recorded at 200 MHz in CHCl3.
Figure 4.6. 13C NMR spectrum of carbohydrazide calixarene 265, recorded at 50 MHz in
CDCl3.
104 Theoretical Part
Figure 4.7. 13C NMR spectrum of calixarene 266, recorded at 50 MHz in CDCl3.
Figure 4.8. Partial 1H NMR of the oxadiazole and hydrazonoyl chloride model compounds 253
(top) and 247 (middle) versus the crude product obtained from the reaction to 266
(bottom), recorded at 200 MHz in CHCl3.
substituted by chlorine as also observed for the model compound. There are no signals
higher at around 160 ppm, which would indicate the formation of the corresponding
oxadiazole. Two sets of signals appear for the propoxy groups in the 13C NMR
spectrum, confirming two different phenol units. Again, two signals are superimposed
by the chloroform signal. A peak at δ = 149.7 ppm is characteristic for the pyridyl ring.
Syntheses of unsymmetrical tetrazines 105
Purification of the brown residue by flash chromatography, however, proved to be
difficult as already observed for the starting material. Therefore, no material was
obtained in sufficient purity for unambiguous identification.
Material thus obtained was reacted with hydrazine dihydrochloride in pyridine in
analogy to the model compound. Flash column chromatography with PE/EtOAc 3:1 to
1:2 yielded little amounts of colorless solid in two fractions. However, NMR spectra of
the fractions gave no clear evidence of the formation of the desired dihydrotetrazine
267. A FAB mass spectrum obtained from one fraction shows a peak at m/z = 832,
which would be consistent with the loss of one pyridyl group, but no molecular ion is
detected. Comparison of the 1H NMR spectra of a second fraction and the pyridyl
tetrazine shows great similarities, but interestingly the material is colorless (Figure 4.9).
Upon oxidation with sodium nitrite in acetic acid an orange solid precipitated from the
reaction mixture, but the 1H NMR spectrum obtained from the crude product showed no
change. The same applies to the attempted oxidization of the other fraction.
Figure 4.9. Partial 1H NMR spectra of pyridyl model tetrazine (top) and a substance obtained by
flash chromatography of the dihydrotetrazinecalixarene crude product (bottom),
recorded in CDCl3 at 200 MHz.
4.4 Conclusion
The two model compounds 249 and 262 have been successfully prepared, albeit in
moderate yields. First attempts to apply the tested reaction conditions to the calixarene
indicate that the 1,2-diaroylhydrazine 265 as well as the hydrazonoyl chloride 266 are
indeed formed. However, purification and unambiguous identification have been
106 Theoretical Part
unsuccessful so far. When the crude calixarene mixture was further converted, no
evidence for the formation of the corresponding tetrazine could be observed.
The main problem in the synthetic route is the preparation of the hydrozonoyl
chloride, which is formed in varying yields along with 1,3,4-oxadiazole. Optimization
of this step, concerning the reproducibility and the yield of the reaction, is crucial for
the synthesis of unsymmetrical tetrazines, especially at a calixarene. Gautun et al.167 use
1,2-dichlorobenzene as solvent instead of chloroform, but the yields for the four
hydrazonoyl chlorides reported are mostly moderate between 28 and 75 %.
The only alternative reported in literature for the synthesis of hydrazonoyl chlorides,
is the chlorination of benzaldehyde azine 269 with chlorine in acetic acid or CCl4
(Scheme 4.15).188 However, Rosenberg et al.188b also detected 38 % of the
corresponding oxadiazole by GC, indicating that this method is unlikely to solve the
problem. Moreover, this method is unfavorable on a small scale and hardly any
unsymmetrical azines like 269 are known.
Scheme 4.15. Alternative for the synthesis of chloro(phenyl)methylene)benzo-hydrazonoyl
chloride 270: a) Cl2, HOAc, rt and b) Cl2, CCl4, K2CO3.
Scheme 4.16. Alternative approach to tetrazinecalixarenes by nucleophilic aromatic substitution
of dichlorotetrazine 272.
Syntheses of unsymmetrical tetrazines 107
Audebert et al. reported the functionalization of hydroxy groups with tetrazines in the
synthesis of supramolecular compounds.158b,159 Consequently, another approach to
tetrazinecalixarenes might be considered (Scheme 4.16). Starting from the p-
hydroxycalixarene 271, coupling with 3,6-dichloro-1,2,4,5-tetrazine would yield
calixarene 273, in which the tetrazine moieties are linked to the calixarene by an oxygen
atom. Tetrazines substituted by a heteroatom have fluorescent properties,159 which
might be an interesting aspect of calixarene 273. Moreover, the chlorine offers another
reaction site for further functionalization of the tetrazine by nucleophilic aromatic
substitution. Although the oxygen bridge adds flexibility to the tetrazine moeity, Diels–
Alder reaction of the tetrasubstituted analogue should lead to endo-orientation of the
nitrogens. In fact, being less rigid might be an advantage for the complexation of
differently sized guests.
Recently, bistriazoylcalixarene 274, bisisochinolinylcalixarene 275 and
bislutidinylcalixarene 276 depicted in Figure 4.10 were successfully synthesized in our
group.189 Considering the difficulties in synthesizing unsymmetrical tetrazines, these N-
heteroaryl substituted calixarenes might be a more promising route to calixarenes with
endo-oriented nitrogen coordination sites.
Figure 4.10. N-heteroaryl functionalized calixarenes.
However, the reaction conditions leading to these compounds have also to be
optimized. Moreover, tetrazine moieties could be functionalized in the 6-position. This
would offer the advantage of adding coordination sites, as already planned with the
pyridyl substituent, and further enhancement of the calixarene cavity.
109
5 Conclusion and Outlook
New members of the calix[4]phenanthrene family have been prepared by intramolecular
oxidative photocyclization of styrylcalixarenes (Figure 5.1). Introduction of an
additional methyl group was necessary to prevent the transannular [2+2] cycloaddition
of opposite styryl moieties in the synthesis of 86a by steric hindrance.
184a
OO OO
81a
OO OO
86a
OO OO
146a
OO OO
221a
OO OO
OO
Figure 5.1. Newly synthesized calix[4]phenanthrenes and examples of the new classes of
calix[4]fluorenones, calix[4]dihydrophenanthrenes and calix[4]triphenylenes.
Only one of the possible stereoisomers is depicted, respectively.
Furthermore, several other inherently chiral calixarenes containing anellated subunits
have been synthesized by palladium-catalyzed intramolecular direct arylation. Thereby,
the first examples of the new classes of calix[4]fluorenones (184a),
calix[4]dihydrophenanthrenes (146a) and calix[4]triphenylenes (221a) have been
isolated. This may also provide an alternative route to calixphenanthrenes, which should
be accessible either by oxidation of the calixdihydrophenanthrene 146a or
intramolecular cyclization of the corresponding Z-styrylcalixarene. The latter can be
obtained by reduction of the bromophenylacetylenecalixaren 141b with Lindlar catalyst.
The acetylene calixarene has already been prepared in the synthesis of the
calixdihydrophenanthrenes.
110 Theoretical Part
Scheme 5.1. Alternative routes to calix[4]phenanthrenes.
Further oxidation of calixphenanthrenes and subsequent reductive amination should
further enhance the calixarene cavity. Moreover, in the N-heterocyclic 279 the electron-
rich cavity has been converted into an electron-deficient one (Scheme 5.2).
Calix[4]fluorenones 184 already provide the carbonyl groups for further
functionalization by reductive amination.
Scheme 5.2. Oxidation of calixdiphenanthrene 64 and subsequent reductive amination.
Although double cyclization might be more problematic, calixdibenzotetracene 281
seems to be a realistic development from calix[4]triphenylenes (Scheme 5.3). The
molecule provides the advantage of being symmetric, whereby separation of
stereoisomers would not be a problem. Nevertheless, molecule 281 should set the limit
Conclusion and Outlook 111
to this reaction as multifold cyclizations leading to polyaromatic hydrocarbon
substructures at calixarenes seem unlikely.
Scheme 5.3. Envisioned double intramolecular cyclization to calixdibenzotetracene 281.
However, so far the yields of the Pd-catalyzed direct arylations are only low to
moderate and the reaction conditions employed require further optimization. Moreover,
the reaction yields a mixture of stereoisomers. The first cyclization obviously does not
influence the regioselectivity of the second, neither for the photo- nor the Pd-catalyzed
cyclizations. If the regioselective outcome cannot be influenced, the separation has to be
greatly improved. It seems unlikely that higher homologues of the anellated calixarenes
will be obtained due to steric crowding as well as the complex mixtures of steroisomers
that would be formed.
Figure 5.2. Unsymmetrical tetrazine model compounds synthesized and tetrazinecalixarene
precursors, which seem to have been formed but were not isolated pure.
112 Theoretical Part
A first step towards tetrazine-substituted calixarenes has been made with the
successful synthesis of two asymmetric model tetrazines 249 and 262 (Figure 5.2). The
moderate yields, however, are insufficient for the multifold functionalization at
calixarenes. First attempts to employ the reaction conditions tested in the synthesis of
tetrazinecalixarenes indicated that carbohydrazide 265 and the hydrazonoyl chloride
266 have indeed been formed. The purification of the complex mixtures obtained has so
far been unsuccessful.
Subsequent Diels–Alder reaction of the tetrazinecalixarenes with sterically demanding
acetylenes should provide the corresponding pyridazinecalixarenes like 282. These
would provide interesting ligands with endo-oriented coordination sites for the
complexation of transition metal salts or complexes. However, considering the
difficulties in the synthesis of asymmetric tetrazines, the easier accessible tetrazoles
might provide a better alternative for calixarenes with endo-coordination sites.
Figure 5.3. Pyridazinecalixarene 282 and triazolecalixarene 274.
113
II. Experimental Part
1 Methods and Materials
1.1 Reaction control and separation methods
Thin-layer chromatography:
Reactions were monitored by thin-layer chromatography (TLC) using commercial TLC
plates “Polygram SIL G/UV254” with fluorescence indicator from Macherey-Nagel &
Co. Substances were detected by absorption of UV light (254 nm and 366 nm). Spots
were coloured with basic KMnO4 solution or ethanolic vanillin solution and subsequent
heating in a hot-air stream in the case of weakly absorbing substances.
Flash chromatography:
Separation and purification of products was achieved by flash chromatography using
glass columns with silica gel 60 (0.040–0.063 mm by Fluorochem Ltd. or Geduran® by
Merck), as stationary phase and applying overpressure. For the separation an eluent with
a Rf value of about 0.2–0.5 for the desired compound was chosen. Eluent mixtures were
prepared by volumetric measurement. Column length and diameter were adjusted
depending on the respective separation.
HPLC:
HPLC was performed using a unit consisting of a Knauer HPLC pump 64, a Knauer
differential refractometer and a mechanical recorder. Separations were carried out with
a LiChrospher Si 60 (5 µ) column from Merck of 20 cm length and 2 cm diameter.
Injections of about 200 µl were carried out over a six-port injection valve.
Distillation and sublimation:
Distillations and sublimations, respectively, were either carried out under reduced
pressure using short-path stills or by bulb-to-bulb distillation with a ball tube oven by
Büchi.
114 Experimental Part
1.2 Analytical chemistry: apparatus, instruments, acquisition
methods and comments on analytical data
Melting-point determination:
Melting points (°C) were determined with a Kofler instrument, model Reichert
Thermovar, or a melting-point apparatus by Dr. Tottoli from Büchi and are uncorrected.
Elemental analysis:
Elemental analyses were determined with a Vario EL by the analytical department of
the faculty for chemistry and biochemistry. Substance samples may deviate
∆C,H,N = ± 0.4 % from the calculated formula.
Infrared spectroscopy:
Infrared spectroscopy was performed with a Bruker Equinox 55 FT-IR. Solid
substances are scanned as KBr pellets. The position of absorption bands (ν~ ) is given in
cm-1. The following abbreviations are used for the characterization of absorption bands:
vs = very strong, s = strong, m = medium, w = weak, br = broad.
UV-VIS spectroscopy:
UV/Vis spectra were recorded on a Varian Cary 1. Absorption bands (λmax) are given in
nm, the corresponding absorption coefficient (ε) in cm² mmol-1. The following
abbreviations are used for the characterization of absorption bands: sh = shoulder,
br = broad
1H NMR spectroscopy:
1H NMR spectra were recorded with a Bruker DPX 200 (200.1 MHz), a Bruker DPX
250 (250.1 MHz), a Bruker DPX 400 (400.1 MHz) or a Bruker DRX 600 (600.1 MHz).
The chemical shifts (δ) are given in ppm, the coupling constant (J) in Hertz (Hz). The
spectra were calibrated on the internal solvent peak δ(CHCl3) = 7.26 ppm, δ(CH2Cl2) =
5.32 ppm or δ(DMSO-d6) = 2.50 ppm.190 Spectra were recorded at 303 K if not stated
otherwise. Spectra were processed and analyzed with MestReNova (6.0.4 and preceding
versions). The following abbreviations are used describing the style of signals: s =
singlet, d = doublet, t = triplet, q = quartet, m = multiplet, double letters like i.e. dd
stand for doublet of doublets etc., broad signals are marked with br as prefix. Multiplets
Methods and Materials 115
with a strong basic signal structure are marked with the appropriate letter in quotation
marks. Signal assignments to the structural fragment given are marked in italics
Residual solvent signals in the NMR spectra depicted are marked with an asterisk.
13
C NMR spectroscopy:
13C NMR spectra were recorded with a Bruker DPX 200 (50.1 MHz), a Bruker DPX
250 (250.1 MHz), a Bruker DPX 400 (100.1 MHz) or a Bruker DRX 600 (150.1 MHz).
All 13C NMR spectra are proton decoupled. Signal multiplicities are determined by
HMQC and HMBC experiments and are assigned the same abbreviations as for 1H NMR spectra. The chemical shifts (δ) are given in ppm. The spectra were calibrated
on the internal solvent peak δ(CHCl3) = 77.16 ppm, δ(CH2Cl2) = 54.00 ppm or
δ(DMSO-d6) = 39.52 ppm.190 Spectra were recorded at 303 K if not stated otherwise.
Spectra were processed and analyzed with MestReNova (6.0.4 and preceding version).
Signal assignments to the structural fragment given are marked in italics Residual
solvent signals in the NMR spectra depicted are marked with an asterisk.
31
P NMR spectroscopy:
31P NMR spectra were recorded with a Bruker DPX 250 (250.1 MHz) and are
decoupled and uncalibrated. The chemical shifts (δ) are given in ppm. Spectra were
processed and analyzed with MestReNova (6.0.4 and preceding versions).
Mass spectrometry:
Mass spectroscopy was performed with a Varian MAT CH5, a VG Autospec or a Jeol
AccuTOF GCv. The m/z ratios are given as dimensionless numbers. The abundance of
the peaks is given relative to the base peak (100 % abundance). For EI experiments
(electron-impact ionization) with 70 eV only peaks with an intensity of at least 5 % or
particularly characteristic fragments are listed. The spectra were recorded in mNBA (m-
nitrobenzyl alcohol) or lactic acid as matrix. High-resolution mass spectrometry
(HRMS) was performed as EI measurement at the Jeol Accu TOF GCv. Substance
samples may deviate less than 10 ppm from the calculated formula.
116 Experimental Part
X-ray structure analysis:
The intensity data were collected on an Oxford Diffraction Xcalibur2 diffractometer
with a Sapphire2 CCD. The crystal structures were solved by direct methods using
SHELXS-97191 and refined with SHELXL-97191. For refinement details see appendix or
cif-files. CCDC-787366 (for 60), CCDC-787367 (for 81a), and CCDC-787368 (for
86a). These data are also available from The Cambridge Crystallographic Data Centre
via www.ccdc.cam.ac.uk/data_request/cif.
1.3 Solvents and reagents
Solvents were dried according to common methods.192 Anhydrous solvents were stored
under argon in flasks with T-type connectors over molecular sieve and kept oxygen- and
moisture-free. Small amounts were dried by filtration over aluminium oxide 90 active
basic (0.003-0.200 nm), activity stage I from Merck. Solvents for extraction and column
chromatography are technical grade and distilled over Vigreux columns at standard
pressure prior to use. All commercially available chemicals were used without further
purification.
2,2,2-Trifluoroethanol: Riedel de Häen.
2-Butanone: Purchased from Riedel de Häen.
Acetone: Purchased from J. T. Baker.
Acetonitrile (for UV/Vis): spectrophotometric grade 99+%, Acros Organics.
Acetonitrile: Purchased from J. T. Baker.
Acetonitrile (dry): Refluxed over phosporus pentoxide for 3–4 h, distilled and stored
over molecular sieves 3 Å.
Benzene: Purchased from Normapur or J. T. Baker.
Chloroform: Purchased from Normapur or J. T. Baker.
Deuterochloroform-d1: 99.8 % D, Deutero GmbH.
Dichloromethane: technical grade, distilled.
Dichloromethane-d2: 99.6 % D, Deutero GmbH.
Dichloromethane (dry): Refluxed over calcium hydride, distilled and stored over
molecular sieves 4 Å under argon.
Diethylether: anhydrous, purchased from J. T. Baker.
Dimethyl sulphoxide-d6: 99.9 % D, Deutero GmbH.
Methods and Materials 117
Dimethylformamide: DMF, purchased from J. T. Baker, dried twice over molecular
sieve 3 Å for 24 h each.
Ethanol: technical grade, distilled.
Ethanol: anhydrous, purchased from Aldrich or Baker.
Ethyl acetate: technical grade, distilled.
i-Propanol: technical grade, distilled.
Methanol: technical grade, distilled.
Methyl-tert-butyl ether: technical grade, distilled.
N,N-Dimethylacetamide: 99+%, extra pure, purchased from Acros.
n-Hexane (for UV/Vis): 95+%, spectrophotometric grade purchesed from Sigma-
Aldrich.
n-Hexane: technical grade, distilled.
Nitromethane: Purchased from Merck, dried over CaCl2, distilled and stored over
molecular sieve 3 Å under argon.
Pentane: technical grade, distilled.
Petroleum ether 40/60: technical grade, distilled.
Pivalic acid: Purchased from Fluka.
Tetrahydrofurane (dry): Refluxed over sodium or a sodium dispersion in
paraffin/benzophenone until blue, distilled and used directly.
Toluene: technical grade, distilled.
Toluene (dry): Refluxed over sodium or a sodium dispersion in paraffin/benzophenone
until blue, distilled and stored over molecular sieves 3 Å under argon.
Triethylamine (dry): Purchased from J.T.Baker and dried over CaH2, distilled and
stored over molecular sieves 4 Å under argon.
Trifluoroacetic acid: 99 %, extra pure, purchased from Acros.
Reagents were used and stored as follows:
1-Bromopropane: Purchased from Riedel de Haën or 99 % from Acros and stored in a
refrigerator.
1-Iodpropane: Purchased from Fluka, ≥ 98 % (GC).
2-Biphenylboronsäure (190): Purchased from Aldrich.
2-Bromobenzaldehyde: 97 % from Acros.
118 Experimental Part
2-Bromobenzoic acid: 97 % from Aldrich.
2-Bromobenzonitrile: 99 % Acros.
2-Bromobenzoyl chloride: 98 % Acros.
2-Bromophenylacetic acid: Purchased from Fluka oder 98 % from Acros.
2-Chlorobenzaldehyde: purum, ≥ 98% (GC) from Fluka.
2-Chlorobenzoic acid: Merck or 98 % from Aldrich.
2-Chlorobenzonitrile: 98 % from Aldrich.
2-Iodobenzoic acid: Laboratory chemical.
2-Methyl-3-butyn-2-ol: 98 % from Aldrich.
Aluminium chloride: 98 %, anhydrous, sublimated, purchased from Merck or 99 %,
extra pure, anhydrous from Acros.
Benzoyl chloride: Purchased from Merck.
Benzyl bromide: Purchased from Riedel de Haën.
Benzyltrimethylammonium chloride: 98+% from Acros.
Benzyltriphenylphosphonium chloride: Purchased from Janssen Chimica.
Bromine: Riedel de Häen or Merck.
Chlorotrimethylsilane: Laboratory chemical.
Copper(I) iodide: Purchased from Acros, 98 %.
Ceasium carbonate: 99 % from Aldrich.
Ethyl 2-picolinate: 99 % from Aldrich and ABCR.
Ethylene glycol: Laboratory chemical.
Hexamethylenetetramine (HMTA): Purchased from Riedel de Haën.
Hydrazine hydrate: 100 % (64 % hydrazine) from Acros.
Hydroxylamine hydrochloride: Merck.
Potassium carbonate: J.T.Baker or 98-100% from Riedel de Häen. Was dried in
vacuum prior to use at 250 °C.
Potassium hydroxide: J.T.Baker.
Methyl benzoate: Riedel de Häen.
N,O-Dimethylhydroxylamine hydrochloride: 98 % EGA-Chemie.
Sodium carbonate: anhydrous from Riedel de Häen or J.T.Baker.
Sodium borohydride: 98 % from Aldrich.
Sodium hydride: 60 % dispersion in mineral oil. Purchased from Fluka and Acros,
stored in a desiccator over silica gel and washed with pentane or hexane under argon
prior to use to remove the mineral oil.
Methods and Materials 119
N-Bromosuccinimide (NBS): 99 %, purchased from Acros and ABCR and stored in a
refrigerator.
Oxalyl chloride: Riedel de Häen or 98 % from Acros.
Phosphorus pentachloride: Purchased from Merck.
Palladium(II) acetate: Purchased from Merck 47 % Pd.
Pd(PPh3)2Cl2: 98 % from Acros.
Tetrakis(triphenylphosphine)palladium(0): 99% purchased from Aldrich.
Bis(triphenylphosphine)palladium(II) chloride: Janssen Chimica (59 % Pd) or 98 %
from Aldrich and Acros.
Phthalic anhydride: Purchased from Acros.
PIFA ([Bis(trifluoroacetoxy)iodo]benzene): 98 % from Acros.
p-Toluenesulfonyl hydrazide: From Merck.
Sodium chlorite (NaClO2): Purchased from Acros and Aldrich, 80 %, technical grade.
Sodium peroxodisulfate (Na2S2O8): 98 % from Acros.
Sulfamic acid: Purchased from Acros.
Tetramethylammonium iodide: 99 % from Acros.
Tricyclohexylphosphonium tetrafluoroborate: 99 %, purchased from Acros.
Trimethyl borate: 99 % from AcroSeal®.
Trimethylsilylacetylene: 98 % from Aldrich.
Triphenylphosphine: Riedel de Häen.
Thionyl chloride: 95.5 % from Acros or > 99 % from Merck.
Iodine: Baker Grade 99.5-110.5 % from J.T.Baker or 99.9 % from Aldrich.
1,8-Diazabicyclo[5.4.0]undec-7-ene (DBU): 98 % from Aldrich.
1,2-Dibromobenzene: 99 % from Acros.
2,6-Dimethylanisole: 98 % from Avocado or purchased from ABCR.
n-Butyllithium: 15 % in hexane from Merck or 1.6 M in hexane from AcroSeal® and
stored in a refrigerator.
t-Butyllithium: 15 % in pentane from Merck or 1.6 M in pentane from AcroSeal® and
stored in a refrigerator.
4-Bromo-2,6-dimethylphenol (208): 99 % from Acros.
121
2 Syntheses
2.1 Syntheses of reagents and model compounds
2.1.1 Triphenyl(1-phenylethyl)phosphonium bromide (84)
(1-Bromoethyl)benzene (83) (2.71 g, 14.6 mmol) and triphenylphosphine (283) (4.00 g,
15.3 mmol) were dissolved in toluene (15 mL) and stirred at 110–120 °C for 3 d in a
srew-cap flask. The colorless precipitate was filtered off, washed with toluene and dried
in vacuo (0.76–2.5 mbar, 100 °C, 3 h) to give 5.77 g (88 %) of 84 as a solid with mp
229–231 °C (lit.193 mp 231–234 °C).
1H NMR (200 MHz, CDCl3): δ = 1.82 (dd, J = 19.1 Hz, J = 7.2 Hz, 3 H, CH3), 6.82
(dq, J = 14.2 Hz, J = 7.3 Hz, J = 7.1 Hz, 1 H, CH), 7.10–7.26 (m, 5 H, ArH), 7.58–7.88
(m, 15 H, ArH) ppm.
31
P{1H} NMR (101 MHz, CDCl3): δ = 27.30 ppm.
MS (FAB): m/z (%) = 367 (100) M+.
NMR spectroscopic data are in accord with the literature.89,90
122 Experimental Part
1H NMR (200 MHz, CDCl3): Triphenyl(1-phenylethyl)phosphonium bromide (84)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0
f1 (ppm)
3.03
1.00
4.83
14.66
1.82
6.82
7.10
7.25
7.58
7.88
Syntheses 123
2.1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone (118)
2,6-Dimethyl anisole (117) (1.22 mL, 8.45 mmol), aluminium chloride (686 mg, 5.09
mmol) and 2-bromophenylacetyl chloride (116) (1.00 g, 4.28 mmol) were suspended in
dry dichloromethane (10 mL) and refluxed for 1 h 15 min. After addition of HCl (2 N,
15 mL), the layers were separated and the aqueous layer was extracted twice with
dichloromethane (20 mL). The combined organic extracts were washed with NaOH
(10 %, 20 mL), water (20 mL), dried over MgSO4 and the solvent was removed at a
rotary evaporator. Excess dimethylanisole was removed in vacuo (0.78 mbar, 50 °C).
The resulting yellow solid was washed with methanol and dried in vacuo (0.89 mbar,
50 °C, 30 min) to yield 1.35 g (94 %) of 118 as a colorless solid with mp 101 °C.
C17H17BrO2 (333.22)
calcd.: C 61.28, H 5.14
found: C 61.52, H 5.24
IR (KBr): ν~ = 3058 (w), 2948 (w), 2915 (w), 2857 (w), 2828 (w), 1684 (s, C=O), 1595
(m), 1567 (w), 1471 (m), 1439 (w), 1408 (m), 1377 (w), 1332 (s), 1293 (m), 1272 (w),
1225 (w), 1178 (w), 1147 (s), 1059 (w), 1045 (w), 1025 (m), 1009 (m), 946 (w), 892
(w), 868 (w), 837 (w), 779 (w), 760 (w), 744 (s) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 260 (4.0) nm.
1H NMR (400 MHz, CDCl3): δ = 2.34 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 4.40 (s, 2 H,
C(O)CH2), 7.14 ( “t”, “J” = 7.6 Hz , 1 H, ArH), 7.23–7.30 (m, 2 H, ArH), 7.59 (d, J =
8.0 Hz, 1 H BrArH), 7.73 (s, 2 H, m-ArH) ppm.
124 Experimental Part
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.43 (q, CH3), 45.78 (t, C(O)CH2), 59.81 (q,
OCH3), 125.26 (s, Ar’CBr), 127.63 (d, Ar’CH), 128.77 (d, Ar’CH), 129.57 (d, m-
ArCH), 131.44 (s, ArCCH3), 131.80 (d, Ar’CH), 132.49 (s, ArCC=O), 132.92 (d,
Ar’CH), 135.42 (s, Ar’CCH2)), 161.61 (s, ArCO), 195.80 (s, C=O) ppm.
MS (FAB): m/z (%) = 333 (55) [M+H]+, 169 (16), 163 (100) [M–C7H6Br]+.
Syntheses 125
1H NMR (400 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanone (118)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
2.96
2.90
2.00
0.91
2.10
0.85
1.88
2.34
3.77
4.40
7.14
7.23
7.30
7.59
7.73
13C NMR (100 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanone (118)
0102030405060708090100110120130140150160170180190200f1 (ppm)
16.4
45.8
59.8
125.3
127.6
128.8
129.6
131.4
131.8
132.5
132.9
135.4
161.6
195.8
127128129130131132133f1 (ppm)
127.6
128.8
129.6
130.4
131.4
131.8
132.5
132.9
126 Experimental Part
2.1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124)
Under argon ketone (118) (650 mg, 1.95 mmol) was dissolved in 15 mL dry
tetrahydrofuran and NaBH4 (170 mg, 98 %, 4.40 mmol) was added. The mixture was
refluxed for 24 hours. After cooling down to room temperature water (20 mL) followed
by HCl (2 N, 20 mL) were added. The mixture was extracted with diethyl ether
(2 x 25 mL). The organic layers were dried over MgSO4 and the solvent was removed
by rotary evaporation. After purification by flash chromatography (silica gel, PE/EtOAc
10:1, Rf (PE/EtOAc 10:1) = 0.14) and subsequent drying in vacuo (1.6 mbar, 75 °C,
45 min) 570 mg (87 %) of 2-(2-bromophenyl)-1-(3,5-dimethyl-4-methoxyphenyl)-
ethanol (124) were obtained as a white solid with a melting point of 104 °C.
C16H19BrO2 (335.24)
calcd.: C 60.91, H 5.71
found: C 60.94, H 5.67
IR (KBr): ν~ = 3446 (vs, OH), 3056 (w), 2998 (w), 2972 (w), 2947 (w), 2919 (m), 2880
(w), 2835 (w), 1597 (w), 1556 (w), 1475 (m),1436 (m), 1393 (w), 1341 (w), 1314 (w),
1276 (w), 1214 (m), 1172 (w), 1135 (m), 1114 (w), 1068 (m), 1023 (m), 1000 (m), 939
(w), 878 (w), 856 (w), 833 (w), 769 (w), 744 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 265 (3.1) nm.
1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.05 (dd, J = 13.7 Hz, J = 9.2 Hz,
1 H, CH2), 3.19 (dd, J = 13.7 Hz, J = 4.0 Hz, 1 H, CH2), 3.72 (s, 3 H, OCH3), 4.92 (dd,
Syntheses 127
J = 9,2 Hz, J = 4.0 Hz, 1 H, CH), 7.06 (s, 2 H, m-ArH), 7.09–7.14 (m, 1 H, ArH’), 7.24
(d, J = 4.1 Hz, 2 H, ArH’), 7.58 (d, J = 7.9 Hz, 1 H, Ar-3’-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 46.3 (t, CH2), 59.8 (q, OCH3),
73.3 (d, CH(OH)), 125.0 (s, Ar’CBr), 126.3 (d, m-ArCH), 127.5 (d, Ar’CH), 128.4 (d,
Ar’CH), 131.0 (s, ArC), 132.2 (d, Ar’CH), 133.1 (d, Ar’CH), 138.1 (s, ArC), 139.3 (s,
Ar’C), 156.6 (s, ArCO) ppm.
MS (FAB): m/z (%): 335 (6) [M+H]+, 319 (49) [M–CH3]+, 165 (100) [M–C6H7Br]+, 154
(16), 137 (12).
128 Experimental Part
1H NMR (400 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanol (124)
13C NMR (100 MHz, CDCl3): 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethanol (124)
Syntheses 129
2.1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethyl-
silane (125)
A solution of 2-(2-bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol (124)
(343 mg, 1.02 mmol), chlorotrimethylsilane (274 mg, 2.53 mmol) and imidazole
(351 mg, 5.15 mmol) in anhydrous DMF (25 mL) was stirred under argon at 40 °C for
18 h. The mixture was hydrolyzed with water (25 mL), extracted with CH2Cl2 (3 x
20 mL) and dried over sodium sulfate. The solvent was removed under reduced pressure
and the crude product purified by flash chromatography (silica gel, PE/EtOAc 10:1;
Rf = 0.56) and dried in vacuo (2.6–5.1 mbar, 50–75 °C). The product 125 (309 mg,
74 %) was obtained as slightly yellow oil.
HRMS (EI, 70 eV): C20H27BrO2Si (407.42)
calcd.: 406.0964 g/mol
found: 406.0898 g/mol
1H NMR (400 MHz, CDCl3): δ = -0.19 (s, 9H, SiCH3), 2.28 (s, 6H, CH3), 2.89 (dd, J =
9.4 Hz, J = 13.3 Hz, 1H, CH2), 3.12 (dd, J =3.6 Hz, J = 13.3 Hz, 1H, CH2), 3.72 (s, 3H,
OCH3), 4.86 (dd, J = 3.6 Hz, J = 9.3 Hz, 1H, CH), 7.01 (s, 2H, m-ArCH), 7.05–7.09 (m,
ArCH), 7.15–7.21 (m, ArCH), 7.55 (dd, J = 0.9 Hz, J = 7.9 Hz, 1H, ArCBrH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = –0.24 (q, SiCH3),16.3 (q, CH3), 47.8 (t, CH2),
59.8 (q, OCH3), 73.4 (d, CH), 124.9 (s, Ar’CBr), 126.0 (d, m-ArCH), 127.0 (d, Ar’CH),
128.1 (d, Ar’CH), 130.4 (s, CCH3), 132.6 (d, Ar’CH), 133.2 (d, Ar’CH), 138.8 (s,
Ar’C), 140.3 (s, p-ArC), 156.1 (s, ArCO) ppm.
130 Experimental Part
MS (EI, 70 eV): m/z (%): 407 M+, 393, 378, 317 (3) [M–OTMS]+, 237 (100)
[M–C7H6Br]+, 73 (32).
Syntheses 131
1H NMR (400 MHz, CDCl3): (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethoxy)trimethylsilane (125)
13C NMR (100 MHz, CDCl3): (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)-ethoxy)trimethylsilane (125)
132 Experimental Part
2.1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethyl-
phenyl)methanone) (120a) and Phenanthrene-9,10-diylbis((4-methoxy-3,5-
dimethylphenyl)methanone) (120b)
Ketone 118 (334 mg, 1.00 mmol), potassium carbonate (276 mg, 2.00 mmol) and
tricyclohexylphosphonium tetrafluoroborate (42 mg, 113 µmol) were suspended in
DMA (5 mL) in a screw-cap flask. The suspension was degassed with argon for 10 min
before Pd(OAc)2 (11 mg, 49 µmol) was added. The mixture was heated to 145 °C for
24 h, cooled to room temperature and extracted with CH2Cl2 (3 x 20 mL). The organic
layer was washed with HCl (2 N, 20 mL), water (20 mL), brine (20 mL) and dried over
MgSO4. The solvents were removed under reduced pressure and the residue purified by
flash chromatography (silica gel, PE/EtOAc 15:1 to 10:1) to yield after subsequent
drying in vacuo (1.7 mbar, 75 °C, 45 min):
1st fraction (Rf (PE/EtOAc 5:1) = 0.26): 47 mg (19 %) of dihydrophenanthrene 120a
after recrystallization from DCM/MeOH as colorless crystalline solid with
mp 222–224 °C.
C34H32O4 (504.62)
calcd.: C 80.93, H 6.39
found: C 80.61, H 6.15
IR (KBr): ν~ = 3063 (w), 2990 (w), 2949 (w), 2927 (w), 2864 (w), 2828 (w), 1674 (vs),
1592 (s), 1483 (s), 1445 (m), 1411 (w), 1339 (s), 1293 (s), 1231 (m), 1206 (m), 1886
(w), 1144 (vs), 1056 (w), 1008 (s), 952 (w), 828 (w), 905 (w), 874 (w), 856 (w), 793
(w), 773 (w), 753 (s), 731 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 267 (4.7) nm.
Syntheses 133
1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 12 H, CH3), 3.77 (s, 6 H, OCH3), 5.47 (s, 2 H,
CH), 6.95 (d, J = 7.5 Hz, 2 H, PhenH), 7.17 (td, J = 7.6 Hz, J = 1.1 Hz, 2 H, PhenH),
7.37 (td, J = 7.7 Hz, J = 1.0 Hz, 2 H, PhenH), 7.77 (s, 4 H, ArH), 7.83 (dd, J = 7.8 Hz, J
= 1.0 Hz, 2 H, PhenH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 48.9 (d, CH), 59.8 (q, OCH3),
124.5 (d, PhenCH), 127.0 (d, PhenCH), 127.9 (d, PhenCH), 128.2 (d, PhenCH), 130.0
(d, ArCH), 131.7 (s, CCH3), 133.8 (s, ArC), 134.4 (s, PhenC), 136.4 (s, PhenC), 162.0
(s, ArCO), 201.7 (s, C=O) ppm.
MS (FAB): m/z (%):505 (20) [M+H]+, 163 (79).
134 Experimental Part
1H NMR (400 MHz, CDCl3): (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethylphenyl)methanone) (120a)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
12.42
6.07
2.00
1.94
1.96
1.96
3.90
2.22
2.30
3.77
5.47
6.95
7.17
7.37
7.77
7.83
7.07.27.47.67.8f1 (ppm)
1.94
1.96
1.96
3.90
2.22
6.95
7.17
7.37
7.77
7.83
13C NMR (100 MHz, CDCl3): (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-dimethylphenyl)methanone) (120a)
0102030405060708090100110120130140150160170180190200f1 (ppm)
16.4
48.8
59.8
124.5
127.0
127.9
128.2
130.0
131.7
133.8
134.4
136.4
162.0
201.7
Syntheses 135
2nd fraction (Rf (PE/EtOAc 5:1) = 0.19): 96 mg (38 %) of phenanthrene 120b as a
colorless solid of which some was recrystallized from DCM/MeOH to yield colorless
crystals with mp 242–243 °C.
C34H30O4 (502.60)
calcd.: C 81.25 , H 6.02
found: C 81.14, H 6.34
IR (KBr): ν~ = 3060 (w), 3037 (w), 2946 (w), 2925 (w), 2861 (w), 2829 (w), 1664 (vs),
1592 (s), 1480 (m), 1446 (s), 1413 (m), 1374 (m), 1323 (vs), 1297 (s), 1222 (s), 1185
(s), 1172 (s), 1147 (vs), 1111 (w), 1092 (w), 1070 (w), 1042 (w), 1006 (s), 951 (w), 906
(w), 886 (w), 864 (w), 814 (w), 787 (w), 761 (s), 724 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 244 (4.9), 252 (4.9) nm.
1H NMR (400 MHz, CDCl3): δ = 2.18 (s, 12 H, CH3), 3.72 (s, 6 H, OCH3), 7.44 (s, 4 H,
ArH), 7.53 (“t”, “J” = 7.6 Hz, 2 H, Phen-H), 7.69 (d, J = 8.3 Hz, 2 H, Phen-H), 7.73
(„t“, „J“ = 7.6 Hz, 2 H, Phen-H), 8.81 (d, J = 8.4 Hz, 2 H, Phen-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59.7 (q, OCH3), 123.1 (d,
PhenCH), 127.5 (d, PhenCH), 127.9 (d, PhenCH), 128.9 (s, PhenC), 130.6 (s, PhenC),
131.3 (s, CCH3), 131.4 (d, ArH), 133.6 (s, ArC), 135.5 (s, PhenC), 162.0 (s, ArCO),
197.6 (s, C=O) ppm.
MS (FAB): m/z (%): 525 (15) [M+Na]+, 503 (76) [M+H]+, 367 (39), 163 (100) [M–phenanthrene]+.
136 Experimental Part
1H NMR (400 MHz, CDCl3): Phenanthrene-9,10-diylbis((4-methoxy-3,5-dimethyl-phenyl)methanone) (120b)
11.90
6.00
3.60
2.05
2.01
2.13
1.96
2.18
3.72
7.44
7.53
7.69
7.73
8.81
2.05
2.01
2.13
7.53
7.69
7.73
13C NMR (100 MHz, CDCl3): Phenanthrene-9,10-diylbis((4-methoxy-3,5-dimethyl-phenyl)methanone) (120b)
0102030405060708090100110120130140150160170180190200f1 (ppm)
16.3
59.7
123.1
127.5
127.9
128.8
130.6
131.3
131.4
133.6
135.5
162.0
197.6
Syntheses 137
2.1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and
1-(4-hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)
(2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)trimethylsilane (125)
(257 mg, 631 µmol), potassium carbonate (177 mg, 1.28 mmol) and tricyclohexyl-
phosphonium tetrafluoroborate (25 mg, 67 µmol) were suspended in DMA (3 mL) in a
screw-cap flask. The suspension was degassed with argon for 5 min before Pd(OAc)2
(7 mg, 31 µmol) was added. The mixture was heated to 170 °C for 3 d, cooled to room
temperature, hydrolyzed with water (10 mL) and extracted with DCM (3 x 10 mL). The
organic layer was washed with HCl (2 N, 10 mL), water (10 mL), brine (10 mL) and
dried over MgSO4. The solvents were removed under reduced pressure and the residue
purified by flash chromatography (silica gel, PE/EtOAc 20:1 to 5:1) to yield:
1st fraction (Rf (PE/EA 15:1) = 0.28): 90 mg (56 %) of 127 after drying in vacuo (0.65
mbar, 75 °C, 20 min) as colorless solid with mp 85-87 °C (lit.: 85°C)
1H NMR (400 MHz, CDCl3): δ = 2.32 (s, 6 H, CH3), 3.75 (s, 3 H, OCH3), 4.23 (s, 2 H,
CH2), 7.22–7.27 (m, 3 H, Ar’H), 7.30–7.34 (m, 2 H, Ar’H), 7.69 (s, 2 H, m-ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 45.4 (t, CH2), 59.8 (q, OCH3),
126.9 (d, p-Ar’CH), 128.8 (d, o-Ar’CH), 129.6 (d, m-Ar’CH), 129.9 (d, m-ArCH),
131.4 (s, CCH3), 132.5 (s, p-ArC), 135.1 (s, Ar’C), 161.5 (s, ArCO), 197.2 (s, C=O)
ppm.
MS (FAB): m/z (%) = 255 (98) [M+H]+, 163 (100), 91 (32).
138 Experimental Part
1H NMR (400 MHz, CDCl3): 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127)
13C NMR (100 MHz, CDCl3): 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127)
Syntheses 139
2nd fraction (Rf (PE/EA 15:1) = 0.07): 42 mg (28 %) of 128 after drying in vacuo
(0.61 mbar, 75 °C, 20 min) as colorless solid with mp 116 °C.
1H NMR (400 MHz, CDCl3): δ = 2.28 (s, 6 H, CH3), 4.21 (s, 2 H, CH2), 5.16 (s, 1 H,
OH), 7.21-7.33 (m, 5 H, Ar’H), 7.69 (s, 2 H, m-ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.0 (q, CH3), 45.3 (t, CH2), 123.1 (s, CCH3),
126.8 (d, p-Ar’CH), 128.7 (d, Ar’CH), 129.4 (s, ArC), 129.5 (d, Ar’CH), 130.1 (d,
m-ArCH), 135.3 (s, Ar’C), 156.9 (s, ArCO), 196.8 (s, C=O) ppm.
MS (FAB): m/z (%) = 263 (38) [M+Na]+, 241 (100) [M+H]+, 149 (94).
140 Experimental Part
1H NMR (400 MHz, CDCl3): 1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)
13C NMR (100 MHz, CDCl3): 1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)
Syntheses 141
2.1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)
A mixture of ketone 118 (501 mg, 1.50 mmol), hydrazine hydrate (0.77 mL) and
ethylene glycol (8 mL) was refluxed until a homogenous solution resulted. KOH
(1.12 g, 19.9 mmol) was added in small portions to the refluxing mixture over a period
of 2 h and heated for another hour. After cooling to room temperature, the mixture was
poured onto ice cold conc. HCl (10 mL) and extracted with MTBE (3 x 15 mL). The
organic layer was washed with water (3 x 15 mL), dried over MgSO4 and the solvent
was removed at a rotary evaporator. The crude product was purified by flash
chromatography (silica gel, PE/EtOAc 10:1 to 5:1, Rf (5:1) = 0.66) and dried in vacuo
(4.5 mbar, 100 °C) to yield 129 (339 mg, 71 %) as a colorless oil.
HRMS (EI, 70 eV): C17H19BrO (319.24)
calcd.: 318.0619 g/mol
found: 318.0630 g/mol
1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 6 H, CH3), 2.78–2.82 (m, CH2), 2.98-3.02 (m,
CH2), 3.73 (s, 3 H, OCH3), 6.89 (s, m-ArH), 7.05–7.10 (m, Ar’H), 7.19–7.25 (m, Ar’H),
7.56 (dd, 2J = 7.9 Hz, 3J = 0.9 Hz, Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.2 (q, CH3), 35.8 (t, CH2) , 38.7 (t, CH2), 59.9
(q, OCH3), 124.6 (s, Ar’CBr), 127.5 (d, Ar’CH), 127.8 (d, ArC’H), 128.9 (d, ArCH),
130.6 (d, Ar’CH), 130.7 (ArCCH3), 133.0 (d, ArC’H), 136.9 (s, ArC), 141.3 (s, Ar’C),
155.4 (s, ArCO) ppm.
142 Experimental Part
MS (FAB): m/z (%): 319 (37) [M+H]+, 183 (13) [M–C9H11O]+, 149 (100) [M–
C7H6Br]+.
Syntheses 143
1H NMR (400 MHz, CDCl3): 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)
13C NMR (100 MHz, CDCl3): 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)
144 Experimental Part
2.1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)
5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129) (299 mg, 937 µmol),
potassium carbonate (262 mg, 1.90 mmol) and tricyclohexylphosphonium
tetrafluoroborate (37 mg, 99 µmol) were suspended in DMA (5 mL) in a screw-cap
flask. The suspension was degassed with argon for 10 min before Pd(OAc)2 (10 mg,
45 µmol) was added. The mixture was heated to 170 °C for 3 d, cooled to room
temperature, hydrolyzed with water (15 mL) and extracted with DCM (3 x 15 mL). The
organic layer was washed with HCl (2 N, 15 mL), water (15 mL), brine (15 mL) and
dried over MgSO4. The solvents were removed under reduced pressure and the residue
purified by flash chromatography (silica gel, PE/EtOAc 10:1 to 5:1, Rf (5:1) = 0.28).
Recrystallization from DCM/MeOH and drying in vacuo (4 mbar, 50 °C) gave 130
(153 mg, 69 %) as colorless solid with mp 86–88 °C.
IR (KBr): ν~ = 3098 (w), 3057 (w), 3013 (w), 2981 (w), 2938 (m), 2890 (w), 2829 (w),
1558 (w), 1476 (m), 1442 (m), 1400 (w), 1373 (w), 1344 (w), 1324 (w), 1291 (w), 1243
(w), 1224 (m), 1194 (w), 1139 (s), 1107 (w), 1046 (w), 1013 (s), 990 (w), 969 (w), 947
(w), 881 (w), 799 (w), 781 (w), 747 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 299 (3.8, sh), 266 (4.3) nm.
1H NMR (400 MHz, CDCl3): δ = 2.32 (s, 3 H, CH3), 2.55 (s, 3 H, CH3), 2.71 (dd, 1
J =
16.6 Hz, 2J = 7.5 Hz, 4 H, CH2), 3.79 (s, 3 H, OCH3), 6.95 (s, 1H, Ar-1-H), 7.20 (“t”,
“J” = 7.3 Hz, 1 H, ArH), 7.26–7.30 (m, 2 H, ArH), 7.63 (d, J = 7.9 Hz, 1 H, Ar-5-H)
ppm.
Syntheses 145
13C{
1H} NMR (100 MHz, CDCl3): δ = 15.8 (q, CH3), 16.2 (q, CH3), 30.3 (t, CH2), 30.4
(t, CH2), 59.9 (q, OCH3), 125.8 (d, ArCH), 126.6 (d, ArCH), 127.6 (d, ArCH), 127.9 (d,
ArCH), 128.0 (s, ArC), 128.5 (d, ArCH), 129.4 (s, ArC), 133.8 (s, ArC), 135.0 (s, ArC),
135.3 (s, ArC), 139.9 (s, ArC), 156.9 (s, ArCO) ppm.
MS (EI, 70 eV): m/z (%) = 238 (100) M+, 223 (28) [M–CH3]+, 208 (16), 200 (10), 178
(11), 165 (15).
146 Experimental Part
1H NMR (400 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)
13C NMR (100 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)
Syntheses 147
2.1.9 (2-Bromophenylethynyl)trimethylsilane (144)
In a screw-capped flask 1,2-dibromobenzene (142) (1.19 g, 4.95 mmol), palladium(II)
acetate (45 mg, 200 µmol), triphenylphosphine (209 mg, 797 µmol), copper(I) iodide
(80 mg, 412 µmol) and trimethylsilylacetylene (284) (0.86 mL, 5.96 mmol) were
suspended in dry triethylamine (11 mL) and heated to 70 °C for 17 hours. The solvent
was removed and the residue was dissolved in MTBE (20 mL) and water (20 mL), the
layers were separated and the organic layer washed with water (20 mL), dried over
MgSO4 and the solvent was removed in vacuo. The remaining residue was purified by
flash chromatography (silica gel, PE and PE/EtOAC 50:1, Rf in PE = 0.35) to yield Z
(982 mg, 78 %) as a yellow oil.
1H NMR (400 MHz, CDCl3): δ = 0.28 (s, 9 H, Si(CH3)3), 7.15 (“t”, “J” = 7.5 Hz, 1 H,
ArH), 7.24 (td, J = 7.6 Hz, J = 1.0 Hz, 1 H, ArH)), 7.49 (dd, J = 7.4 Hz, J = 1.7 Hz, 1 H,
ArH), 7.57 (d, J = 7.6 Hz, 1 H, ArH) ppm.
NMR data are in accord with the literature.126
148 Experimental Part
1H NMR (200 MHz, CDCl3): (2-Bromophenylethynyl)trimethylsilane (144)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
8.69
2.00
1.00
0.94
0.28
7.15
7.24
7.49
7.57
7.07.17.27.37.47.57.6f1 (ppm)
2.00
1.00
0.94
7.15
7.24
7.49
7.57
Syntheses 149
2.1.10 1-Bromo-2-ethynylbenzene (140)
4-(2-Bromophenyl)-2-methylbut-3-yn-2-ol (143) (1.28 g, 5.37 mmol) and sodium
hydride (1.58 g, 39.5 mmol, 60 % dispersion in oil) were suspended in dry toluene
(12.5 mL) and heated to reflux for 1 h, after which half the solvent was removed at a
water separator. Water was added to the mixture (35 mL), the layers were separated and
the aqueous layer was extracted with dichloromethane (3 x 20 mL), the combined
organic layers were dried over MgSO4 and the solvent was removed in vacuo. The
resulting liquid (1.74 g) was submitted to flash chromatography (silica gel, PE,
Rf = 0.38) to yield 317 mg (33 %) 140 as colorless oil.
1H NMR (400 MHz, CDCl3): δ = 3.37 (s, 1 H, ≡CH), 7.20 and 7.27 (both td,
superimposed, J = 7.6, 1.9 Hz and J = 7.5, 1.6 Hz, 2 H, ArH), 7.54 (dd, J = 7.3, 2.0 Hz,
1 H, ArH), 7.59 (dd, J = 7.7, 1.4 Hz, 1 H, ArH) ppm.
NMR data are in accord with the literature.126
150 Experimental Part
1H NMR (200 MHz, CDCl3): 1-Bromo-2-ethynylbenzene (140)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
1.00
2.47
1.12
1.00
3.37
7.20
7.27
7.54
7.59
7.17.27.37.47.57.67.7f1 (ppm)
2.47
1.12
1.00
7.20
7.27
7.54
7.59
Syntheses 151
2.1.11 2-Chlorobenzoyl chloride (148a), 2-Bromobenzoyl chloride (148b),
2-Iodobenzoyl chloride (148c)
General procedure A:
2-Halobenzoic acid 147 (1 mmol) was dissolved in dry dichloromethane (2 mL), oxalyl
chloride (1.14 mmol) and one drop DMF were added and the mixture was stirred at
room temperature for 3.5 h. The solvent was removed at a rotary evaporator and the
crude product was used without further purification.
X = Cl: 99 % of 2-Chlorobenzoyl chloride 148a as slightly yellow oil.
X = Br: According to NMR nearly quantitative yield of 2-Bromobenzoyl chloride 148b
as slightly yellow oil.
General procedure B:
2-Halobenzoic acid 147 (1 mmol), thionyl chloride (2.2 mmol) and one drop DMF were
refluxed in dry dichloromethane (1.5–2 mL) for 3 h. The mixture was cooled to room
temperature, washed twice with aqueous NaHCO3 (10 %, 2 mL), water (2 mL) and
dried over MgSO4. The solvent was removed at a rotary evaporator to yield 148. The
compound was used without further purification.
X = Cl: 86-94 % of 2-Chlorobenzoyl chloride 148a as colorless oil.
X = Br: 92-98 % of 2-Bromobenzoyl chloride 148b as slightly yellow oil.
X = I: 81 % of 2-Iodobenzoyl chloride 148c as brown oil.
152 Experimental Part
2-Chlorobenzoyl chloride (148a):
1H NMR (200 MHz, CDCl3): δ = 7.38–7.55 (m, 3 H, ArH), 8.08–8.13 (m, 1 H, ArH)
ppm.
2-Bromobenzoyl chloride (148b):
1H NMR (200 MHz, CDCl3): δ = 7.38–7.51 (m, 2 H, ArH), 7.67–7.76 (m, 1 H, ArH),
8.02–8.11 (m, 1 H, ArH) ppm.
2-Iodobenzoyl chloride (148c):
1H NMR (200 MHz, CDCl3): δ = 7.25 (td, 3J = 7.8, 4
J = 1.6 Hz, 1 H, ArH), 7.50 (td, 3J
= 7.8, 4J = 1.1, 1 H, ArH), 8.05 and 8.07 (both dd, 3
J = 7.9, 4J = 1.0 Hz and 3
J = 7.9, 4J
= 1.6 Hz, superimposed, 2 H, ArH) ppm.
1H NMR (200 MHz, CDCl3): 2-Chlorobenzoyl chloride (148a)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
3.17
1.00
7.38
7.55
8.08
8.13
7.47.57.67.77.87.98.08.1f1 (ppm)
3.17
1.00
7.38
7.55
8.08
8.13
Syntheses 153
1H NMR (200 MHz, CDCl3): 2-Bromobenzoyl chloride (148b)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
1.99
0.98
1.00
7.38
7.51
7.67
7.76
8.02
8.11
7.47.57.67.77.87.98.08.1f1 (ppm)
1.99
0.98
1.00
7.38
7.51
7.67
7.76
8.02
8.11
1H NMR (200 MHz, CDCl3): 2-Iodobenzoyl chloride (148c)
154 Experimental Part
2.1.12 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a)
2,6-Dimethylanisole (117) (1.13 mL, 7.82 mmol), aluminium chloride (641 mg,
4.76 mmol) and 2-chlorobenzoyl chloride (148a) (678 mg, 3.87 mmol) were suspended
in dry dichloromethane (10 mL) and refluxed for 1 h 15 min. After addition of HCl
(2 N, 15 mL), the layers were separated and the aqueous layer was extracted twice with
dichloromethane (15 mL). The combined organic extracts were washed with 10 %
NaOH (15 mL), water (15 mL), dried over MgSO4 and the solvent was removed in
vacuo to yield 1.48 g of a slightly yellow liquid. The crude product was purified by
flash chromatography (silica gel, PE/EtOAc 15:1 to 5:1, Rf (10:1 PE/EtOAc) = 0.33).
After drying in vacuo (2.6 mbar, 50 °C, 35 min) 935 mg (88 %) of 149a were obtained
as slightly yellow oil which crystallized to give a colorless solid with mp 47–48 °C.
C16H15ClO2 (274.74)
calcd.: C 69.95, H 5.50
found: C 70.00, H 5.57
IR (KBr): ν~ = 3046 (w), 3034 (w), 2959 (w), 2920 (w), 2855 (w), 2835 (w), 2728 (w),
1760 (w), 1691 (w), 1665 (s), 1594 (m), 1565 (w), 1521 (w), 1481 (w), 1468 (w), 1453
(w), 1433 (m), 1417 (w), 1376 (w), 1320 (s), 1268 (w), 1237 (w), 1216 (m), 1162 (w),
1127 (s), 1062 (w), 1030 (w), 1010 (m), 978 (w), 955 (w), 906 (w), 882 (w), 844 (w),
772 (m), 751 (w), 738 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 270 (4.1) nm.
1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.32-7.38 (m,
2 H, Ar’H), 7.40-7.47 (m, 2 H, Ar’H), 7.49 (s, 2 H, Ar-2/6-H) ppm.
Syntheses 155
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 126.7 (d,
Ar’CH), 129.0 (d, Ar’CH), 130.2 (d, Ar’CH), 131.0 (d, Ar’CH), 131.3 (d, ArC-2/6-H),
131.5 (s, ArC, CCH3), 132.2 (s, ArC), 139.2 (s, ArCCl), 162.1 (s, ArCO), 194.7 (s,
C=O) ppm.
MS (EI, 70 eV): m/z (%) = 274 (37) M+, 163 (100) [M– PhCl]+, 139 (8), 105 (9), 91 (8).
156 Experimental Part
1H NMR (400 MHz, CDCl3): (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149a)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.40
3.00
2.09
2.24
1.81
2.30
3.78
7.32
7.38
7.40
7.47
7.49
7.357.407.457.50f1 (ppm)
2.09
2.24
1.81
7.32
7.38
7.40
7.47
7.49
13C NMR (100 MHz, CDCl3): (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149a)
0102030405060708090100110120130140150160170180190200f1 (ppm)
16.4
59.8
126.7
129.0
130.2
131.0
131.3
131.5
132.2
139.2
162.1
194.7
129130131132f1 (ppm)
129.0
130.2
131.0
131.3
131.5
132.2
Syntheses 157
2.1.13 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b)
2,6-Dimethylanisole (117) (1.13 mL, 7.82 mmol), aluminium chloride (620 mg, 4.60
mmol) and 2-bromobenzoyl chloride (148b) (852 mg, 3.88 mmol) were suspended in
dry dichloromethane (10 mL) and refluxed for 1 h 15 min. After addition of HCl (2 N,
15 mL), the layers were separated and the aqueous layer was extracted twice with
dichloromethane (15 mL). The combined organic extracts were washed with 10 %
NaOH (15 mL), water (15 mL), dried over MgSO4 and the solvent was removed in
vacuo. The crude product was purified by flash chromatography (silica gel, PE/EtOAc
15:1, Rf (10:1 PE/EtOAc) = 0.29). After drying in vacuo (2.6 mbar, 75 °C, 1 h) 1.12 g
(91 %) of 149b were obtained as slightly yellow oil which crystallized to give a
colorless solid with mp 63 °C.
C16H15BrO2 (319.19)
calcd.: C 60.21, H 4.74
found: C 60.35, H 4.75
IR (KBr): ν~ = 3057 (w), 2953 (w), 2919 (w), 2836 (w), 1757 (w), 1694 (w), 1652 (s),
1591 (s), 1481 (m), 1465 (w), 1426 (s), 1375 (w), 1320 (s), 1268 (w), 1239 (w), 1217
(s), 1160 (w), 1126 (s), 1055 (w), 1009 (s), 978 (w), 952 (w), 904 (w), 882 (w), 846
(m), 765 (s), 749 (m), 731 (w) cm-1.
UV/Vis (CH3CN): λmax (lgε) = 272 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.30 and 7.34
(“d” and “t”, “J” = 7.4 Hz and “J” = 7.7 Hz, 2 H, Ar’-4/6-H), 7.40 (“t”, “J” = 7.4 Hz, 1
H, Ar’-5-H), 7.48 (s, 2 H, m-Ar-2/6-H), 7.64 (d, J = 7.9 Hz, 1 H, Ar’-3-H) ppm.
158 Experimental Part
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.38 (q, CH3), 59.83 (q, OCH3), 119.60 (s,
Ar’C-2-Br), 127.21 (d, Ar’C-5-H), 128.90 (d, Ar’C-6-H), 131.00 (d, Ar’C-4-H), 131.46
(d, ArC-2/6-H), 131.55 (s, ArC-3/5), 131.81 (s, ArC-1), 133.28 (d, Ar’C-3-H), 141.20
(s, Ar’C-1), 162.12 (s, ArC-4-O), 195.31 (s, ArC=O) ppm.
MS (FAB): m/z (%): 343 (7) [M+Na]+, 319 (100) [M+H]+, 183 (47), 163 (33), 154 (21),
136 (18).
Syntheses 159
1H NMR (400 MHz, CDCl3): (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149b)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.39
3.20
1.14
0.98
1.09
2.05
1.00
2.29
3.77
7.30
7.34
7.40
7.48
7.64
7.307.357.407.457.507.557.607.65f1 (ppm)
1.14
0.98
1.09
2.05
1.00
7.30
7.34
7.40
7.48
7.64
*
13C NMR (100 MHz, CDCl3): (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149b)
0102030405060708090100110120130140150160170180190f1 (ppm)
16.4
59.8
119.6
127.2
128.9
131.0
131.5
133.3
141.2
162.1
195.3
131132133134f1 (ppm)
131.0
131.5
131.6
131.8
133.3
*
160 Experimental Part
2.1.14 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c)
2,6-Dimethylanisole (117) (1.00 mL, 6.92 mmol), aluminium chloride (571 mg,
4.28 mmol) and 2-iodobenzoyl chloride (148c) (863 mg, 3.24 mmol) were suspended in
dry dichloromethane (8 mL) and refluxed for 1 h 15 min. After addition of HCl (2 N,
15 mL), the layers were separated and the aqueous layer was extracted twice with
dichloromethane (15 mL). The combined organic extracts were washed with 10 %
NaOH (15 mL), water (15 mL), dried over MgSO4 and the solvent was removed in
vacuo. The crude product was purified by flash chromatography (silica gel, PE/EtOAc
15:1 to 5:1, Rf (10:1 PE/EtOAc) = 0.30). After drying in vacuo (0.74 mbar, 50–100 °C
°C, 1 h) 984 mg (83 %) of 149c were obtained as slightly yellow oil which crystallized
to give a colorless solid with mp 88–90 °C.
C16H15ClO2 (366.01)
calcd.: C 52.48, H 4.13
found: C 52.59, H 4.30
IR (KBr): ν~ = 3047 (w), 2947 (w), 2919 (w), 2855 (w), 1663 (m), 1589 (w), 1481 (w),
1456 (w), 1426 (w), 1374 (w), 1313 (s), 1242 (w), 1216 (w), 1126 (m), 1006 (w), 975
(w), 949 (w), 919 (w), 885 (w), 843 (w), 768 (w), 734 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 273 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.17 (td, 3J =
7.7 Hz, 4J = 1.7 Hz, 1 H, Ar’-4-H), 7.27 (dd, 3
J = 7.1 Hz, 4J = 1.6 Hz, 1 H, Ar’-6-H),
7.43 (td, 3J = 7.5 Hz, 4J = 1.1 Hz, 1 H, Ar’-5-H), 7.48 (s, 2 H, Ar-2/6-H), 7.92 (dd, 3
J =
8.0 Hz, 4J = 0.8 Hz, 1 H, Ar’-3-H) ppm.
Syntheses 161
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 92.4 (s, ArCI),
127.8 (d, Ar’C-5-H), 128.4 (d, Ar’C-6-H), 131.0 (d, Ar’C-4-H), 131.3 (s, ArC-1), 131.6
(s, ArCCH3), 131.7 (d, ArC-2/6-H), 139.8 (s, Ar’C-3-H), 144.9 (s, Ar’C-1), 162.1 (s,
ArCO), 196.8 (s, C=O) ppm.
MS (EI, 70 eV): m/z (%) = 366 (79) M+, 239 (14) [M–I]+, 231 (19), 203 (11), 163 (100),
105 (14), 91 (18), 76 (11).
162 Experimental Part
1H NMR (400 MHz, CDCl3): (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149c)
13C NMR (100 MHz, CDCl3): (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)-methanone (149c)
Syntheses 163
2.1.15 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)
Procedure A:
(2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149a) (274 mg,
1.00 mmol) or (2-bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b)
(319 mg, 1.00 mmol), potassium carbonate (278 mg, 2.01 mmol) and
tricyclohexylphosphonium tetrafluoroborate (39 mg, 105 µmol) were suspended in
DMA (5 mL) in a screw-cap flask. The suspension was degassed with argon for 10 min
before Pd(OAc)2 (11 mg, 49 µmol) was added. The mixture was heated to 170 °C for 3
d, cooled to room temperature, hydrolyzed with water (15 mL) and extracted with
CH2Cl2 (4 x 15 mL). The organic layer was washed with HCl (2 N, 15 mL), water (15
mL), brine (15 mL) and dried over MgSO4. The solvents were removed under reduced
pressure and the residue purified by flash chromatography (silica gel, toluene, Rf =
0.30). After drying in vacuo (1.7 mbar, 50 °C) Z was obtained a yellow crystalline solid
with mp 97–99 °C.
X = Cl: 175 mg, 74 %
X = Br: 158 mg, 66 %
Procedure B:
(2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149b) (319 mg,
1.00 mmol), potassium carbonate (829 mg, 6.00 mmol) and pivalic acid (102 mg,
1.00 mmol) were dissolved in DMA (10 mL) and toluene (5 ml) in a screw-cap flask
under argon. After addition of Bedford catalyst 150 (47 mg, 30 µmol) the reaction
mixture was heated to 120 °C for 10 h, cooled to room temperature and hydrolyzed with
HCl (2 N, 20 mL). The mixture was extracted with CH2Cl2 (3 x 10 mL), the organic
layer was washed with water (15 mL) dried over MgSO4 and the solvents were removed
164 Experimental Part
under reduced pressure. The residue was purified by flash chromatography (silica gel,
toluene, Rf = 0.30) to yield 151 (215 mg, 90 %) as a yellow solid after drying in vacuo
(2.1 mbar, 50 °C).
IR (KBr): ν~ = 3015 (w), 3000 (w), 2950 (w), 2935 (w), 2917 (w), 2884 (w), 2847 (w),
2826 (w), 1731 (w), 1707 (s), 1604 (m), 1577 (m), 1467 (w), 1448 (m), 1437 (m), 1401
(w), 1363 (m), 1301 (m), 1229 (m), 1185 (m), 1166 (w), 1127 (s), 1088 (w), 1035 (w),
1005 (s), 956 (w), 885 (w), 864 (w), 800 (w), 767 (w), 750 (m), 718 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 336 (3.4), 323 (3.4), 301 (3.6), 289 (3.5), 255 (4.5) nm.
1H NMR (400 MHz, CDCl3): δ = 2.29 (s, 3 H, CH3), 2.50 (s, 3 H, CH3), 3.76 (s, 3 H,
OCH3), 7.25 (td, J = 7.5 Hz, J = 0.8 Hz, 1 H, ArH), 7.38 (s, 1 H, Ar-H), 7.45 (td, J = 7.6
Hz, J = 1.2 Hz, 1 H, ArH), 7.60 (d, J = 7.6 1 H, ArH), 7.63 („d“, „J“ = 7.3 Hz, 1 H,
ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 12.8 (q, CH3), 16.6 (q, CH3), 60.3 (q, OCH3),
123.1 (d, ArCH), 124.2 (d, ArCH), 125.0 (d, ArC-H), 127.6 (s, ArC), 128.3 (d, ArCH),
130.2 (s, ArC), 131.7 (s, ArC), 134.5 (d, ArCH), 135.1 (s, ArC), 142.5 (s, ArC), 145.2
(s, ArC), 162.8 (s, ArCO), 193.7 (s, C=O) ppm.
MS (EI, 70 eV): m/z (%) = 238 (100) M+, 223 (36) [M–CH3]+, 195 (10), 165 (24), 152
(15).
1H NMR data are in accord with those reported in the literature.133
Syntheses 165
1H NMR (400 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
2.96
3.01
3.00
1.20
0.88
0.96
1.00
0.85
2.29
2.50
3.76
7.25
7.38
7.45
7.60
7.63
7.27.37.47.57.6f1 (ppm)
1.20
0.88
0.96
1.00
0.85
7.25
7.38
7.45
7.60
7.63
13C NMR (100 MHz, CDCl3): 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)
0102030405060708090100110120130140150160170180190f1 (ppm)
12.8
16.6
60.3
123.1
124.2
125.0
127.6
128.3
130.2
131.7
134.5
135.1
142.5
145.2
162.8
193.7
166 Experimental Part
2.1.16 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)
To a solution of 2,6-dimethylanisole (117) (0.962 g, 6.92 mmol) and phthalic anhydride
(153) (1.13 g, 7.61 mmol) in dry dichloromethane (10 mL) was added a solution of
AlCl3 (1.19 g, 8.89 mmol) in dry nitromethane (1.7 mL) at room temperature. The
mixture was refluxed for 1 h 15 min and poured into water (10 mL). The aqueous layer
was extracted with dichloromethane (2 x 10 mL), the organic layer was washed with
hydrochlorid acid (2 N, 10 mL), water (10 mL) and brine (10 mL), dried over MgSO4
and the solvent was removed in vacuo. The residue was purified by flash
chromatography (silica gel, PE/DCM to remove unreacted starting material and then
PE/EtOAc 2:1, Rf = 0.13) and the product dried in vacuo (1.1 mbar, 75 °C, 30 min) to
yield 154 (172 mg, 9 %) as colorless solid with mp 171 °C.
HRMS (EI, 70 eV): C17H16O4 (284.31)
calcd.: 284.1049
found: 284.1046
IR (KBr): ν~ = 2984 (w), 2956 (w), 2933 (w), 2823 (w), 2667 (w), 2537 (w), 1693 (s),
1669 (s), 1593 (m), 1575 (w), 1481 (w), 1451 (w), 1418 (m), 1386 (w), 1312 (s), 1237
(w), 1210 (m), 1166 (w), 1146 (w), 1124 (m), 1088 (w), 1043 (w), 997 (w), 942 (w),
909 (w), 848 (w), 810 (w), 767 (w), 708 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 266 (4.1) nm.
1H NMR (400 MHz, CDCl3): δ = 2.27 (s, 6 H, CH3), 3.76 (s, 3 H, OCH3), 7.34 (dd, 3J =
7.5 Hz, 4J = 0.9 Hz, 1 H, Ar’H), 7.41 (s, 2 H, Ar-2/6-H), 7.56 (td, 3
J = 7.6 Hz, 4J = 1.2
Hz, 1 H, Ar’H), 7.65 (td, 3J = 7.5 Hz, 4
J = 1.2 Hz, 1 H, Ar’H), 8.09 (dd, 3J = 7.8 Hz, 4
J
= 0.9 Hz, 1 H, Ar’H) ppm.
Syntheses 167
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 127.9 (d,
PHCH), 128.0 (s, Ar’CCOOH), 129.5 (d, Ar’CH), 130.9 (d, ArC-2/6-H), 131.1 (d,
Ar’CH), 131.3 (s, ArCCH3), 132.6 (s, ArC), 133.1 (d, Ar’CH), 143.0 (s, Ar’C), 161.7 (s,
ArCO), 169.7 (s, COOH), 196.6 (s, C=O) ppm.
MS (EI, 70 eV): m/z (%) = 284 (37) M+, 225 (12), 209 (14), 163 (100), 149 (13), 105
(14), 91 (14), 65 (11)
168 Experimental Part
1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)
13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)
Syntheses 169
2.1.17 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)
Phthaloyl dichloride (159) (0.21 mL, 1.38 mmol) and aluminium chloride (216 mg,
1.62 mmol) were dissolved in dry dichloromethane (15 mL). 2,6-Dimethylanisole (117)
(0.20 mL, 1.38 mmol) was added dropwise to the yellow solution which turned dark red
upon addition. The mixture was stirred for 18 hours at room temperature before adding
again aluminium chloride (216 mg, 1.62 mmol) and stirring for further 26 hours. It was
hydrolysed with hydrochloric acid (2 N, 7 mL) and the aqueous layer was extracted
with dichloromethane (3 x 10 mL), the combined organic layers were washed with
sodium hydrogencarbonate (10 mL), water (2 x 10 mL), dried over MgSO4 and the
solvent was removed in vacuo. The brown liquid was subjected to flash chromatography
(silica gel, PE/EtOAc 5:1 to 2:1, Rf (2:1) = 0.54) to yield 371 mg (67 %) 161 as a
colorless solid with mp 194–196 °C.
C26H26O4 (402.48)
calcd.: C 77.59, H 6.51
found: C 77.37, H 6.72
IR (KBr): ν~ = 2950 (w), 2928 (w), 2822 (w), 1769 (s), 1659 (w), 1597 (w), 1482 (w),
1463 (w), 1416 (w), 1376 (w), 1310 (w), 1290 (w), 1249 (w), 1228 (w), 1150 (w), 1110
(w), 1093 (w), 1008 (w), 979 (w), 935 (w), 912 (w), 882 (w), 859 (w), 818 (w), 797 (w),
763 (w), 746 (w), 722 (w), 695 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 275 (3.5) nm.
170 Experimental Part
1H NMR (400 MHz, CDCl3): δ = 2.22 (s, 12 H, CH3), 3.70 (s, 6 H, OCH3), 6.94 (s, 4 H,
Ar-2/6-H), 7.54 (m, 2 H, Ar’H), 7.69 (“t”, “J” = 7.6 Hz, 1 H, Ar’H), 7.92 (d, J = 7.6 Hz,
1 H, Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.8 (q, OCH3), 91.8 (s, ArC),
124.3 (d, Ar’CH), 125.7 (s, Ar’CC=O), 126.1 (d, Ar’CH), 127.7 (d, ArC-2/6-H), 129.3
(d, Ar’CH), 131.0 (s, ArCCH3), 134.1 (d, Ar’CH), 136.2 (s, ArC), 152.7 (s, Ar’C),
157.2 (s, ArCO), 170.1 (s, C=O) ppm.
MS (FAB): m/z (%) = 403 (100) [M+H]+, 307 (12), 267 (24).
Syntheses 171
1H NMR (400 MHz, CDCl3): 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)
13C NMR (100 MHz, CDCl3): 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one (161)
172 Experimental Part
2.1.18 4-Bromo-2,6-dimethylphenol (208)
2,6-Dimethylphenol (155) (1.22 g, 9.99 mmol) was dissolved in chloroform (40 mL)
and a solution of bromine (1.50 g, 9.96 mmol) in chloroform (25 mL) was added
dropwise. The reaction mixture was stirred 1.5 h at room temperature after complete
addition, washed with aqueous sodium sulfite (10 %, 15 mL) aqueous ammonium
chloride (1 N, 15 mL) and dried over MgSO4. The solvent was avaporated and the
resulting solid (1.93 g) was recrystallized from PE (25 mL) to yield 1.36 g (69 %) of
208 as colorless solid with mp 79 °C (lit.194 79.5 °C)
1H NMR (200 MHz, CDCl3): δ = 2.21 (s, 6 H, CH3), 4.56 (s, 1 H, OH), 7.10 (s, 2 H, m-
ArH) ppm.
MS (EI): m/z (%) = 199 (199) M+, 121 (75) [M–Br]+, 103 (13), 91(31), 77 (26).
NMR data are in accord with the literature.149
Syntheses 173
1H NMR (200 MHz, CDCl3): 4-Bromo-2,6-dimethylphenol (208)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
6.25
1.00
1.99
2.22
4.57
7.10
174 Experimental Part
2.1.19 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)
4-Bromo-2,6-dimethylphenol (208) (314 mg, 1.55 mmol) and 2-biphenylboronic acid
(190) (328 mg, 1.66 mmol) were dissolved in anhydrous THF (5 mL) in a screw-cap
flask. After addition of 2 M K2CO3 (5 mL) the solution was degassed with argon for
5 min, Pd(PPh3)4 (89 mg, 73 µmol) was added and the mixture was heated to 120 °C for
20 h. After cooling to room temperature it was extracted with dichloromethane
(2 x 10 mL), the combined organic layers were washed with brine (20 mL), dried over
MgSO4 and the solvent was removed at a rotary evaporator. The residue was purified by
flash chromatography (silica gel, PE/EtOAc 10:1, Rf = 0.25) to yield 209 as a pale
yellow highly viscous oil (282 mg, 66 %) after drying in vacuo (0.81 mbar, 50 °C, 1 h).
HRMS (EI): C20H18O
calcd.: 274.1358 g/mol
found: 274.1360 g/mol
IR (ATR): ν~ = 3566 (w), 3021 (w), 2917 (w), 1659 (w), 1599 (w), 1489 (w), 1471 (w),
1448 (w), 1431 (w), 1377 (w), 1312 (w), 1235 (w), 1200 (w), 1181 (m), 1114 (w), 1080
(w), 1022 (w), 1008 (w), 985 (w), 941 (w), 913 (w), 883 (w), 869 (w), 803 (w), 760
(m), 743 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 270 nm (3.9, sh), 240 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 2.12 ppm (s, 6 H, CH3), 4.50 (s, 1 H, OH), 6.73 (s, 2
H, m-ArH), 7.16–7.21 (m, 5 H, biphenylH), 7.35–7.42 (m, 4 H, biphenylH) ppm.
Syntheses 175
13C{
1H} NMR (100 MHz, CDCl3): δ = 15.9 ppm (q, CH3), 122.5 (d, biphenylCH ),
126.4 (s, ArC), 127.0 (s, ArC), 127.5 (d, biphenylCH), 127.9 (d, biphenylCH), 130.0 (d,
biphenylCH), 130.3 (d, m-ArCH), 130.6 (d, biphenylCH), 130.7 (d, biphenylCH), 133.6
(s, ArC), 140.5 (s, ArC), 140.6 (s, ArC), 142.0 (s, ArC), 151.0 (s, COH) ppm.
MS (FAB): m/z (%) = 274 (100) M+.
176 Experimental Part
1H NMR (400 MHz, CDCl3): 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.52
1.00
2.04
5.19
4.42
2.12
4.50
6.74
7.15
7.23
7.35
7.42
7.17.27.37.4f1 (ppm)
5.19
4.42
7.15
7.23
7.35
7.42
13C NMR (100 MHz, CDCl3): 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)
0102030405060708090100110120130140150f1 (ppm)
15.9
122.5
126.4
127.0
127.5
127.9
130.0
130.3
130.6
130.6
133.6
140.5
140.6
142.0
151.0
126127128129130131f1 (ppm)
126.4
127.0
127.5
127.9
130.0
130.3
130.6
130.6
Syntheses 177
2.1.20 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)
Biphenylphenol 209 (190 mg, 693 µmol) were dissolved in dichloromethane (2 mL)
and 2,2,2-trifluroroethanol (6 mL) and PIFA was added (334 mg, 761 µmol). The
mixture was stirred at room temperature for 20 min. The solvents were removed at a
rotary evaporator and the residue purified by flash chromatography (silica gel,
PE/toluene 1:1, Rf = 0.15). After drying in vacuo (1.7–2.6 mbar, 60 °C, 2 h) 210
(132 mg, 70 %) was obtained as colorless solid with mp 143 °C. An analytically pure
sample was obtained by crystallization from DCM/MeOH.
C20H16O (272.34)
calcd.: C 88.20, H 5.92
found: C 88.15, H 5.85
IR (ATR):ν~ = 3011 (w), 2955 (w), 2923 (w), 1698 (w), 1662 (w), 1638 (m), 1602 (w),
1472 (w), 1446 (w), 1396 (w), 1367 (w), 1278 (w), 1234 (w), 1202 (w), 1162 (w), 1095
(w), 1036 (w), 933 w), 867 (w), 757 (m), 730 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 302 (3.8), 291 (3.7), 267 (4.2, sh), 245 (4.3, sh), 234
(4.5), 223 (4.6) nm.
1H NMR (400 MHz, CDCl3): δ = 1.98 (s, 6 H, CH3), 6.30 (s, 2 H, CH=C), 7.21 (d, J =
7.5 Hz, 2 H, ArH), 7.30 (td, J = 7.5 Hz, J = 1.1 Hz, 2 H, ArH), 7.43 (td, J = 7.5 Hz, J =
1.1 Hz, 2 H, ArH), 7.79 (d, J = 7.6 , 2 H, ArH) ppm.
178 Experimental Part
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 56.9 (s, Spiro-C), 120.7 (d,
ArCH), 125.0 (d, ArCH), 128.1 (d, ArCH), 128.7 (d, ArCH), 135.5 (s, ArC), 141.6 (s,
ArC), 143.9 (s, ArC), 144.6 (d, CH=C), 187.9 (s, C=O) ppm.
MS (FAB): m/z (%) = 273 (100) [M+H]+, 258 (14).
Syntheses 179
1H NMR (400 MHz, CDCl3): 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)
13C NMR (100 MHz, CDCl3): 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)
180 Experimental Part
2.1.21 1,3-Dimethyltriphenylen-2-yl acetate (211)
Spiro compound 210 (150 mg, 551 µmol) was suspended in acetic anhydride (3 mL)
and one drop of concentrated sulfuric acid was added before heating the mixture to
100 °C for 30 min. The mixture was poured onto ice and extracted with
dichloromethane (2 x 15 mL). The combined organic layers were washed with water
(15 mL), brine (15 mL) dried over MgSO4 and the solvent was removed at a rotary
evaporator. The brown residue was purified by flash chromatography (silica gel,
PE/EtOAc 10:1, Rf = 0.25) to yield 211 (159 mg, 92 %) as a colorless solid with
mp 153 °C after drying in vacuo (1.3 mbar, 75°C). An analytically pure sample was
obtained by crystallization from DCM/PE.
C22H18O2 (314.38)
calcd.: C 84.05, H 5.77
found: C 83.85, H 5.72
IR (KBr):ν~ = 3078 (w), 3050 (w), 3002 (w), 2966 (w), 2917 (w), 1749 (s), 1607 (w),
1539 (w), 1490 (w), 1439 (m), 1422 (w), 1373 (m), 1343 (w), 1315 (w), 1218 (s), 1169
(w), 1154 (w), 1127 (m), 1082 (w), 1045 (w), 1010 (w), 996 (w), 946 (w), 923 (w), 880
(w), 857 (w), 814 (w), 757 (s), 721 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 289 nm (4.3), 280 (4.3, sh), 262 (4.9), 255 (4.9, sh) nm.
1H NMR (400 MHz, CDCl3): δ = 2.42 ppm (s, 3 H, CH3), 2.46 (s, 3 H, CH3), 2.76 (s, 3
H, C(O)CH3), 7.54 (“t”, “J” = 7.7 Hz, 1 H, ArH), 7.59–7.63 (m, 3 H, ArH), 8.37 (s, 1 H,
m-ArH), 8.41 (d, J = 8.3 Hz, 1 H, ArH), 8.52–8.58 (m, 2 H, ArH), 8.60 (d, J = 8.2 Hz, 1
H, ArH) ppm.
Syntheses 181
13C{
1H} NMR (100 MHz, CDCl3): δ = 17.4 (q, CH3), 18.4 (q, CH3), 20.8 (q, C(O)CH3),
12.9 (m-ArCH), 123.2(ArCH), 123. 5 (d, ArCH), 123.6 (d, ArCH), 125.55 (d, ArCH),
126.8 (s, ArC), 127.1 (s, ArC), 127.2 (ArCH), 127.4 (s, ArC), 128.9 (d, ArCH), 129.2
(s, ArC), 130.0 (ArC), 130.1 (s, ArC), 130.3 (s, ArC), 130.4 (s, ArC), 131.2 (s, ArC),
149.01 (s, ArCO), 169.1 (s, C=O) ppm.
MS (FAB): m/z (%) = 314 (23) M+, 272 (100) [M+–C(O)CH3], 256 (13), 239 (11).
182 Experimental Part
1H NMR (400 MHz, CDCl3): 1,3-Dimethyltriphenylen-2-yl acetate (211)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
1.46
1.45
1.50
0.50
1.45
0.49
0.50
1.00
0.42
2.42
2.46
2.76
7.54
7.59
7.63
8.37
8.41
8.52
8.58
8.60
7.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)
0.50
1.45
0.49
0.50
1.00
0.42
7.54
7.59
7.63
8.37
8.41
8.52
8.58
8.60
13C NMR (100 MHz, CDCl3): 1,3-Dimethyltriphenylen-2-yl acetate (211)
0102030405060708090100110120130140150160170f1 (ppm)
17.4
18.4
20.8
31.0
122.9
123.2
123.4
123.5
125.6
126.8
127.1
127.2
127.4
128.9
129.2
130.0
130.1
130.3
130.4
131.2
149.0
169.1
122123124125126127128129130131f1 (ppm)
122.9
123.2
123.4
123.5
125.6
126.8
127.1
127.2
127.4
128.9
129.2
130.0
130.1
130.3
130.4
131.2
Syntheses 183
2.1.22 4-Methoxy-3,5-dimethylbenzaldehyde (250)
2-Methoxy-1,3-dimethylbenzene 117 (1.92 g, 13.8 mmol) and HMTA (3.96 g,
28.3 mmol) were dissolved in trifluoroacetic acid (20 mL) under argon and heated to
90 °C overnight. The resulting brownish solution was hydrolyzed with 4 N HCl (60 mL)
and stirred at room temperature for 15 min. The mixture was extracted with DCM
(4 x 30 mL) and the organic layer was washed with water (2 x 30 mL), saturated
aqueous Na2CO3 (30 mL) and dried over MgSO4. The solvent was removed at a rotary
evaporator. The obtained brown liquid (2.59 g) was submitted to flash chromatography
(silica gel, PE/DCM 1:1, Rf = 0.24) to yield colorless 250 (1.94 g, 85 %) after drying in
vacuo (2.2 mbar, rt to 50 °C).
1H NMR (200 MHz, CDCl3): δ = 2.34 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.55 (s, 2 H
ArH), 9.87 (s, 1 H, CHO) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 16.3 (q, CH3), 59.8 (q, OCH3), 130.8 (d, ArCH),
132.1 (s, ArCCH3), 132.4 (s, ArC), 162.5 (s, ArCO), 191.8 (s, CHO) ppm.
MS (EI, 70 eV): m/z (%) = 164 (100) M+, 149 (18) [M–CH3]+, 137 (16), 121 (12), 105
(22), 91 (25), 77 (22).
The NMR spectroscopic data are in accord with those reported in literature.172
184 Experimental Part
1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzaldehyde (250)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.0f1 (ppm)
6.12
3.07
2.01
1.00
2.34
3.77
7.55
9.87
13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzaldehyde (250)
0102030405060708090100110120130140150160170180190f1 (ppm)
16.3
59.8
130.8
132.1
132.4
162.5
191.8
131132f1 (ppm)
130.8
132.1
132.4
Syntheses 185
2.1.23 4-Methoxy-3,5-dimethylbenzoic acid (251)
4-Methoxy-3,5-dimethylbenzaldehyde 250 (897 mg, 5.46 mmol) and sulfamic acid
(904 mg, 9.31 mmol) were suspended in water (65 mL) and acetone (6 mL). To this a
solution of sodium chlorite (739 mg, 6.54 mmol) in water (5 mL) was added dropwise
upon which a colorless solid precipitated. The mixture was stirred 1 h at room
temperature and extracted with ethyl acetate (4 x 20 mL). The organic layer was washed
with brine (30 mL), dried over MgSO4 and the solvent removed at a rotary evaporator.
After drying in vacuo (0.73 mbar, 50 °C) 251 (959 mg, 97 %) was obtained as colorless
to pale yellow solid with mp 193-194 °C (lit.173 192–194 °C).
1H NMR (200 MHz, CDCl3): δ = 2.33 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.79 (s, 2 H,
ArH) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 16.3 (q, CH3), 59.8 (q, OCH3), 124.7 (s, ArC),
131.3 (d, ArCH), 131.4 (s, ArCCH3), 162.0 (s, ArCO), 172.4 (s, COOH) ppm.
186 Experimental Part
1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoic acid (251)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.03
3.00
2.00
2.33
3.77
7.79
13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoic acid (251)
0102030405060708090100110120130140150160170f1 (ppm)
16.3
59.8
124.7
131.3
131.4
162.0
172.4
131.2131.3131.4f1 (ppm)
131.3
131.4
Syntheses 187
2.1.24 4-Methoxy-3,5-dimethylbenzoyl chloride (245)
4-Methoxy-3,5-dimethylbenzoic acid 251 (645 mg, 3.58 mmol) was suspended in dry
CH2Cl2 (4 mL), thionyl chloride (0.6 mL, 7.85 mmol, 95.5 %) and one drop DMF were
added and the mixture was refluxed for 3 h. The solvent was removed at a rotary
evaporator and the residue dissolved in CH2Cl2, washed with aqueous NaHCO3 (10 %,
2 x 10 mL), water (10 mL) and dried over MgSO4. The solvent was removed by rotary
evaporation and the residue distilled at a Kugelrohr oven (1.3 mbar, 150 °C) to yield
245 (643 mg, 90 %) as pale yellow liquid, which solidified with mp 38–39 °C
(lit.175 40 °C).
1H NMR (200 MHz, CDCl3): δ = 2.34 (s, 6 H, CH3), 3.79 (s, 3 H, OCH3), 7.80 (s, 2 H,
ArH) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 16.4 (q, CH3), 59.9 (q, OCH3), 128.4 (s, ArC),
132.0 (s, ArCCH3), 132.7 (s, ArCH), 163.4 (s, ArCO), 167.8 (s, C=O) ppm.
188 Experimental Part
1H NMR (200 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoyl chloride (245)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
6.34
3.06
2.00
2.34
3.79
7.80
13C NMR (50 MHz, CDCl3): 4-Methoxy-3,5-dimethylbenzoyl chloride (245)
0102030405060708090100110120130140150160170f1 (ppm)
16.4
59.9
128.4
132.0
132.7
163.4
167.8
Syntheses 189
2.1.25 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)
Benzoyl chloride 245 (1.69 g, 8.52 mmol) was dissolved in THF (12 mL) and cooled to
0 °C. A solution of picolinohydrazide (244) (1.10 g, 8.04 mmol) and sodium carbonate
(793 mg, 7.48 mmol) in water (10 mL) and THF (12 mL) was added dropwise and the
mixture was stirred at 0 °C for 3 h. The reaction mixture was extracted with CH2Cl2
(3 x 30 mL), the organic layer was washed with water (30 mL) and brine (30 mL), dried
over MgSO4 and the solvents were removed by rotary evaporation. The obtained solid
(2.69 g) was recrystallized from ethanol (16 mL) and methanol (4 mL) under reflux to
yield 246 (1.96 g, 82 %) as a colorless solid with mp 170 °C after drying in vacuo.
C16H17N3O3 (299.32)
calcd.: C 64.20, H 5.72, N 14.04
found: C 64.24, H 5.80, N 13.93
IR (KBr): ν~ = 3230 (w), 3051 (w), 3016 (w), 2972 (w), 2938 (w), 2822 (w), 1681 (m),
1643 (s), 1602 (w), 1589 (w), 1570 (w), 1552 (w), 1500 (m), 1485 (m), 1463 (m), 1432
(w), 1377 (w), 1334 (w), 1296 (w), 1222 (w), 1185 (w), 1166 (m), 1119 (w), 1088 (w),
1074 (w), 1042 (w), 1020 (w), 999 (w), 964 (w), 906 (w), 891 (w), 815 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 245 (4.3) nm.
1H NMR (400 MHz, CDCl3): δ = 2.30 (s, 6 H, CH3), 3.74 (s, 3 H, OCH3), 7.47 (ddd, 3J
= 7.6 Hz, 3J = 4.8 Hz, 4
J = 1.2 Hz, 1 H, PyH), 7.56 (s, 2 H, ArCH), 7.86 (“td”, 3J = 7.8
Hz, 3J = 7.7 Hz, 4J = 1.7 Hz, 1 H, PyH), 8.15 (“dt”, J = 37.8 Hz, 5J = 0.9 Hz, 1 H, PyH),
8.61 (ddd, 3J = 4.7 Hz, 4
J = 1.5 Hz, 5J = 0.8 Hz, 1 H, PyH), 9.18 (d, J = 5.1 Hz, 1 H,
NH), 10.52 (d, J = 5.9 Hz, 1 H, NH) ppm.
190 Experimental Part
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59.9 (q, OCH3), 122.6 (d, PyCH),
126.9 (d, PyCH), 127.0 (s, ArC), 128.2 (d, ArCH), 131.7 (s, ArCCH3), 137.5 (d, PyCH),
148.4 (s, PyC), 148.8 (d, PyCH), 160.68 (s, ArCO), 160.70 (s, C=O), 164.0 (s, C=O)
ppm.
MS (EI, 70 eV): m/z (%) = 299 (6) M+, 163 (100) [M–C6H6N3O]+.
Syntheses 191
1H NMR (400 MHz, CDCl3): N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
6.15
3.08
1.02
2.07
1.02
1.00
1.01
1.00
0.94
2.30
3.74
7.47
7.56
7.86
8.15
8.61
9.18
10.52
7.57.67.77.87.98.08.18.28.38.48.58.6f1 (ppm)
1.02
2.07
1.02
1.00
1.01
7.47
7.56
7.86
8.15
8.61
13C NMR (100 MHz, CDCl3): N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)
0102030405060708090100110120130140150160f1 (ppm)
16.3
59.9
122.6
126.9
127.0
128.2
131.7
137.5
148.4
148.8
160.7
160.7
164.0
127.0f1 (ppm)
126.9
127.0
160.6160.7f1 (ppm)
160.68
160.70
192 Experimental Part
2.1.26 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolinohydrazonoyl
chloride (247)
Picolinohydrazide 246 (669 mg, 2.24 mmol) was dissolved in chloroform (45 mL), PCl5
(9.00 g, 42.8 mmol) was added and the supension heated to reflux for 24 h. The cooled
mixture was poured onto ice water (50 mL), the layers were separated and the aqueous
layer was extracted with DCM (3 x 30 mL). The combined organic layers were washed
with saturated aqueous NaHCO3 (2 x 25 mL), brine (30 mL) and dried over MgSO4.
The solvent was removed by rotary evaporation and the residue purified by flash
chromatography (silica gel, PE/EtOAc 5:1 to 2:1, Rf (2:1) = 0.46) to yield 247 (455 mg,
61 %) as yellow oil, which solidified upon standing. Analytically pure material was
obtained by crystallization from DCM/isopropanol as delicate colorless needles with
mp 66 °C after drying in vacuo (1.6 mbar, 75 °C, 1 h).
C16H15Cl2N3O (336.22)
calcd.: C 57.16, H 4.50, N 12.50
found: C 56.78, H 4.47, N 12.23
IR (KBr): ν~ = 3137 (w), 3055 (w), 2990 (w), 2958 (w), 2919 (w), 2857 (w), 2829 (w),
1603 (m), 1588 (m), 1565 (w), 1481 (w), 1464 (m), 1427 (w), 1374 (w), 1318 (w), 1296
(w), 1272 (w), 1233 (w), 1186 (w), 1153 (m), 1094 (w), 1049 (w), 1011 (m), 948 (w),
896 (w), 871 (w), 815 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 284 (4.5), 269 (4.5, sh) nm.
1H NMR (400 MHz, CDCl3): δ = 2.36 (s, 6 H, CH3), 3.77 (s, 3 H, OCH3), 7.43 (ddd, 3J
= 7.5 Hz, 3J = 4.8 Hz, 4
J = 1.1 Hz, 1 H, PyH), 7.80 (s, 2 H, ArH)), 7.83 (“td”, 3J = 7.7
Hz, 4J = 1.7 Hz, 1 H, PyH), 8.24 (“dt”, 3
J = 8.0 Hz, 5J = 0.9 Hz, 1 H, PyH), 8.78 (ddd,
3J = 4.8 Hz, 4J = 1.6 Hz, 5J = 0.8 Hz, 1 H, PyH) ppm.
Syntheses 193
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.9 (q, OCH3), 123.5 (d, PyCH),
125.8 (d, PyCH), 128.9 (s, ArC), 129.5 (d, ArCH), 131.5 (s, ArCCH3), 136.9 (d, PyCH),
143.9 (CClPy), 144.2 (s, ArCCl), 149.7 (d, PyCH), 150.9 (s, PyC), 160.6 (s, ArCO)
ppm.
MS (FAB): m/z (%) = 358 (11) [M+Na]+, 336 (100) [M+H]+, 300 (53), 196 (50), 161
(18), 137 (15), 105 (15), 78 (33).
194 Experimental Part
1H NMR (400 MHz, CDCl3): N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)-picolinohydrazonoyl chloride (247)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
6.16
3.00
0.99
1.80
1.05
1.00
0.94
2.36
3.77
7.43
7.80
7.83
8.24
8.78
7.58.08.5f1 (ppm)
0.99
1.80
1.05
1.00
0.94
7.43
7.80
7.83
8.24
8.78
13C NMR (100 MHz, CDCl3): N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)-picolinohydrazonoyl chloride (247)
0102030405060708090100110120130140150160f1 (ppm)
16.4
59.9
123.5
125.8
128.9
129.5
131.5
136.9
143.9
144.2
149.7
150.9
160.6
Syntheses 195
2.1.27 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)
Picolinohydrazonoyl chloride 247 (211 mg, 0.63 mmol) was dissolved in anhydrous
acetonitrile (5 mL) and hydrazine hydrate (30 µl, 0.60 mmol) was added. The mixture
was heated to 50 °C for 1 h, then potassium carbonate (169 mg, 1.22 mmol) was added
and the mixture refluxed for 24 h. After renewed addition of hydrazine hydrate (90 µl,
1.83 mmol) it was refluxed for another hour and cooled to room temperature. The solid
was collected by filtration, washed with ethanol and purified by flash chromatography
(silica gel, PE/EtOAc 5:1 to 1:1, Rf (2:1) = 0.18). Oxadiazole 253 (50 mg, 28 %) was
obtained as pale brown solid, which was recrystallized from ethanol to yield analytically
pure material (32 mg, 18 %) after drying in vacuo (1 mbar, 50–75 °C) with
mp 157–158 °C.
C16H15N3O2 (281.31)
calcd.: C 68.31, H 5.37, N 14.94
found: C 68.24, H 5.33, N 14.90
IR (KBr): ν~ = 3094 (w), 3060 (w), 2986 (w), 2952 (w), 2938 (w), 2922 (w), 2856 (w),
2830 (w), 1608 (w), 1588 (w), 1546 (w), 1476 (m), 1462 (s), 1443 (m), 1410 (m), 1375
(w), 1310 (w), 1293 (w), 1243 (m), 1207 (m), 1171 (w)1142 (w), 1116 (m), 1092 (w),
1046 (w), 1015 (m), 989 (w), 973 (w), 955 (w), 888 (w), 803 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 292 (4.3), 267 (4.2, sh) nm.
1H NMR (400 MHz, CDCl3): δ = 2.36 (s, 6 H, CH3), 3.79 (s, 3 H, OCH3), 7.47 (ddd, 3J
= 7.6 Hz, 3J = 4.8 Hz, 4
J = 1.1 Hz, 1 H, PyH), 7.90 (s and “td”, superimposed, 3J = 7.8
Hz, 4J = 1.4 Hz, 3 H, ArH, PyH), 8.32 (“dt”, 3
J = 8.0 Hz, 5J = 0.9 Hz, 1 H), 8.82 (ddd,
3J = 4.8 Hz, 4J = 1.6 Hz, 5J = 0.9 Hz, 1 H, PyH) ppm.
196 Experimental Part
13C{
1H} NMR (100 MHz, CDCl3): δ = 16.2 (q, CH3), 59.9 (q, OCH3), 119.1 (s, ArC),
123.4 (d, PyCH), 125.8 (d, PyCH), 128.2 (d, ArCH), 132.2 (s, CCH3), 137.3 (d, PyCH),
144.0 (s, PyC), 150.4 (d, PyCH), 160.5 (s, ArCO), 163.8 (s, PyCC), 165.8 (s, ArCC)
ppm.
MS (EI, 70 eV): m/z (%) = 281 (100) M+, 238 (15), 210 (15), 163 (82), 78 (19).
Syntheses 197
1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.0f1 (ppm)
6.40
3.00
0.97
2.97
0.89
0.93
2.36
3.79
7.47
7.90
8.32
8.82
7.47.67.88.08.28.48.68.8f1 (ppm)
0.97
2.97
0.89
0.93
7.47
7.90
8.32
8.82
13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-oxadiazole (253)
0102030405060708090100110120130140150160170f1 (ppm)
16.2
59.9
119.1
123.4
125.8
128.2
132.2
137.3
144.0
150.4
160.5
163.8
165.8
198 Experimental Part
2.1.28 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)
Hydrazonoyl chloride 247 (220 mg, 0.65 mmol) and hydrazine dihydrochloride (310
mg, 98 %, 2.89 mmol) were dissolved in dry pyridine under argon and refluxed for 1 h.
The solvent was removed in vacuo, the residue taken up in CHCl3 (20 mL) and washed
with water (3 x 20 mL), dried over MgSO4 and the solvent was evaporated. The brown
residue was purified by flash chromatography (silica gel, PE/EtOAc 5:1 to 2:1,
Rf (2:1) = 0.24) to yield 248 as red film (~ 94 mg, 49 %) already containing traces of
tetrazine due to oxidation in air. The mixture was used without further purification.
Dihydrotetrazine 248 (80 mg, 0.27 mmol) was dissolved in conc. acetic acid (2 mL) at 0
°C and aqueous 10 % NaNO2 (2 mL) was added dropwise. Diethylether (1 mL) was
added to the highly viscous purple mixture and it was stirred for 20-30 min. The
precipitated solid was collected by filtration, purified by flash chromatography (silica
gel, PE/EtOAc 1:1, Rf = 0.23) and dried in vacuo (1.3 mbar, 75–100 °C, 2 h) to yield
tetrazine 249 (21 mg, 47 %) as purple solid with mp 154–155 °C.
HRMS: C16H15N5O (293.32)
calcd.: 293.1277
found: 293.1294
IR (KBr): ν~ = 3042 (w), 2983 (w), 2920 (w), 2830 (w), 1598 (w), 1582 (w), 1571 (w),
1491 (w), 1466 (w), 1436 (w), 1390 (s), 1326 (w), 1246 (w), 1212 (m), 1173 (w), 1118
(w), 1090 (w), 1072 (w), 1058 (w), 1040 (w), 1005 (w), 993 (w), 955 (w), 915 (w), 893
(w), 834 (w), 778 (w), 765 (w), 737 (w), 714 (w) cm-1.
Syntheses 199
UV/Vis (CH3CN): λmax (lg ε) = 538 (2.7), 310 (4.6), 303 (4.5), 235 (4.1) nm.
1H NMR (400 MHz, CDCl3): δ = 2.43 (s, 6 H, CH3), 3.83 (s, 3 H, OCH3), 7.55 (ddd, 3J
= 7.6 Hz, 3J = 4.8 Hz, 4J = 1.1 Hz, 1 H, PyH), 7.98 (“td”, 3J = 7.8 Hz, 4J = 1.8 Hz, 1 H,
PyH), 8.37 (s, 2 H, ArH), 8.67 (d, 3J = 7.9 Hz, 1 H, PyH), 8.96 (ddd, 3
J = 4.7 Hz, 4J =
1.6 Hz, 5J = 0.8 Hz, 1 H PyH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.5 (q, CH3), 59.9 (q, OCH3), 123.9 (d, PyCH),
126.3 (d, PyCH), 126.9 (s, ArC), 129.5 (d, ArCH), 132.4 (s, CCH3), 137.5 (d, PyCH),
150.7 (s, PyC), 151.0 (d, PyCH), 161.7 (s, ArCO), 163.3 (s, PyCC), 164.3 (s, ArCC)
ppm.
MS (FAB): m/z (%) = 316 (17) [M+Na]+, 294 (100) [M+H]+, 161 (33), 105 (46).
200 Experimental Part
1H NMR (400 MHz; CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)
13C NMR (100 MHz; CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-tetrazine (249)
Syntheses 201
2.1.29 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)
Benzoyl chloride 245 (1.61 g, 8.09 mmol) was dissolved in THF (12 mL) and cooled to
0 °C. A solution of benzohydrazide (257) (1.03, 7.59 mmol) and sodium carbonate
(754 mg, 7.11 mmol) in water (10 mL) and THF (12 mL) was added dropwise and a
colorless solid precipitated. The mixture was stirred for 3 h at 0 °C and the solid
collected by filtration, washed with MTBE and dried in vacuo (2.4 mbar, 100–125 °C).
258 (2.55 g, 89 %) was obtained as colorless solid with mp 207–209 °C.
HRMS (EI, 70 eV): C17H18N2O3 (298.34)
calcd.: 298.1317
found: 298.1280
IR (KBr): ν~ = 3226 (w), 3040 (w), 3005 (w), 2939 (w), 2824 (w), 1668 (m), 1637 (s),
1604 (w), 1580 (w), 1527 (m), 1483 (m), 1451 (m), 1377 (w), 1306 (m), 1276 (w), 1245
(w), 1222 (m), 1188 (w), 1164 (w), 1115 (w), 1079 (w), 1046 (w), 1019 (w), 962 (w),
935 (w), 903 (w), 884 (w), 833 (w), 803 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 238 (4.0) nm.
1H NMR (400 MHz, DMSO-d6): δ = 2.28 (s, 6 H, CH3), 3.70 (s, 3 H, OCH3), 7.49 (t, J
= 7.3 Hz, 2 H, m-Ar’H), 7.56 (t, J = 7.3 Hz, 1 H, p-Ar’H), 7.62 (s, 2 H, ArH), 7.92 (d, J
= 7.1 Hz, 2 H, o-Ar’H), 10.38 (br s, 2 H, NH) ppm.
13
C{1H} NMR (100 MHz, DMSO- d6): δ = 15.9 (q, CH3), 59.4 (q, OCH3), 127.3 (d, p-
Ar’CH), 128.1 (d, ArCH), 128.3 (d, m-Ar’CH), 128.4 (s, ArC), 130.3 (s, CCH3), 131.4
(d, p-Ar’CH), 133.3 (s, Ar’C), 159.1 (s, ArCO), 165.0 (s, C=O), 165.3 (s, C=O) ppm.
MS (FAB): m/z (%) = 321 (67) [M+Na]+, 299 (42) [M+H]+, 163 (100).
202 Experimental Part
1H NMR (400 MHz, DMSO-d6): N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.59.09.510.010.5f1 (ppm)
6.37
3.22
1.96
1.22
2.00
1.58
2.28
3.70
7.47
7.58
7.62
7.92
10.38
7.47.57.67.77.87.98.0f1 (ppm)
1.96
1.22
2.00
7.47
7.58
7.62
7.92
13C NMR (100 MHz, DMSO-d6): N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)
0102030405060708090100110120130140150160f1 (ppm)
15.9
59.4
127.3
128.1
128.3
128.4
130.3
131.4
133.3
159.3
165.0
165.3
127128129130131132133f1 (ppm)
127.3
128.1
128.3
128.4
130.3
131.4
133.3
Syntheses 203
2.1.30 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzo-hydrazonoyl
chloride (259) and 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-
oxadiazole (260)
Benzohydrazide 258 (700 mg, 2.35 mmol) was dissolved in dry chloroform (50 mL),
PCl5 (9.77 g, 46.4 mmol) was added and the supension heated to reflux for 24 h. The
cooled mixture was poured into ice water (50 mL), the layers were separated and the
aqueous layer was extracted with DCM (3 x 30 mL). The combined organic layers were
washed with saturated aqueous NaHCO3 (2 x 50 mL), brine (30 mL) and dried over
MgSO4. The solvent was removed by rotary evaporation, the residue purified by flash
chromatography (silica gel, PE/EtOAc 10:1 to 2:1) to yield hydrazonoyl chloride 259
(Rf (2:1) = 0.70 and oxadiazole 260 (Rf (2:1) = 0.48). Analytically pure material of 259
was obtained by crystallization from ethanol and subsequent drying in vacuo (1.4 mbar,
75–100 °C), while 260 was crystallized from DCM/Et2O in the cold and dried
(1.3 mbar, 50–75 °C).
1st fraction (Rf = 0.70): hydrazonoyl chloride 259 (510 mg, 65 %) as colorless solid with
mp 80 °C.
HRMS (EI, 70 eV): C17H16Cl2N2O (335.23)
calcd.: 334.0640
found: 334.0633
IR (KBr): ν~ = 3059 (w), 3008 (w), 2961 (w), 2919 (w), 2873 (w), 1603, (w)1579 (w),
1509 (w), 1481 (w), 1446 (w), 1416 (w), 1375 (w), 1317 (w), 1247 (w), 1236 (w), 1182
(w), 1150 (m), 1048 (w), 996 (w), 953 (w), 927 (w), 893 (w), 880, (w) 814 (w), 759 (w)
cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 285 (4.3), 238 (4.4) nm.
204 Experimental Part
1H NMR (400 MHz, CDCl3): δ = 2.36 (s, 6 H, CH3), 3.78 (s, 3 H, OCH3), 7.43–7.55
(m, 3 H, m-Ar’H, p-Ar’H ), 7.80 (s, 2 H, ArH), 8.13 (dd, J = 8.3 Hz, J = 1.2 Hz, 2 H, o-
Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.4 (q, CH3), 59.9 (q, OCH3), 128.66 (d, m-
Ar’CH), 128.69 (d, o-Ar’CH), 129.1 (s, ArC), 129.5 (d, ArCH), 131.4 (s, CCH3), 131.9
(d, p-Ar’CH), 133.9 (s, Ar’C), 144.1 (s, Ar’CCCl), 144.3 (s, ArCCCl), 160.5 (s, ArCO)
ppm.
MS (FAB): m/z (%) = 335 (100) [M+H]+, 299 (39) [M–Cl]+, 196 (88), 161 (22), 138
(49), 105 (26), 91 (15), 77 (48), 55 (22), 43 (20).
Syntheses 205
1H NMR (400 MHz, CDCl3): N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethyl-benzohydrazonoyl chloride (259)
13C NMR (100 MHz, CDCl3): N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethyl-benzohydrazonoyl chloride (259)
206 Experimental Part
2nd fraction (Rf = 0.48): oxadiazole 260 (114 mg, 17 %) as colorless solid with
mp 103 °C.
C17H16N2O2 (280.32)
calcd.: C 72.84, H 5.75, N 9.99
found: C 72.67, H 5.50, N 9.88
IR (KBr): ν~ = 3074 (w), 3044 (w), 2950 (w), 2916 (w), 2851 (w), 1608 (w), 1550 (w),
1477 (m), 1412 (w), 1375 (w), 1339 (w), 1316 (w), 1300 (w), 1285 (w), 1243 (w), 1206
(w), 1175 (w), 1109 (w), 1083 (w), 1067 (w), 1015 (w), 997 (w), 959 (w), 921 (w), 887
(w), 871 (w), 776 (w), 762 (w), 727 (w), 687 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 286 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 2.38 (s, 6 H, CH3), 3.79 (s, 3 H, OCH3), 7.51–7.56
(m, 3 H, m-Ar’H, p-Ar’H), 7.81 (s, 2 H, ArH), 8.13–8.16 (m, 2 H, o-Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 60.0 (q, OCH3), 119.5 (s, ArC),
124.3 (s, Ar’C), 127.1 (d, o-Ar’CH), 127.8 (d, ArCH), 129.2 (d, m-Ar’CH), 131.7 (d, p-
Ar’CH), 132.2 (s, CCH3), 160.3 (s, ArCO), 164.5 (s, Ar’CC), 164.8 (s, ArCC) ppm.
MS (FAB): m/z (%) = 281 (100) [M+H]+, 163 (16).
Syntheses 207
1H NMR (400 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-oxadiazole (260)
13C NMR (100 MHz, CDCl3): 2-(4-Methoxy-3,5-dimethylphenyl)-5-phenyl-1,3,4-oxadiazole (260)
208 Experimental Part
2.1.31 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine
(261)
Hydrazonoyl chloride 259 (439 mg, 1.31 mmol) and hydrazine hydrate (80 µl,
1.05 mmol) were dissolved in dry ethanol (8 mL) under argon to give a red reaction
mixture, which was refluxed for 30 min. The precipitate was collected by filtration and
washed with cold ethanol to yield 261 (201 mg, 52 %) as yellow solid with
mp 189–191 °C after drying in vacuo (4.2 mbar, 75 °C, 1 h). The compound was used
without further purification.
IR (KBr): ν~ = 3268 (m), 3147 (w), 3044 (w), 2949 (w), 2828 (w), 2704 (w), 2584 (w),
1641 (w), 1601 (w), 1578 (w), 1493 (w), 1449 (w), 1421 (w), 1402 (w), 1351 (m), 1312
(w), 1293 (w), 1240 (w), 1206 (w), 1172 (w), 1117 (w), 1101 (w), 1009 (w), 970 (w),
926 (w), 882 (w), 845 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 251 (4.1) nm.
1H NMR (400 MHz, CDCl3): δ = 2.31 (s, 6 H, CH3), 3.74 (s, 3 H, OCH3), 7.12 (br s, 2
H, NH), 7.34 (s, 2 H, ArH), 7.41–7.47 (m, 3 H, m-Ar’H, p-Ar’H), 7.67 (dd, J = 7.8 Hz,
J = 1.6 Hz, 2 H, o-Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.3 (q, CH3), 59 9 (q, OCH3), 125.5 (s, ArC),
126.1 (d, o-Ar’CH), 126.8 (d, ArCH), 129.0 (m-Ar’CH), 130.4 (s, Ar’C), 130.8 (d, p-
Ar’CH), 131.9 (s, CCH3), 148.8 (s, tetrazine-C), 159.5 (s, ArCO) ppm.
MS (FAB): m/z (%) = 294 (100) M+, 186 (12), 162 (12).
Syntheses 209
1H NMR (400 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine (261)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
6.12
3.01
1.81
2.00
3.28
1.99
2.31
3.74
7.12
7.34
7.41
7.47
7.67
13C NMR (100 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-tetrazine (261)
0102030405060708090100110120130140150160f1 (ppm)
16.3
59.9
125.5
126.1
126.8
129.0
130.4
130.8
131.9
148.8
125127129131f1 (ppm)
125.5
126.1
126.8
129.0
130.4
130.8
131.9
34567f2 (ppm)
155
160 f1 (ppm)
{2.33,159.56}
{3.73,159.45}
{7.35,159.51}
210 Experimental Part
2.1.32 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)
Dihydrotetrazine 261 (175 mg, 0.59 mmol) was dissolved in conc. acetic acid (2 mL) at
0 °C and aqueous NaNO2 (10 %, 2 mL) was added dropwise. Diethylether (1 mL) was
added to the purple mixture and it was stirred for 15 min. The precipitated solid was
collected by filtration, washed with methanol and dried in vacuo (1.6 mbar, 100 °C) to
yield tetrazine 262 (47 mg, 27 %) as purple solid with mp 124 °C. The mother liquor
was washed with water (2 x 10 mL), aqueous NaHCO3 (10 %, 2 x 10 mL) and water
(15 mL), dried over MgSO4 and the solvent was removed by rotary evaporation to yield
further 25 mg according to NMR, giving an overall yield of 41 %.
HRMS: C17H16N4O (292.34)
calcd.: 292.1324
found: 292.1348
IR (KBr): ν~ = 3061 (w), 2959 (w), 2923 (w), 2834 (w), 1600 (w), 1490 (w), 1447 (w),
1420 (w), 1293 (s), 1308 (w), 1245 (w), 1209 (m), 1174 (w), 1109 (w), 1069 (w), 1045
(w), 1005 (w), 955 (w), 914 (w), 895 (w), 848 (w), 828 (w), 797 (w), 757 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 514 (2.4), 305 (4.3) nm.
1H NMR (400 MHz, CDCl3): δ = 2.43 (s, 6 H, CH3), 3.83 (s, 3 H, OCH3), 7.61–7.63
(m, 3 H, m-Ar’H, p-Ar’H), 8.33 (s, 2 H, ArH), 8.64 (dd, 3J = 7.4 Hz, 4
J = 2.0 Hz, 2 H,
o-Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 16.5 (q, CH3), 60.0 (q, OCH3), 127.2 (s, ArC),
128.0 (s, o-Ar’CH), 129.0 (d, ArCH), 129.4 (d, m-Ar’CH), 132.1 (s, Ar’C), 132.4 (s,
CCH3), 132.6 (d, p-Ar’CH), 161.4 (s, ArCO), 163.8 (s, Ar’CC), 163.9 (s, ArCC) ppm.
212 Experimental Part
1H NMR (400 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)
13C NMR (100 MHz, CDCl3): 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine (262)
Syntheses 213
2.2 Syntheses at the upper rim of calixarenes
2.2.1 Transannular cyclization-product (cone) (61)
In three parallel reactions, a suspension of calixarene 60 (124, 126 and 127 mg,
16 µmol), iodine (91–99 mg, 0.36–0.38 µmol) and potassium carbonate (1.199–1.202 g,
8.68–8.70 µmol) in benzene (200 mL) was degassed with argon (30 min) and irradiated
for 15 h (125-W medium-pressure lamp, quartz filter), while a permanent argon stream
was bubbled through the solution. Benzene was removed in vacuo and the combined
residues were suspended in dichloromethane (600 mL) and insoluble material was
filtered off. The solvent was evaporated and the black residue (~ 600 mg) was purified
by flash chromatography (silica gel, PE to PE/EtOAc 10:1, Rf (20:1) = 0.42) to yield
339 mg (90 %) of cyclization products. By HPLC (n-hexane/EtOAc 80:1,
p = 1.6–1.7 MPa, flow = 10 mL/min) and subsequent drying in vacuo (0.31 mbar, 50
°C, 1.5 h) 141 mg (37 %) of 61 were isolated as a colorless solid with mp 266–268 °C.
Crystals suitable for XRS were obtained by crystallization from DCM/MeOH. 1H NMR spectra of other HPLC fractions indicated also compounds 62 and 63 in minor
amounts and purity: approximate yields were determined from NMR spectra to be about
6 % for the desired diphenanthrene 62 and about 25 % for compound 63 (Figure 2.3).
C56H60O4 (797.07)
calcd.: C 84.38, H 7.59
found: C 83.98, H 7.22
214 Experimental Part
IR (KBr): ν~ = 3056 (w), 3026 (w), 2962 (m), 2930 (m), 2874 (m), 1601 (w), 1584 (w),
1463 (s), 1383 (w), 1278 (w), 1214 (m), 1172 (w), 1128 (w), 1073 (w), 1037 (w), 1008
(m), 966 (m), 920 (w), 890 (w), 870 (w), 833 (w), 799 (w), 768 (w), 721 (w).
UV/Vis (n-hexane): λmax (lgε) = 271 (3.4), 225 (4.8, sh).
1H NMR (400 MHz, CDCl3): δ = 0.85 und 0.86 (t, superimposed, both J = 7.4 Hz, 6 H,
CH3), 1.12 (t, J = 7.4 Hz, 6 H, CH3), 1.75–1.88 (m, 8 H, CH2), 3.15 (d, J = 14.4 Hz, 2
H, ArCH2Ar), 3.21 (d, J = 14.3 Hz, 2 H, ArCH2Ar), 3.69 (t, J = 6.4 Hz, 4 H, OCH2),
3.76 („d“, AA’BB’, „J“ = 7.0 Hz, 2 H, cyclobutane-H), 3.86 („d“, AA’BB’, „J“ = 7.0
Hz, 2 H, cyclobutane-H), 3.88–3.93 (m, 4 H, OCH2), 4.45 and 4.49 (both d,
superimposed, both J = 13.9 Hz, 4 H, ArCH2Ar), 5.50 (d, 3J = 2.0 Hz, 2 H, m-ArH),
5.86 (d, 3J = 2.0 Hz, 2 H, m-ArH), 6.87–6.89 (m, 4 H, o-PhH), 6.94–7.05 (m, 8 H, PhH,
p-ArH), 7.13 (d, J = 7.3 Hz, 2 H, m-ArH), 7.21 (d, J = 7.4 Hz, 2 H, m-ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.00, 10.02, 11.1 (all q, CH3), 23.2, 23.3, 23.7
(all t, CH2), 31.4, 31.6 (both t, ArCH2Ar), 45.0 (d, cyclobutane-C-Ph), 48.7 (d,
cylclobutane-C), 76.26, 76.31, 76.34 (all t, OCH2), 121.5 (d, p-ArCH), 125.1 (d, m-
ArCH), 125.5 (d, p-PhCH), 127.7 (d, m-PhCH), 128.3 (d, o-PhCH), 128.7 (m-ArCH),
129.4 (d, m-ArCH), 129.6 (d, m-ArCH), 133.9 (s, ArCCH2Ar, p-ArC), 134.3
(ArCCH2Ar), 138.0, 138.1 (both s, ArCCH2Ar), 141.7 (PhC), 154.4, 159.4, 159.5 (all s,
ArCO) ppm.
MS (FAB): m/z (%) = 796 (100) M+.
Syntheses 215
1H NMR (400 MHz, CDCl3): Transannular cyclization-product (cone) (61)
13C NMR (100 MHz, CDCl3): Transannular cyclization-product (cone) (61)
216 Experimental Part
2.2.2 cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]arene (73)
Calixarene 72 (2.89 g, 3.79 mmol) was dissolved in dry toluene (200 mL), anhydrous
AlCl3 (1.01 g, 7.52 mmol) was added at 0 °C and the mixture was stirred at 0 °C for 45
min and additional 20 min at room temperature. The reaction was quenched with HCl
(1 N, 50 mL) and the separated aqueous layer was extracted twice with dichloromethane
(40 mL). The combined organic layer was washed with water (50 mL), dried over
MgSO4 and solvents were removed in vacuo. The residue was treated with
CH2Cl2/MeOH (1:1), concentrated to 25 % of the volume, the resulting precipitate was
filtered off and dried in vacuo (0.82–1.7 mbar, 100 °C, 3 h) to give 1.88 g (85 %) of
calixarene 73 as a colorless solid with mp > 300 °C (lit.80c mp > 300 °C).
1H NMR (200 MHz, CDCl3): δ = 3.49 (br s, 4 H, ArCH2Ar), 4.18 (br s, 4 H, ArCH2Ar),
6.77 (t, J = 7.5 Hz, 2 H, p-ArH), 7.02–7.11 (m, 4 H, m-ArH), 7.14 (d, 3J = 2.4 Hz, 2 H,
BrArH), 7.19 (d, 3J = 2.4 Hz, 2 H, BrArH ), 10.04 (s, 4 H, OH) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 31.5, 31.6, 31.7 (all t, all ArCH2Ar), 114.1 (s),
122.7 (d), 127.4 (s), 128.3 (s), 129.2 (d), 129.5 (d), 129.6 (s), 130.6 (s), 131.6 (d), 131.9
(d), 148.2, 148.7 (both s) ppm.
NMR spectroscopic data are in accord with the literature.80c
Syntheses 217
1H NMR (200 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]-arene (73)
13C NMR (50 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetrahydroxycalix[4]-arene (73)
218 Experimental Part
2.2.3 cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]arene (74)
NaH (60 % in mineral oil, 2.47 g, 61.7 mol) was washed with hexane (3 x 15 mL),
suspended in dry DMF (80 mL) and the mixture was heated to 60 °C for 30 min after
addition of calixarene 73 (1.80 g, 3.09 mmol). Propyl iodide was added and after
stirring at room temperature for 30 min the reaction mixture was heated an additional
2 h at 60–70 °C. The reaction was quenched with ice cold water (110 mL) and the
aqueous layer was extracted with dichloromethane (3 x 30 mL). The organic layer was
washed with aq. ammonium chloride (1 N, 2 x 50 mL), water (50 mL), brine (50 mL),
dried over MgSO4 and the solvent was evaporated. The residue was purified by flash
chromatography (silica gel, PE/DCM 8:1, Rf in 2.5:1 PE/DCM = 0.51) and dried in
vacuo (1.4–3.9 mbar, 100 °C, 2 h). 1.66 g (94 %) of calixarene 74 were obtained as a
colorless solid with mp 80–82 °C (lit.80c 117–119 °C).
1H NMR (200 MHz, CDCl3): δ = 0.97 and 0.98 (both t, superimposed, J = 7.4 and 7.5
Hz, 12 H, OCH3), 1.77–1.97 (m, 8 H, CH2), 3.04, 3.11 and 3.17 (all d, J = 13.9 Hz, J =
13.6 Hz, J = 13.0 Hz, 4 H, ArCH2Ar), 3.75–3.86 (m, 8 H, OCH2), 4.35, 4.39 and 4.44
(all d, J = 13.6 Hz, J = 13.6 Hz, J = 13.4 Hz, 4 H, ArCH2Ar), 6.56–6.72 (m, 10 H, ArH)
ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 10.4, 10.5 (both q, CH3), 23.27, 23.28 (both t,
CH2), 30.9, 31.0, 31.1 (all t, ArCH2Ar), 76.8, 76.9 (both t, OCH2), 114.8, 122.4, 128.1,
128.7, 130.6, 131.2, 134.4, 135.4, 136.7, 137.8, 156.0, 156.7 (both s, ArCO) ppm.
MS (FAB): m/z (%) = 750 (82) M+.
NMR spectroscopic data are in accord with literature. 80c,82
Syntheses 219
1H NMR (200 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]-arene (74)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.0f1 (ppm)
11.61
8.40
4.13
8.01
4.00
9.74
0.97
0.98
1.77
1.97
3.04
3.11
3.17
3.75
3.86
4.35
4.39
4.44
6.56
6.72
13C NMR (50 MHz, CDCl3): cone-5,11-Dibromo-25,26,27,28-tetra-n-propoxycalix[4]-arene (74)
220 Experimental Part
2.2.4 cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]arene (75)
To a cooled (–78 °C) solution of calixarene 74 (1.24 g, 1.65 mmol) in dry THF, nBuLi
(2.77 mL, 15 % in hexane, 4.41 mmol) was added. The reaction mixture was stirred
45 min at –78 °C and after addition of DMF (2.52 mL, 15.5 mmol) 2 h at room
temperature. The reaction was hydrolyzed with HCl (1 N, 40 mL), the aqueous layer
was extracted with dichloromethane (3 x 30 mL), the organic layer was washed with
water (3 x 30 mL), brine (30 mL) and dried over MgSO4. The solvent was evaporated
and the residue purified by flash chromatography (silica gel, PE/EtOAc 20:1 to 10:1,
Rf in PE/EtOAc 5:1 = 0.28). Diformylcalixarene 75 was obtained after drying in vacuo
(1.8 mbar, 50 °C, 2.5 h) in 632 mg (45 %) yield as a colorless solid.
1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.01 (two t, superimposed, both J = 7.4 Hz,
12 H, CH3), 1.81–1.99 (m, 8 H, CH2), 3.16 (d, J = 13.6 Hz, 1 H, ArCH2Ar), 3.25 (d, J =
14.0 Hz, 2 H, ArCH2Ar), 3.32 (d, J = 14.7 Hz, 1 H, ArCH2Ar), 3.77–4.10 (m, 8 H,
OCH2), 4.42 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.47 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 4.52
(d, J = 13.6 Hz, 1 H, ArCH2Ar), 6.47–6.61 (m, 6 H, ArH), 7.12 and 7.14 (two d, both 3J
= 1.9 Hz, 4 H, m-ArH), 9.65 (s, 2 H, ArCHO) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 10.4, 10.5 (both q, CH3), 23.4, 23.5 (both t, CH2),
31.1 (t, ArCH2Ar), 76.9 (t, OCH2), 122.4, 128.2, 128.8, 130.0, 130.8, 131.2, 134.3,
135.5, 135.6, 136.7, 156.6, 162.4, 191.7 ppm.
MS (FAB): m/z (%) = 671 (80) [M+Na]+, 648 (100) M+.
NMR spectroscopic data are in accord with the literature.86
Syntheses 221
1H NMR (200 MHz, CDCl3): cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]-arene (75)
13C NMR (50 MHz, CDCl3): cone-5,11-Diformyl-25,26,27,28-tetra-n-propoxycalix[4]-arene (75)
222 Experimental Part
2.2.5 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene
(65)
To a cooled (–78 °C) suspension of benzyltriphenylphosphonium chloride (285)
(939 mg, 2.42 mmol) in dry THF (20 mL), nBuLi (1.78 mL, 15 % in hexane, 2.85
mmol) was added. The reaction mixture was stirred 45 min at –78 °C and 30 min at
room temperature, during which the color changed from yellow to orange and finally
dark red. The reaction mixture was cooled to –78 °C and a solution of
diformylcalixarene 75 (607 mg, 0.94 mmol) in dry THF (25 mL) was added. The
reaction was allowed to warm to room temperature over night. After hydrolyzing with
water 20 mL) the aqueous layer was extracted with dichloromethane (2 x 50 mL), the
organic layer was washed with water (4 x 50 mL), once with brine (100 mL) and dried
over MgSO4. Solvents were removed in vacuo. 1.463 g of the resulting solid were
purified by flash chromatography (silica gel, PE/EtOAc 20:1, Rf = 0.35) and dried in
vacuo (1.0–5.2 mbar, 50 °C, 2.5 h). 691 mg (93 %) of distilbene 65 were obtained as a
colorless solid with mp 79–81 °C. Isomerization to the E/E isomer was achieved by
adding a crystal of iodine to the NMR sample and subsequent heating with a heat gun.
C56H60O4 (797.07)
calcd.: C 84.38, H 7.59
found: C 84.37, H 7.82
IR (KBr): ν~ = 3055 (w), 3020 (w), 2959 (s), 2930 (s), 2872 (s), 2735 (w), 1631 (w),
1594 (w), 1492 (w), 1461 (s), 1401 (w), 1383 (m), 1304 (w), 1280 (w), 1246 (m), 1216
(s), 1193 (m), 1159 (w), 1125 (m), 1083 (w), 1068 (w), 1037 (m), 1005 (s), 963 (s), 916
(w), 888 (w), 836 (w), 807 (w), 763 (s) cm-1.
Syntheses 223
UV/Vis (n-hexane): λmax (lgε) = 296 (4.5).
E/Z isomer: 1H NMR (400 MHz, CDCl3): δ = 0.96–1.04 (m, 12 H, CH3), 1.85–1.96 (m, 8 H, CH2),
2.89, 2.98, 2.99, 3.03, 3.16, 3.19 (all d, J = 13.3, 13.4, 14.0, 14.0, 13.4, 13.4 Hz, 4 H,
ArCH2Ar), 3.76–3.93 (m, 8 H, OCH2), 4.31, 4.36, 4.37, 4.39, 4.45, 4.46, 4.47 (all d, J =
13.2, 13.1, 13.3, 12.9, 13.4, 13.4, 13.4 Hz, 4 H, ArCH2Ar), 6.27–6.85 (m, 14 H, ArH,
alkene-H), 7.08–7.25 (m, 8 H, ArH), 7.32 (t, J = 7.6 Hz, 1 H, ArH), 7.42–7.54 (m, 1 H,
ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.37, 10.46, 10.48, 10.50, 10.60 (all q, CH3),
23.36, 23.38, 23.45 (all t, CH2), 31.0, 31.1, 31.2, 31.3 (all t, ArCH2Ar), 76.8 (t, OCH2),
122.0, 122.1, 122.2, 126.3, 126.4, 126.5, 126.6, 126.62, 126.66, 126.75, 126.83, 126.9,
127.06, 127.10, 128.0, 128.17, 128.22, 128.35, 128.41, 128.5, 128.6, 128.7, 128.9,
129.2, 129.4, 129.47, 129.53, 130.77, 130.81, 130.9 , 131.3, 134.5, 134.7, 134.8, 134.9,
135.0, 135.2, 135.26, 135.33, 135.38, 135.41, 135.60, 135.64, 135.7, 135.9, 137.95,
138.00, 138.12, 138.13, 156.2 (s, ArCO), 156.3 (s, ArCO), 156.55 (s, ArCO), 156.58 (s,
ArCO), 156.64 (s, ArCO), 156.8 (s, ArCO), 157.0 (s, ArCO), 157.2 (s, ArCO) ppm.
E/E isomer: 1H NMR (200 MHz, CDCl3): δ = 0.99 and 1.00 (two t, superimposed, J = 7.3 and 7.4
Hz, 12 H, CH3), 1.82-2.01 (m, 8 H, CH2), 3.15, 3.17 and 3.19 (three d, superimposed, J
= 13.6 Hz, J = 13.5 Hz, J = 13.6 Hz, 4 H, ArCH2Ar), 3.81–3.91 (m, 8 H, OCH2), 4.46
(d, J = 13.5 Hz, 4 H, ArCH2Ar), 6.48–6.64 (m, 6 H, ArH), 6.73 and 6.77 (d, J = 16.2 Hz
and s, superimposed, 6 H, alkene-H, m-ArH), 6.87 (d, J = 16.3 Hz, 2 H, alkene H),
7.16–-7.24 (m, 2 H, p-Ar’H), 7.32 ( “t”, “J” = 7.7 Hz, 4 H, m-Ar’H), 7.45 ( “d”, “J” =
7.8 Hz, 4 H, o-Ar’H) ppm.
MS (FAB): m/z (%) = 796 (100) M+.
224 Experimental Part
1H NMR (400 MHz, CDCl3): isomer mixture of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)
Syntheses 225
13C NMR (100 MHz, CDCl3): isomer mixture of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)
0102030405060708090100110120130140150160f1 (ppm)
10.4
10.5
10.5
10.5
10.6
23.4
23.4
23.4
31.0
31.1
31.2
31.3
122.0
122.1
122.1
130.8
130.8
130.9
137.9
138.0
138.1
138.1
156.2
156.3
156.5
156.6
156.6
157.0
157.2
77.077.5f1 (ppm)
76.8
134.4134.6134.8135.0135.2135.4135.6135.8136.0136.2f1 (ppm)
134.5
134.7
134.8
134.9
134.9
135.0
135.2
135.3
135.3
135.4
135.4
135.6
135.6
135.7
135.9
126.5127.0127.5128.0128.5129.0129.5f1 (ppm)
126.3
126.4
126.5
126.6
126.6
126.7
126.8
126.8
126.9
127.1
127.1
128.0
128.2
128.2
128.4
128.4
128.5
128.6
128.7
128.9
129.2
129.4
129.5
129.5
1H NMR (200 MHz, CDCl3): E isomer of cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxycalix[4]-arene (65)
226 Experimental Part
2.2.6 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c)
In four parallel reactions, a suspension of calixarene 65 (108, 109, 111 and 126 mg,
135-158 µmol), iodine (79–92 mg, 311–362 µmol) and potassium carbonate
(1.05–1.30 g, 76–87 µmol) in benzene (200 mL) was degassed with argon (30 min) and
irradiated for 17 h (125-W medium-pressure lamp, quartz filter). During the reaction a
permanent argon stream was bubbled through the solution. Benzene was removed in
vacuo, the combined residue was suspended in dichloromethane and insoluble material
was filtered off. The filtrate was washed with aqueous Na2S2O3 (10 %, 60 mL) and
dried over MgSO4 to give 573 mg of a brown residue. 301 mg (67 %) cyclization
products were obtained as a mixture after successive flash chromatography (silica gel,
PE/EtOAc 50:1 and PE/EtOAc 20:1, Rf = 0.32 in PE/EtOAc 20:1). 235 mg of this
mixture were subjected to HPLC (PE/EtOAc 200:1, p = 1.1–1.2 MPa) and the isolated
compounds dried in vacuo (1.1–1.8 mbar, 75–100 °C, 1.5 h).
1st Fraction: 123 mg (27 %) of 81a were isolated as a colorless solid with
mp 243–245 °C. Crystals suitable for XRS were obtained from chloroform/ethanol.
C56H56O4 (793.04)
calcd.: C 84.81, H 7.12
found: C 84.41, H 7.13
IR (KBr): ν~ = 3048 (w), 2959 (s), 2918 (m), 2872 (m), 1590 (w), 1511 (w), 1452 (s),
1442 (s), 1412 (w), 1377 (w), 1330 (w), 1285 (m), 1252 (m), 1206 (m), 1166 (w), 1137
(w), 1096 (w), 1083 (w), 1062 (w), 1033 (w), 1001 (s), 966 (s), 885 (w), 868 (w), 838
(w), 805 (m), 765 (m), 745 (m) cm-1.
UV/Vis (n-hexane): λmax (lgε) = 309 (4.0, sh), 259 (4.7), 221 (4.6, sh) nm.
Syntheses 227
1H NMR (600 MHz, CDCl3): δ = 0.79 (t, J = 7.5 Hz, 3 H, CH3), 0.94 (t, J = 7.4 Hz, 3
H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.33 (t, J = 7.4 Hz, 3 H, CH3), 1.72-2.14 (m, 8
H, CH2), 3.04 (d, J = 14.3 Hz, 1 H, ArCH2Ar), 3.25 (d, J = 13.3 Hz, 1 H, ArCH2Ar)
3.31 (d, J = 14.0 Hz, 1 H, ArCH2Ar), 3.56–3.63 (m, 2 H, OCH2), 3.90-3.97 (m, 2 H,
OCH2), 4.03–4.07 (m, 1 H, OCH2), 4.16–4.29 and 4.26 (m and d, superimposed, J =
12.9 Hz, 3 H, OCH2, ArCH2Ar), 4.49 (d, J = 13.2 Hz, 1 H, ArCH2Ar), 4.79 (d, J = 13.8
Hz, 1 H, ArCH2Ar), 5.30 (d, J = 7.3 Hz, 1 H, m-ArH), 5.71 (t, J = 7.2 Hz, 1 H, Phen-6-
H), 5.76 (d, J = 15.8 Hz, ArCH2Ar), 5.81 (d, J = 15.9 Hz, 1 H, ArCH2Ar), 6.00 (s, 1 H,
Phen-1-H), 6.16 (t, J = 7.5 Hz, 1 H, p-ArH), 6.23 (d, J = 7.2 Hz, 1 H, m-ArH), 6.80 (d, J
= 8.6 Hz, 1 H Phen-10-H), 6.84 (t , J = 7.3 Hz, 1 H, Phen-7-H), 7.04 (s, 1 H, Phen-1-H),
7.07 (d, J = 8.6 Hz, 1 H, Phen-9-H), 7.09 (t, J = 7.5 Hz, 1 H, p-ArH), 7.24-7.26 (m, 3 H,
m-ArH, Phen-8-H, Phen-10-H), 7.54 (d, J = 8.7 Hz, 1 H, Phen-9-H), 7.61 (d, J = 8.4 Hz,
1 H, Phen-5-H), 7.66 (t, J = 7.3 Hz, 1 H, Phen-7-H), 7.71 (t, J = 7.5 Hz, 1 H, Phen-8-H),
8.00 (d, J = 7.5 Hz, 1 H, Phen-8-H), 8.70 (d, J = 8.2 Hz, 1 H, Phen-5-H) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 9.8, 10.1, 11.0, 11.3 (all q, CH3), 22.2, 23.1,
23.7, 23.9 (all t, CH2), 30.7, 31.0, 31.5, 31.6 (all t, ArCH2Ar), 77.0, 77.2 (both t, OCH2),
122.1 (d, p-ArCH), 122.5 (d, Phen-C-6), 123.3 (d, p-ArCH), 123.9 (d, Phen-C-9), 124.3
(d, Phen-C-7), 124.6 (d, Phen-C-9), 124.9 (d, Phen-C-6), 125.8 (d, Phen-C-7), 125.9 (d,
m-ArCH), 126.6, 126.8, 127.0 (three d, Phen-C-8, Phen-C-10, m-ArCH), 127.3 (d,
Phen-C-5), 127.4 (s, Phen-C), 127.8 (d, Phen-C-5), 128.0 (d, Phen-C-1), 128.2 (d, Phen-
C-8), 128.3 (s, Phen-C), 128.5, 128.6 (both d, both Phen-C), 129.0 (s, Phen-C), 129.1
(d, m-ArCH), 129.5 (s, Phen-C), 129.8 (d, m-ArCH), 130.6 (s, PhenCCH2Phen), 131.1
(s, Phen-C), 131.5 (s, PhenCCH2Phen), 132.0 (s, Phen-C), 132.86 (s, ArCCH2Phen),
132.87 (s, ArCCH2Phen), 133.47, 133.49, 133.6 ( three s, PhenCCH2Ar, two Phen-C),
135.7 (s, PhenCCH2Ar), 137.0 (s, ArCCH2Phen), 138.3 (s, ArCCH2Ar), 155.0 (s,
ArCO), 156.9 (s, PhenCO), 158.7 (s, ArCO), 159.8 (s, PhenCO) ppm.
MS (FAB): m/z (%) = 815 (7) [M+Na]+, 792 (100) M+.
228 Experimental Part
1H NMR (600 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81a)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
13C NMR (150 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81a)
Syntheses 229
2nd Fraction: 31 mg (7 %) of 81b were isolated as a colorless solid with mp 129–131
°C.
IR (KBr): ν~ = 3046 (w), 2959 (s), 2930 (m), 2872 (m), 1592 (w), 1510 (w), 1454 (s),
1441 (s), 1413 (w), 1380 (w), 1332 (w), 1288 (w),1249 (w), 1214 (m), 1201 (m), 1177
(w), 1134 (w), 1101 (m), 1082 (w), 1064 (w), 1037 (w), 1004 (s), 967 (m), 882 (w), 838
(w), 804 (m), 758 (m), 744 (m), 700 (w) cm-1.
UV/Vis (n-hexane): λmax (lgε) = 310 (4.3), 269 (5.0) nm.
1H NMR (400 MHz, CDCl3): δ = 1.02 (t, J = 7.4 Hz, 6 H, CH3), 1.08 (t, J = 7.4 Hz, 6
H, CH3), 1.88–1.96 (m, 4 H, CH2), 1.98–2.11 (m, 4 H, CH2), 2.90 (d, J = 14.3 Hz, 1 H,
ArCH2Ar), 3.46 (d, J = 14.2 Hz, 1 H, ArCH2Ar), 3.79-3.92 (m, 4 H, OCH2), 4.03–4.09
(m, 2 H, OCH2) 4.28 (d and m, superimposed, J = 14.2 Hz, 3 H, ArCH2Ar, OCH2), 4.73
(d, J = 14.3 Hz, 2 H, ArCH2Ar), 4.94 and 4.98 (both d, superimposed, J = 14.4 Hz, J =
14.6 Hz, 3 H, ArCH2Ar), 5.84 (br s, 2 H, m-ArH), 6.07 (t, J = 7.3 Hz, 2 H, p-ArH), 6.26
(br s, 2 H, m-ArH), 7.04 (br s, 2 H, Phen-H), 7.38 (s, 2 H, Phen-H), 7.44-7.56 (m, 6 H,
Phen-H), 7.78 (d, J = 7.3 Hz, 2 H, Phen-H), 8.78 (d, J = 8.0 Hz, 2 H, Phen-5-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.5, 10.7 (both q, CH3), 23.3, 23.7 (both t,
CH2), 30.5, 30.9, 31.3 (all d, ArCH2Ar), 76.4, 78.3 (both t, OCH2), 121.3 (d, p-ArCH),
124.3), 124.7, 125.6 (all d, Phen-C), 127.6 (d, Phen-C m-ArCH), 128.1 (d, m-ArCH,
Phen-C), 128.5 (d, m-Phen-C, Phen-C-5), 129.0, 130.5, 130.7, 133.0 (all s, Phen-C),
134.2 (s, PhenCCH2Phen), 134.5 (s, ArCCH2Phen), 134.7 (s, ArCCH2Ar), 156.3 c(s,
ArCO), 159.0 (s, PhenCO) ppm.
MS (FAB): m/z (%) = 792 (100) M+.
230 Experimental Part
1H NMR (400 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81b)
13C NMR (100 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81b)
Syntheses 231
3rd Fraction: 63 mg (14 %) of 81c were isolated as a colorless solid with
mp 134–136 °C.
IR (KBr): ν~ = 3046 (w), 2959 (s), 2930 (m), 2872 (m), 2732 (w), 1590 (w), 1510 (w),
1454 (s), 1440 (s), 1413 (w), 1380 (w), 1335 (w), 1286 (w), 1248 (w), 1215 (m), 1200
(m), 1134 (w), 1101 (m), 1082 (w), 1064 (w), 1036 (w), 1003 (s), 967 (m), 881 (w), 838
(w), 805 (m), 762 (m), 744 (m) cm-1.
UV/Vis (n-hexane): λmax (lgε) = 359 (3.2), 343 (3.3), 307 (4.5, sh), 258 (4.9) nm.
1H NMR (400 MHz, CDCl3): δ = 0.94 (t, J = 7.4 Hz, 3 H, CH3), 1.00 (t, J = 7.4 Hz, 3
H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.11 (t, J = 7.4 Hz, 3 H, CH3), 1.87–2.03 (m, 8
H, CH2), 3.04 d, J = 13.9 Hz, 1 H, ArCH2Ar), 3.41 (d, J = 13.7 Hz, ArCH2Ar), 3.74–
4.13 (m, 7 H, OCH2), 4.22–4.28 (m, 1 H, OCH2), 4.38 (d, J = 13.8 Hz, 1 H, ArCH2Ar),
4.52 (d, J = 14.8 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 15.5 Hz, ArCH2Ar), 4.73 (d, J = 13.6
Hz, 1 H, ArCH2Ar), 4.94 (d, J = 14.8 Hz, 1 H, ArCH2Ar), 5.31 (d, J = 15.5 Hz, 1 H,
ArCH2Ar), 6.18 (t, J = 7.5 Hz, 1 H), 6.39 (br s, 2 H), 6.52 (d, J = 6.9 Hz, 3 H), 6.88 (d,
J = 8.5 Hz, 1 H), 7.19 (d, J = 8.7 Hz, 1 H), 7.38–7.44 (m, 4 H), 7.49 (br s, 2 H), 7.61
and 7.62 (m, 1 H), 7.73 (br „s“, 1 H), 8.73 („d“, „J“ = 7.4 Hz, 2 H, Phen-5-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.3, 10.5, 10.75, 10.78 (all q, CH3), 23.0, 23.3,
23.5 (all t, CH2), 30.0, 30.7, 31.4, 31.5 (all t, ArCH2Ar), 76.2, 77.0, 77.4, 77.8 (all t,
OCH2), 120.9, 122.5, 123.9, 124.0, 124.8, 125.1, 125.4, 125.6, 127.5, 127.6, 127.75,
127.84, 128.1, 128.2, 128.3, 128.5, 128.7 (s), 128.76 (s), 128.83 (s), 129.2 (s), 129.8 (s),
130.4 (s), 130.5 (s), 130.6 (s), 132.8 (s, 133.2 (s), 133.8 (s), 134.5 (s), 134.87 (s), 134.89
(s), 136.2 (s), 156.4, 157.0 (both s, ArCO), 157.9 (s, PhenCO) ppm.
MS (FAB): m/z (%) = 792 (100) M+.
232 Experimental Part
1H NMR (400 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81c)
13C NMR (100 MHz, CDCl3): proximal cone-Calix[4]diphenanthrene (81c)
Syntheses 233
2.2.7 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (85)
To a cooled (–78 °C) suspension of phosphonium bromide 84 (854 mg, 1.92 mmol) in
dry THF (20 mL) nBuLi (1.5 mL, 15 % in hexane, 2.39 mmol) was added. The reaction
mixture was stirred 45 min at –78°C and 30 min at room temperature. A solution of
diformylcalixaren 78 (475 mg, 733 µmol) in dry THF (10 mL) was added at –78 °C.
The reaction was allowed to warm to room temperature overnight. The suspension was
hydrolyzed with water (25 mL) and the aqueous layer was extracted with
dichloromethane (3 x 20 mL). The combined organic layer was washed twice with
water (20 mL), once with brine (30 mL) and dried over MgSO4. The solvent was
evaporated and the residue (1.37 g) purified by flash chromatography (silica gel,
PE/EtOAc 30:1 to 20:1) and dried in vacuo (0.61 mbar, 75 °C, 2 h) to yield 418 mg
(69 %) of calixarene 85 (Rf = 0.46 in PE/EtOAc 20:1) as a colorless solid.
Recrystallization from DCM/ MeOH and DCM/iPrOH gave 252 mg (42 %) crystals
with mp 229–231 °C.
C58H64O4·1/8 CH2Cl2 (835.74)
calcd.: C 83.53, H 7.75
found: C 83.41, H 7.34
IR (KBr): ν~ = 3057 (w), 3023 (w), 2958 (m), 2929 (m), 2871 (m), 1592 (w), 1492 (m),
1459 (s), 1383 (m), 1308 (m), 1287 (w), 1247 (m), 1219 (s), 1196 (m), 1169 (w), 1136
(m), 1106 (w), 1082 (m), 1037 (m), 1005 (s), 965 (m), 889 (w), 858 (w), 837 (w), 801
(w), 757 (s) cm-1.
234 Experimental Part
UV/Vis (n-hexane): λmax (lgε) = 280 (4.2), 228 (4.3, sh) nm.
1H NMR (400 MHz, CD2Cl2, diagnostic signals of the minor isomer are marked with an
asterisk): δ = 0.89*, 0.95*, 0.99*, 1.03, 1.05 (all t, 12 H, J = 7.4 Hz, CH2CH3), 1.89 und
2.12* (both br s), 6 H, CH3), 1.93–2.08 (m, 8 H, CH2), 2.88*, 3.16*, 3.19 (all d, J = 13.2
Hz, J = 13.1 Hz, 4 H, ArCH2Ar), 3.78*, 3.87, 3.94 (all t, J = 7.3 Hz, J = 7.4 Hz, J = 7.6
Hz, 8 H, OCH2), 4.32*, 4.46*, 4.50 (all d, J = 13.1 Hz, J = 13.1 Hz, 4 H, ArCH2Ar),
6.23–6.84 (m, 12 H, ArH and alkene-H), 7.10-7.50 (m, 10 H, PhH) ppm.
13
C{1H} NMR (100 MHz, CD2Cl2): δ = 10.7, 10.8 (both q, CH2CH3), 17.6 (q, CH3),
23.8, 24.0 (both t, CH2), 31.6 (t, ArCH2Ar), 77.4, 77.7 (both t, OCH2), 122.6 (d, p-
Ar’CH), 126.3 (d, PhCH), 127.1 (d, PhCH), 128.1 (d, Alken-CH), 128.7 (d, PhCH),
128.8 (d, m-Ar’CH, PhCH), 129.03* (d, PhCH), 129.68* (d, m-Ar’CH), 129.81 (d, m-
ArCH), 132.4, 135.0, 135.97, 136.00, 144.7 (all s), 155.8 (s, styryl-CO), 157.2 (s,
ArCO) ppm.
MS (FAB): m/z (%) = 824 (100) M+, 751 (8).
Syntheses 235
1H NMR (400 MHz, CD2Cl2): cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (85)
13C NMR (100 MHz, CD2Cl2): cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (85)
236 Experimental Part
2.2.8 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)phenanthrene (86a
and 86b)
In three parallel reactions, a suspension of calixarene 85 (84 mg, 102 µmol and twice
100 mg, 121 µmol), iodine (57 mg, 225 µmol; 68 mg, 269 µmol) and potassium
carbonate (759 mg, 5.49 mmol; 903 mg, 6.51 mmol) in benzene (200 mL) was degassed
with argon (30 min) and irradiated for 17 h (125 W medium-pressure lamp, quartz
filter), while a permanent argon stream was bubbled through the solution. Benzene was
removed in vacuo and the combined residues were suspended in dichloromethane
(20 mL) and insoluble material was filtered off. The solvent was evaporated and the
resulting brown solid (307 mg) was purified by flash chromatography (silica gel,
hexane/toluene 5:1 to 2:1, Rf (5:1) = 0.21; silica gel, PE/EtOAc 100:1, Rf = 0.17) to
yield 129 mg (46 %) of cyclization products. By HPLC (PE/EtOAc 200:1, p = 1.1 MPa)
and subsequent drying in vacuo (0.47 mbar, 75–80 °C, 1.5 h) 57 mg (20 %) of a
mixture of isomers 86a and 86b were obtained as a colorless solid with mp 161–163 °C.
C58H60O4 (821.09)
calcd.: C: 84.84, H: 7.37
found: C: 84.62, H: 7.12
IR (KBr): ν~ = 3066 (w), 3020 (w), 2959 (s), 2931 (s), 2872 (s), 2729 (w), 1621 (w),
1589 (w), 1518 (w), 1478 (m), 1452 (s), 1416 (m), 1382 (m), 1338 (m), 1290 (w), 1243
(s), 1196 (m), 1179 (s), 1142 (w), 1128 (w), 1083 (m), 1065 (w), 1036 (m), 1002 (s),
966 (s), 888 (w), 839 (w), 818 (w), 799 (w), 755 (s), 720 (w) cm-1.
UV/Vis (n-hexane): λmax (lgε) = 366 (3.3), 348 (3.4), 315 (4.4), 266 (5.1), 218 (4.9) nm.
Syntheses 237
Isomer 86a:
1H NMR (400 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 6 H, CH2CH3), 1.24 (t, J = 7.4 Hz,
6 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.74 (s, 6 H, CH3), 3.35 and 3.39 (two d,
superimposed, J = 14.9 Hz, J = 13.8 Hz, 2 H, ArCH2Ar), 3.76–3.86 (m, 4 H, OCH2),
4.15–4.26 (m, 2 H, OCH2), 4.32–4.44 (m, 2 H, OCH2), 4.60 (d, J = 13.4 Hz, 1 H,
ArCH2Ar), 4.62 (d, J = 13.2 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 14.9 Hz, 1 H, ArCH2Ar),
4.72 (d, J = 14.6 Hz, 1 H, ArCH2Ar), 4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar), 5.33 (d, J =
6.4 Hz, 2 H, m-ArH (86a)), 5.94 (t, J = 7.6 Hz, 2 H, p-ArH (86a)) 6.03 ( d, J = 6.7 Hz,
2 H, m-ArH (86a)), 7.52–7.62 (m, 8 H, Phen-H), 8.05 ( „t”, J = 7.5 Hz, J = 7.8 Hz, 2 H,
Phen-H), 8.60 (d, J = 7.9 Hz, 2 H, Phen-5-H) ppm.
Isomer 86b:
1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH2CH3), 1.16 (t, J = 7.4 Hz,
3 H, CH2CH3), 1.32 (t, J = 7.4 Hz, 3 H, CH2CH3), 1.89–2.16 (m, 8 H, CH2), 2.73 (s, 6
H, CH3), 3.35 and 3.39 (two d, superimposed, J = 14.9 Hz, J = 13.8 Hz, 2 H, ArCH2Ar),
3.74 (t, J = 6.7 Hz, 2 H, OCH2), 3.87 (t, J =6.5 Hz, 2 H, OCH2), 4.15–4.26 (m, 2 H,
OCH2), 4.32–4.44 (m, 2 H, OCH2), 4.60 (d, J = 13.4 Hz, 1 H, ArCH2Ar), 4.62 (d, J =
13.2 Hz, 1 H, ArCH2Ar), 4.66 (d, J = 14.9 Hz, 1 H, ArCH2Ar), 4.72 (d, J = 14.6 Hz, 1
H, ArCH2Ar), 4.87 (d, J = 14.7 Hz, 2 H, ArCH2Ar), 5.12 (d, J = 7.5 Hz, 2 H, m-ArH
86b), 5.64 (t, J = 7.6 Hz, 1 H, p-ArH 86b), 6.23–6.31 (m, 3 H, p-ArH, m-ArH 86b),
7.52–7.62 (m, 8 H, Phen-H), 8.05 ( „t”, J = 7.5 Hz, J = 7.8 Hz, 2 H, Phen-H), 8.57 (d, J
= 8.0 Hz d, 2 H, Phen-5-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.1, 11.0, 11.2, 11.3 (all q, all CH2CH3), 19.8
(q, CH3), 23.3, 23.4, 23.8, 23.9, 24.0 (all t, all CH2), 30.2, 31.2 (both t, both ArCH2Ar),
76.5, 76.7, 77.0, 77.8, 78.0 (all t, all OCH2), 122.7, 122.8, 122.9 (all d, all p-ArCH),
124.3, 124.4 (both d, both Phen-8-C), 124.5 (d, Phen-6-C), 125.8 (d, Phen-7-C), 126.3,
126.8, 127.1(all d, all m-ArCH), 127.2 (d, Phen-1-C), 127.4 (d, Phen-C), 127.6 (d, m-
ArCH), 127.7, 128.4 (both s, both Phen-C), 128.5, 128.6 (both d, both Phen-5-C), 130.3
(s), 130.6 (s), 131.0, 131.1 ((both s, both Phen-C), 132.2, 132.7 (both s, ArCCH2Phen),
238 Experimental Part
133.27 (s), 133.33 (s), 134.6, 134.9 (both s, both ArCCH2Phen), 136.91, 136.96 (both
s), 154.6, 154.9, 155.3 (all s, all ArCO), 159.6, 159.7 ( both s, both PhenCO) ppm.
MS (FAB): m/z (%) = 820 (100) M+.
Syntheses 239
1H NMR (400 MHz, CDCl3): cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-phenanthrene (86a and 86b)
13C NMR (100 MHz, CDCl3): cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-phenanthrene (86a and 86b)
240 Experimental Part
2.2.9 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (88)
To a cooled (–78 °C) suspension of phosphonium bromide 84 (5.09 g, 11.4 mmol) in
dry THF (70 mL) nBuLi (8.55 mL, 15 % in hexane, 13.6 mmol) was added. The
reaction mixture was stirred 1 h at –78°C and 30 min at room temperature. A solution of
tetraformylcalixaren 87 (802 mg, 1.13 mmol) in dry THF (15 mL) was added at –78 °C.
The reaction was allowed to warm to room temperature overnight. The suspension was
hydrolyzed with water (80 mL), the aqueous layer was extracted with ethyl acetate
(2 x 40 mL) and the organic layer was washed with water (50 mL), brine (50 mL) and
dried over MgSO4. The solvent was evaporated and the residue (3.04 g) purified by
flash chromatography (silica gel, PE/EtOAc 20:1) and dried in vacuo (1.6–2.1 mbar,
75 °C, 1.5 h) to yield 773 mg (64 %) of calixarene 88 (Rf = 0.54 in PE/EtOAc 10:1) as a
colorless solid with mp 167–168 °C.
C76H80O4 (1057.45)
calcd.: C 86.32, H 7.63
found: C 86.33, H 7.46
IR (KBr): ν~ = 3079 (w), 3053 (w), 3020 (w), 2959 (m), 2931 (m), 2873 (m), 1597 (w),
1576 (w), 1542 (w), 1493 (m), 1465 (s), 1444 (m), 1383 (w), 1310 (w), 1288 (w), 1219
(m), 1145 (w), 1126 (w), 1106 (w), 1067 (w), 1036 (w), 1006 (m), 964 (w), 941 (w),
894 (w), 853 (w), 756 (m), 695 (m) cm-1.
UV/Vis (n-hexane): λmax (lgε) = 278 (4.5), 228 (4.4) nm.
Syntheses 241
1H NMR (400 MHz, CDCl3, diagnostic signals of the minor isomer are marked with an
asterisk): δ = 0.96* ppm, 1.00*, 1.02*, 1.05 (all t, J = 7.4, 7.3, 7.4, 7.5 Hz, 12 H,
CH2CH3), 1.83*, 1.96, 2.16* (all s, CH3) and 1.88–2.08 (m, , 20 H), 2.90*, 3.19*, 3.22
(all d, J = 13.0, 12.7, 13.0 Hz, 4 H, ArCH2Ar), 3.79* (t, J = 7.3 Hz) and 3.88–4.01* (m
with 3.94, t, J = 7.6 Hz, 8H, OCH2), 4.34*, 4.49*, 4.53 (all d, J = 12.9 and 13.0 Hz, 4H,
ArCH2Ar), 6.22-6.90 (m, 12 H, C=CH, m-ArH), 7.12-7.49 (m, 20 H, Ar’H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.35* ppm, 10.52, 10.64* (all q, CH2CH3),
17.15*, 17.29, 17.68 (all q, CH3), 23.47, 23.50* (all t, CH2), 31.22*, 31.30 (all t,
ArCH2Ar), 77.0, 77.3 (all t, OCH2), 125.9, 126.0, 126.1*, 126.7*, 126.8 (all d, m-ArCH,
Ar’CH), 127.8, 127.9* (both d, m-ArCH, C=CH), 128.2*, 128.27, 128.33*, 128.6* (all d,
Ar’CH), 129.2*, 129.5 (both d, m-ArCH), 132.1*, 132.4 (all s), 134.63 (s, ArCCH2Ar),
135.6*, 135.7 (both s), 144.2 (s), 154.8*, 155.2 (both s, ArCO) ppm.
MS (FAB): m/z (%) = 1056 (79) [M]+, 940 (17).
242 Experimental Part
1H NMR (400 MHz, CDCl3): cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (88)
13C NMR (100 MHz, CDCl3): cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (88)
Syntheses 243
2.2.10 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-
calix[4]arene (132)
25,26-Dipropoxy-26,28-dihydroxy-calix[4]arene (131) (497 mg, 0.98 mmol) and
aluminium chloride (570 mg, 4.27 mmol) were dissolved in of dichloromethane (40 ml).
2-Bromophenylacetyl chloride (116) (503 mg, 2.15 mmol) was added and the solution
was stirred for 2 hours at room temperature. The mixture was treated with HCl (2 N,
30 mL) and the layers were separated. The organic layer was washed with water (2 x
20 mL), brine (20 mL), dried over MgSO4 and the solvent was evaporated. The crude
product (660 mg) was submitted to flash chromatography (silica gel, PE/EtOAc 5:1,
Rf (PE/EtOAc 1:1) = 0.83) and subsequently recrystallized from DCM/MeOH to yield
pure 132 (116 mg, 13 %) as a colorless solid.
1H NMR (200 MHz, CDCl3): δ = 1.32 (t, J = 7.5 Hz, 6 H, CH2CH3), 2.02–2.12 (m, 4
H, CH2CH3), 3.47 (d, J = 12.9 Hz, 4 H, ArCH2Ar), 3.99 (t, J = 6.2 Hz, 4 H, OCH2),
4.28 (d, J = 13.1 Hz, 4 H, ArCH2Ar), 4.38 (s, 4 H, CH2CO), 6.76 (t, J = 7.6 Hz, 2 H, p-
Ar’H), 6.92 (d, J = 6.8 Hz, 4 H, m-Ar’H), 7.08–7.23 (m, 6 H, PhH), 7.61 (d, J = 7.6 Hz,
2 H, PhH), 7.80 (s, 4 H, m-ArH) ppm.
244 Experimental Part
1H NMR (200 MHz, CDCl3): 5,17-(2-(2-Bromophenyl)acetyl)-25,27-di-n-propoxy-26,28-dihydroxy-calix[4]arene (132)
Syntheses 245
2.2.11 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene
(133) and 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]arene (134)
Calixarene 76 (500 mg, 0.84 mmol) and aluminium chloride (108 mg, 0.81 mmol) were
suspended in dry dichloromethane (35 mL). A solution of 2-bromophenylacetyl chloride
(120) (188 mg, 0.81 mmol) in dry dichloromethane (10 mL) was added dropwise over
1 h 40 min. The resulting yellow solution was stirred for further 10 min and then
hydrolyzed with 2 N HCl (30 mL). The organic layer was separated, washed with water
(2 x 20 mL), brine (20 mL) and dried over MgSO4. The solvent was removed by rotary
evaporation and the residue purified by column chromatography (silica gel, PE/DCM
3:1 to 1:1, Rf (1:1) = 0.71, 0.42) and the isolated products were dried in vacuo
(1.8 mbar, 50 °C).
1st fraction (Rf = 0.71): Tripropoxycalix[4]arene 134 (101 mg, 22 %) as colorless solid
with mp 107-108 °C (lit.131 101–102 °C).
1H NMR (200 MHz, CDCl3): δ = 0.94 (t, J = 7.6 Hz, 3 H, CH3), 1.13 (t, J = 7.4 Hz, 6
H, CH3), 1.82–2.00 (m, 4 H, CH2CH3), 2.19–2.38 (m, 2 H, CH2CH3), 3.23 and 3.31
(both d, superimposed, J = 13.8 Hz, J = 13.2 Hz, 4 H, ArCH2Ar), 3.75 and 3.82 (t and
“t”, superimposed, J = 6.6 Hz, “J” = 8.5 Hz, 6 H, OCH2), 4.39 and 4.43 (both d,
superimposed, J = 13.7 Hz, J = 13.1 Hz, 4 H, ArCH2Ar), 4.70 (s, 1 H, OH), 6.39 (m, 6
H, ArH), 6.79 (t, J = 7.4 Hz, 1 H, ArH), 6.98 (t, J = 7.4 Hz, 1 H, ArH), 7.11 (d, J = 7.4
Hz, 2 H, ArH), 7.19 (d, J = 7.4 Hz, 2 H, ArH) ppm.
246 Experimental Part
1H NMR (200 MHz, CDCl3): 25-Hydroxy-26,27,28-Tri-n-propoxycalix[4]aren (134)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5f1 (ppm)
3.39
6.31
4.21
2.07
4.02
6.23
4.00
0.86
5.96
1.00
1.25
1.94
1.90
0.94
1.13
1.82
2.00
2.19
2.38
3.23
3.31
3.75
3.78
3.86
4.39
4.43
4.70
6.39
6.79
6.98
7.11
7.19
2nd fraction (Rf = 0.42): Ethanone 133 (169 mg, 25 %) as colorless solid with
mp 69–71 °C. Recrystallization of 133 from DCM/MeOH yielded analytically pure
material.
C48H53BrO5 (789.94)
calcd.: C 72.99, H 6.76
found: C 72.97, H 6.59
IR (KBr): ν~ = 3057 (w), 3014 (w), 2960 (s), 2930 (s), 2873 (s), 2736 (w), 1684 (m),
1590 (m), 1457 (s), 1417 (w), 1383 (m), 1326 (m), 1282 (m), 1266 (m), 1245 (m), 1206
(s), 1194 (s), 1164 (m), 1134 (s), 1109 (m), 1085 (s), 1065 (m), 1037 (w), 1005 (m), 964
(s), 889 (s), 834 (w), 799 (w), 760 (s) cm-1.
UV/Vis (n-hexane): λmax (lg ε) = 272 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 0.98 (t, J = 7.5 Hz, 6 H, CH3), 1.02 and 1.04 (both t,
superimposed both J = 7.4 Hz, 6 H, CH3), 1.86 – 1.97 (m, 8 H, CH2CH3), 3.16 (d, J =
Syntheses 247
13.5 Hz, 2 H, ArCH2Ar), 3.21 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 3.81 (t, J = 7.3 Hz, 2 H,
OCH2), 3.84–3.94 (m, 6 H, OCH2), 4.14 (s, 2 H, C(O)CH2), 4.45 (d, J = 13.5 Hz, 2 H,
ArCH2Ar), 4.48 (d, J = 13.6 Hz, 3 H, ArCH2Ar), 6.41 (dd, J = 6.1 Hz, J = 8.6 Hz, 1 H,
p-Ar’’H), 6.47(d, J = 8.1 Hz, 2 H, m-Ar’’H), 6.65 (t, J = 7.4, 2 H, p-Ar’H), 6.71 – 6.74
(m, 4 H, m-Ar’H), 7.11 (“td”, J = 7.6, Hz, J = 1.7 H, Ph-4-H), 7.18 (dd, J = 7.7, J = 1.8
Hz, 1 H, Ph-6-H), 7.21 (s, 2 H, m-ArH), 7.25 (“td”, J = 7.4, Hz, J = 1.2 Hz, , 1 H, Ph-5-
H), 7.57 (dd, J = 8.0 Hz, J = 1.1, Hz, 1 H, Ph-3-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.4, 10.5, 10.6 (all q, CH3), 23.3, 23.46, 23.53
(all t, CH2CH3, 31.1, 31.2 (both, t, ArCH2Ar), 45.3 (t, C(O)CH2), 77.0 (t, OCH2), 122.0
(d, p-Ar’’CH), 122.4 (d, p-Ar’CH), 125.3 (s, CBr), 127.5 (d, Ph-5-CH), 128.09 (d, m-
Ar’’CH), 128.5 (d, m-Ar’CH), 128.6 (d, Ph-4-CH), 128.86 (d, m-ArCH), 128.92 (both
d, m-Ar’CH), 130.8 (s, p-ArC), 131.7 (d, Ph-6-CH), 132.9 (d, Ph-3-CH), 134.9 (s,
ArCCH2Ar), 135.0 (s, ArCCH2Ar), 135.5 (s, ArCCH2Ar), 135.6 (s, PhC), 135.8 (s,
ArCCH2Ar), 156.5 (s, Ar’’CO), 156.9 (s, Ar’CO), 161.2 (s, ArCO), 195.6 (s, C=O)
ppm.
MS (FAB): m/z (%) = 789 (27) [M+H]+, 619 (100) [M-CH2C6H5Br]+.
248 Experimental Part
1H NMR (400 MHz, CDCl3): 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (133)
13C NMR (100 MHz, CDCl3): 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (133)
10.36
10.54
10.58
23.34
23.46
23.53
31.13
31.20
45.32
121.97
122.35
135.83
156.46
156.93
161.23
195.55
121.97
122.35
125.28
127.50
128.09
128.49
128.55
128.86
128.92
130.81
131.73
132.85
134.88
134.95
135.49
135.62
135.83
76.98
23.34
23.46
23.53
10.36
10.54
10.58
31.13
31.20
Syntheses 249
2.2.12 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-
propoxycalixarene (136)
Acid chloride 116 (1.95 g, 8.36 mmol) and aluminium chloride (648 mg, 4.81 mmol)
were suspended in dry dichloromethane (8 mL), calixarene 76 (451 mg, 0.76 mmol)
was added and the mixture heated under reflux for 1 h 15 min. The cooled solution was
hydrolyzed with ice cold 2 N HCl (8 mL), and the aqueous layer was extracted with
dichloromethane (2 x 15 mL). The organic layer was washed with 10 % NaOH (15 mL),
water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed at a
rotary evaporator. The crude product (1.41 g) was purified by multiple flash
chromatography (silica gel, PE/DCM 2:1 and PE/EtOAc 5:1 to 1:1, Rf (2:1) = 0.56) and
dried in vacuo (1.0 mbar, 100 °C) to yield 136 (79 mg, 8 %) as colorless solid.
Analytically pure material with mp 291–293 °C was obtained by recrystallization from
DCM/MeOH.
C72H68Br4O8 (1380.92)
calcd.: C 62.62, H 4.96
found: C 62.28, H 4.99
IR (KBr): ν~ = 3056 (w), 2963 (w), 2932 (w), 2874 (w), 1682 (s), 1593 (w), 1469 (w),
1440 (w), 1415 (w), 1386 (w), 1331 (m), 1288 (w), 1268 (w), 1224 (w), 1197 (w), 1145
(s), 1047 (w), 1027 (w), 999 (w), 959 (w), 930 (w), 885 (w), 868 (w), 837 (w), 818 (w),
805 (w), 745 (m) cm-1.
1H NMR (400 MHz, CDCl3): δ = 1.02 (t, J = 7.4 Hz, 12 H, CH3), 1.88–1.97 (m, J = 7.4,
14.9 Hz, 8 H, CH2CH3), 3.33 (d, J = 13.8 Hz, 4 H, ArCH2Ar), 3.94 (t, J = 7.4 Hz, 8 H,
250 Experimental Part
OCH2), 4.10 (s, 8 H, CH2), 4.50 (d, J = 13.7 Hz, 4 H, ArCH2Ar), 7.02 (“td”, J = 7.7 Hz,
J = 1.7 Hz, 4 H, Ph-4-H), 7.11 (“td”, J = 7.5 Hz, J = 1.2 Hz, 4 H, Ph-5-H), 7.21 (dd, J =
7.6 Hz, J = 1.6 Hz, 4 H, Ph-6-H), 7.38 (s, 8 H, m-ArH), 7.50 (dd, J = 7.9 Hz, J = 1.2 Hz,
4 H, Ph-3-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.4 (q, CH3), 23.5 (t, CH2), 31.3 (t, ArCH2Ar),
45.4 (t, CH2), 77.2 (t, OCH2), 125.0 (s, CBr), 127.6 (d, Ph-5-CH), 128.5 (d, Ph-4-CH),
129.2 (d, m-ArCH), 131.2 (s, ArC), 132.4 (d, Ph-6-CH), 132.6 (d, Ph-3-CH), 135.1 (s,
ArCCH2Ar), 135.7 (s, PhC), 161.1 (s, ArCO), 195.5 (s, C=O) ppm.
MS (FAB): m/z (%) = 1424 (3), 1403 (2) [M+Na]+, 1381 (11) [M+H]+, 1251 (3), 1211
(18).
Syntheses 251
1H NMR (400 MHz, CDCl3): 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalixaren (136)
13C NMR (100 MHz, CDCl3): 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxycalixaren (136)
0102030405060708090100110120130140150160170180190200f1 (ppm)
10.4
23.5
31.3
45.4
125.0
127.6
128.5
129.2
131.2
132.4
132.6
135.1
135.7
161.1
195.5
77.077.5f1 (ppm)
77.2
128130132f1 (ppm)
127.6
128.5
129.2
131.2
132.4
132.6
252 Experimental Part
2.2.13 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)
To a solution of bromocalixarene 135 (1.14 g, 1.70 mmol) in dry THF (80 mL)
n-butyllithium (1.8 mL, 2.87 mmol, 1.6 M in hexane) was added at –78 °C. The solution
was stirred for 15 min, after which a solution of iodine (1.42 g, 5.60 mmol) in dry THF
(10 mL) was added. The reaction mixture was stirred at room temperature overnight.
Saturated aqueous Na2SO3 (90 mL) was added, the aqueous layer was extracted with
ethyl acetate (90 mL) and the organic layer was washed with brine and dried over
MgSO4. The solvent was removed at a rotary evaporator and the crude product (1.14 g)
was purified by flash chromatography (silica gel, 1. PE/EtOAc 15:1, Rf = 0.52;
2. PE/DCM 5:1, Rf in 4:1 = 0.39) and dried in vacuo (0.67 mbar, 50–75 °C, 30 min) to
yield 438 mg (36 %) 139a as colorless solid with mp 60–62 °C.
C40H47IO4 (718.70)
calcd.: C 66.85, H 6.59
found: C 66.98, H 6.40
IR (KBr): ν~ = 3058 (w), 3014 (w), 2960 (m), 2928 (w), 2872 (w), 2734 (w), 1566 (w),
1539 (w), 1456 (m), 1383 (w), 1291 (w), 1246 (w), 1207 (m), 1193 (m), 1159 (w), 1084
(w), 1038 (w), 1006 (m), 964 (w), 910 (w), 889 (w), 864 (w), 837 (w), 799 (w), 761 (w)
cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 272 (3.5) nm.
1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.02 and 1.03 (both t, J
= 7.4 Hz, superimposed, 1 H, CH3), 1.85–1.95 (m, 8 H, CH2CH3), 3.08 (d, J = 13.5 Hz,
2 H, ArCH2Ar), 3.16 (d, J = 13.5 Hz, 2 H, ArCH2Ar), 3.78 and 3.80 (both t, J = 7.2 Hz,
superimposed, 4 H, OCH2), 3.84–3.91 (m, 4 H, OCH2), 4.37 (d, J = 13.4 Hz, 2 H,
Syntheses 253
ArCH2Ar), 4.45 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 6.46 (d, J = 7.5 Hz, 2 H, m-Ar’’H),
6.66–6.78 and 6.73 (m and s, superimposed, 9 H, p-Ar’H, m-Ar’H, p-Ar’’H, m-ArH)
ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.3 (q, CH3), 10.58 (q, CH3), 10.64 (q, CH3),
23.3 (t, CH2CH3), 23.4 (t, CH2CH3), 23.5 (t, CH2CH3), 30.9 (t, ArCH2Ar), 31.2 (t,
ArCH2Ar), 77.0 (t, OCH2) , 86.0 (s, ArCI), 122.2 (d, p-Ar’CH), 122.5 (d, p-Ar’’CH),
128.0 (d, m-Ar’’CH), 128.4 (d, m-Ar’CH), 128.9 (d, m-Ar’CH), 134.7 and 135.0 (both
s, Ar’’CCH2Ar and Ar’CCH2Ar), 136.0 (s, Ar’’CCH2Ar’), 136.8 (d, m-ArCH), 137.6 (s,
ArCCH2Ar’), 156.3 (s, Ar’’CO), 156.5, (s, ArCO) 157.1 (s, Ar’CO) ppm.
MS (FAB): m/z (%) = 741 (12) [M+Na]+, 718 (79) M+, 648 (14), 592 (28).
254 Experimental Part
1H NMR (400 MHz, CDCl3): 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)
13C NMR (100 MHz, CDCl3): 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)
Syntheses 255
2.2.14 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b)
To a solution of dibromocalixarene 138 (2.03 g, 2.70 mmol) in dry THF (120 mL)
n-butyllithium (6 mL, 9.55 mmol, 1.6 M in hexane) was added at –78 °C. The solution
was stirred for 15 min, after which a solution of iodine (4.02 g, 15.8 mmol) in dry THF
(30 mL) was added. The reaction mixture was stirred at –78 °C for 15 min and at room
temperature overnight. Saturated aqueous Na2SO3 (150 mL) was added, the aqueous
layer was extracted with ethyl acetate (150 mL) and the organic layer was washed with
brine and dried over MgSO4. The solvent was removed at a rotary evaporator and the
yellow solid (2.14 g) was recrystallized from DCM/MeOH to yield 1.57 g (69 %) 139b
as colorless crystals with mp 249–251 °C (mp84 204–209 °C) after drying in vacuo
(1.6 mbar, 100 °C, 1 h).
1H NMR (200 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.00 (t, J = 7.4 Hz, 6
H, CH3), 1.80–1.95 (m, 8 H, CH2CH3), 3.09 (d, J = 13.3 , 4 H, ArCH2Ar), 3.77 (t, J =
7.3 Hz, 4 H, OCH2), 3.87 (t, J = 7.7 Hz, 4 H, OCH2), 4.37 (d, J = Hz, 4 H, ArCH2Ar),
6.44-6.55 (m, 6 H, ArH), 7.11 (s, 4 H, m-ArH) ppm.
MS (FAB): m/z (%) = 844 (18) M+, 718 (13) [M–I]+.
Data are in accord with the literature.84
256 Experimental Part
1H NMR (200 MHz, CDCl3): 5,17-Diiodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139b)
Syntheses 257
2.2.15 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(141a)
In a screw-cap flask iodotetrapropoxycalixarene 139a (690 mg, 0.96 mmol), copper(I)
iodide (19 mg, 98 µmol) and triphenylphosphine (25 mg, 95 µmol) were suspended in
dry triethylamine (10 mL) under argon. Palladium(II) chloride (8 mg, 45 µmol) and
1-bromo-2-ethynylbenzene (140) (268 mg, 1.48 mmol) were added and the mixture was
stirred at 80 °C for 3 d. The crude product was diluted with dichloromethane and
filtrated over Celite. The mixture was washed with water (3 x 30 mL), dried over
MgSO4 and the solvent was removed in vacuo. The residue was purified by flash
chromatography (silica gel, 1. PE/EtOAc 15:1 and 2. PE/DCM 6:1 to 2:1, Rf (6:1) =
0.29) to yield 141a (553 mg, 75 %) as colorless solid with mp 76 °C after drying in
vacuo (0.47 mbar, 50–75 °C, 30 min).
C48H51BrO4 (771.82)
calcd.: C 74.70, H 6.66
found: C 74.99, H 6.29
IR (KBr): ν~ = 3058 (w), 3015 (w), 2960 (m), 2929 (w), 2873 (w), 2210 (w, C≡C),
1586 (w), 1455 (m), 1434 (w), 1383 (w), 1337 (w), 1290 (w), 1246 (w), 1209 (m), 1194
(w), 1159 (w), 1112 (w), 1085 (w), 1066 (w), 1041 (w), 1006 (m), 965 (w), 885 (w),
837 (w), 797 (w), 755 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 312 (4.9), 295 (5.0), 271 (sh, 5.0) nm.
258 Experimental Part
1H NMR (400 MHz, CDCl3): δ = 1.00 (three t, J = 7.4 Hz, superimposed, 12 H, CH3),
1.86–1.97 (m, 8 H, CH2CH3), 3.16 (two d, J = 13.5 Hz, superimposed, 4 H, ArCH2Ar),
3.80–3.92 (m, 8 H, OCH2), 4.45 and 4.46 (both d, J = 13.4 and 13.5 Hz, superimposed,
4 H, ArCH2Ar), 6.52-6.65 (m, 8 H, m-Ar’H, m-Ar’’H, p-Ar’H), 6.70 (m, 1 H, p-Ar’’H),
6.88 (s, 2 H, m-ArH), 7.13 (td, J = 7.7 Hz, J = 1.7 Hz, 1 H, PhH), 7.26 (td, J = 7.6 Hz, J
= 1.1 Hz, 1 H, PhH), 7.50 (dd, J = 7.7 Hz, J = 1.6 Hz, 1 H, PhH), 7.59 (dd, J = 8.1 Hz, J
= 1.1 Hz, 1 H, PhH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.45, 10.53 (both q, CH3), 23.40, 23.44 (both t,
CH2CH3), 31.0, 31.2 (both t, ArCH2Ar), 76.7, 76.9 (both t, OCH2), 86.5 (s, PhC≡), 95.3
(s, ArC≡), 116.2 (s, p-ArC), 122.2 (d, p-Ar’CH), 122.3 (d, p-Ar’’CH), 125.7 (s, PhCBr),
126.2 (s, PhC), 127.1 (d, PhCH), 128.3, 128.4, 128.5 (all d, m-Ar’CH, m-Ar’’CH),
128.9 (d, PhCH), 131.9 (d, m-ArCH), 132.5, 133.1 (both d, PhCH), 134.5, 135.3, 135.4,
136.0 (all s, ArCCH2Ar), 156.6 (s, Ar’CO), 156.8 (s, Ar’’CO), 157.9 (s, ArCO) ppm.
MS (FAB): m/z (%) = 772 (90) M+.
Syntheses 259
1H NMR (100 MHz, CDCl3): 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (141a)
13C NMR (100 MHz, CDCl3): 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-pro-poxycalix[4]arene (141a)
260 Experimental Part
2.2.16 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(141b)
In a screw-capped flask diiodotetrapropoxycalixarene 139b (500 mg, 0.59 mmol),
copper(I) iodide (23 mg, 0.12 mmol) and bis(triphenylphosphine)palladium(II) chloride
(42 mg, 59 µmol) were suspended in anhydrous triethylamine (10 mL) and degassed
with argon for 10 min. 1-Bromo-2-ethynylbenzene (140) (332 mg, 1.83 mmol) was
added and the mixture was stirred at 80 °C for 3 d. The crude product was diluted with
dichloromethane and filtrated over Celite. The mixture was washed with water
(3 x 30 mL), dried over MgSO4 and the solvent was removed in vacuo. The residue was
purified by flash chromatography (silica gel, PE/EtOAC 5:1 to 2:1, Rf (2:1) = 0.18),
recrystallized from DCM/MeOH and dried in vacuo (1.1 mbar, 100 °C, 40 min) to yield
141b (396 mg, 70 %) as colorless solid with mp 220–224 °C.
C56H54Br2O4 (950.83)
calcd.: C 70.74, H 5.72
found: C 70.94, H 5.46
IR (KBr): ν~ = 3060 (w), 3020 (w), 2960 (w), 2938 (w), 2873 (w), 2211 (w, C≡C),
1588 (w), 1478 (m), 1457 (m), 1433 (w), 1384 (w), 1336 (w), 1290 (w), 1239 (w), 1210
(w), 1195 (w), 1160 (w), 1114 (w), 1083 (w), 1064 (w), 1042 (w), 1030 (w), 1003 (w),
964 (w), 888 (w), 839 (w), 752 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 312 (4.7), 294 (4.8) nm.
Syntheses 261
1H NMR (600 MHz, CDCl3): δ = 0.92 (t, J = 7.5 Hz, 6 H, CH3), 1.09 (t, J = 7.4 Hz, 6
H, CH3), 1.86–1.92 and 1.92–1.98 (both m, 8H, CH2CH3), 3.18 (d, J = 13.4 Hz, 4 H,
ArCH2Ar), 3.71 (t, J = 6.8 Hz, 4 H, OCH2), (t, J = 8.0 Hz 4 H, OCH2), 4.44 (d, J = 13.4
Hz, 4 H, ArCH2Ar), 6.27 (d, J = 7.5 Hz, 4 H, m-Ar’H), 6.33 (t, J = 7.5 Hz, 2 H p-Ar’H),
7.14 (t, J = 7.8 Hz, 2 H, PhH), 7.24 (t, J = 7.6 Hz, 2 H, PhH), 7.31 (s, 4 H, m-ArH), 7.53
(d, J = 7.7 Hz, 2 H, PhH), 7.60 (d, J = 8.0 Hz, 2 H, PhH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 10.1 (q, CH3), 10.9 (q, CH3), 23.2 (t, CH2CH3),
23.6 (t, CH2CH3), 31.0 (t, ArCH2Ar), 76.9 (t, OCH2), 77.2 (t, OCH2), 87.0 (s, PhC≡),
95.0 (s, ArC≡), 116.1 (s, p-ArC), 122.5 (d, p-Ar’CH), 125.7 (s, PhCBr), 126.1 (s, PhC),
127.1 (d, PhCH), 128.0 (d, m-Ar’CH), 129.0 (d, PhCH), 132.4 (d, m-ArCH), 132.5 (d,
PhCH), 133.0 (s, Ar’CCH2Ar), 133.2 (d, PhCH), 137.2 (s, ArCCH2Ar’), 155.5 (s,
Ar’CO), 158.9 (s, ArCO) ppm.
MS (FAB): m/z (%) = 950 (29) M+.
262 Experimental Part
1H NMR (600 MHz, CDCl3): 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (141b)
13C NMR (150 MHz, CDCl3): 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (141b)
Syntheses 263
2.2.17 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137a)
Calixarene 141a (647 mg, 838 µmol) and p-toluenesulfonyl hydrazide (286) (3.10 g,
16.7 mmol) were dissolved in ethylene glycol dimethyl ether (7.5 mL) and heated to
85 °C. Over a period of 8 h a solution of sodium acetate (1.38 g, 16.8 mmol) in water
(6.5 mL) was added dropwise. The solution was stirred for further 6 h at 85 °C and
cooled to room temperature. Water (30 mL) and dichloromethane (30 mL) were added,
the layers separated and the aqueous layer was extracted with dichloromethane (3 x
15 mL). The organic layer was washed with aqueous ammonium chloride (1 N, 15 mL),
water (3 x 15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed
by rotary evaporation. The residue was purified by flash chromatography (silica gel,
1. PE/EtOAc 15:1, Rf = 0.54, 2. PE/DCM 10:1, Rf = 0.09). After drying in vacuo
(0.55–0.98 mbar mbar, 50, 30 min) 137a (547 mg, 84 %) was obtained as colorless
solid with mp 47–49 °C.
C48H55BrO4 (775.85)
calcd.: C 74.31, H 7.15
found: C 74.33, H 7.10
IR (KBr): ν~ = 3059 (w), 3013 (w), 2960 (m), 2928 (w), 2872 (w), 1587 (w), 1457 (m),
1383 (w), 1343 (w), 1286 (w), 1246 (w), 1213 (w), 1195 (w), 1160 (w), 1128 (w), 1108
(w), 1085 (w), 1039 (w), 1007 (w), 965 (w), 888 (w), 836 (w), 757 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 313 (sh, 3.1), 273 (3.7) nm.
264 Experimental Part
1H NMR (600 MHz, CDCl3): δ = 0.97-1.02 (m, 12 H, CH3), 1.89–1.96 (m, 8 H,
CH2CH3), 2.60 (m, 2 H, ArCH2), 2.79 (m, 2 H, CH2Ph), 3.10 (d, J = 13.3 Hz, 2 H,
ArCH2Ar’), 3.15 (d, J = 13.3 Hz, 2 H, Ar’CH2Ar’’), 3.83–3.87 (m, 8 H, OCH2), 4.43 (d,
J = 13.3 Hz, 2 H, ArCH2Ar’), 4.46 (d, J = 13.3 Hz, 2 H, Ar’CH2Ar’’), 6.49 (s, 2 H, m-
ArH), 6.52–6.59 (m, 7 H, m-Ar’H, p-Ar’H, p-Ar’’H), 6.67 (d, J = 7.5 Hz, 2 H, m-
Ar’’H), 7.04 (t, J = 7.6 Hz, 1 H, PhH), 7.12 (d, J = 7.5 Hz, 1 H, PhH), 7.19 (d, J = 7.4
Hz, 1 H, PhH), 7.53 ( d, J = 8.0 Hz, 1H, PhH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 10.4 (q, CH3), 10.47 (q, CH3), 10.52 (q, CH3),
23.39 (t, CH2CH3), 23.42 (t, CH2CH3), 31.2 (t, ArCH2Ar), 35.5 (d, ArCH2), 38.6 (t,
PhCH2), 76.8 (t, OCH2), 76.9 (t, OCH2), 121.96 (d, p-Ar’’CH), 122.02 (d, p-Ar’CH),
124.6 (s, PhCBr), 127.4 (d, PhCH), 127.6 (d, PhCH), 128.2 and 128.3 (both d, m-ArCH,
m-Ar’CH, m-Ar’’CH), 130.7 (d, PhCH), 132.9 (d, PhCH), 134.6 (s, ArC), 135.07,
135.12, 135.2, 135.5 (all s, ArCCH2Ar), 141.6 (s, PhC), 155.1 (s, ArCO), 156.6 (s,
Ar’CO), 156.9 (s, Ar’’CO) ppm.
MS (FAB): m/z (%) = 774 (45) M+.
Syntheses 265
1H NMR (600 MHz, CDCl3): 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene (137a)
13C NMR (150 MHz, CDCl3): 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxy-calix[4]arene (137a)
266 Experimental Part
2.2.18 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(137b)
Calixarene 141b (490 mg, 515 µmol) and p-toluenesulfonyl hydrazide (286) (3.89 g,
20.9 mmol) were dissolved in ethylene glycol dimethyl ether (5 mL) and heated to
85 °C. Over a period of 8 h a solution of sodium acetate (1.71 g, 20.9 mmol) in water
(4 mL) was added dropwise. The solution was stirred for further 6 h at 85 °C and cooled
to room temperature. Water (20 mL) and dichloromethane (20 mL) were added, the
layers separated and the aqueous layer was extracted with dichloromethane (3 x 15 mL).
The organic layer was washed with aqueous ammonium chloride (1 N, 15 mL), water
(3 x 15 mL) and brine (15 mL), dried over MgSO4 and the solvent was removed by
rotary evaporation. The residue was purified by flash chromatography (silica gel,
PE/EtOAc 4:1, Rf = 0.69) and recrystallized from DCM/MeOH. After drying in vacuo
(0.57 mbar, 100 °C, 20 min) 137b (418 mg, 85 %) was obtained as colorless solid with
mp 167–168 °C.
C56H62Br2O4 (958.90)
calcd.: C 70.14, H 6.52
found: C 70.41, H 6.43
IR (KBr): ν~ = 3060 (w), 3015 (w), 2959 (m), 2930 (m), 2872 (m), 1588 (w), 1467
(m), 1456 (m), 1384 (w), 1342 (w), 1305 (w), 1288 (w), 1247 (w), 1220 (m), 1195 (w),
1166 (w), 1134 (w), 1109 (w), 1082 (w), 1066 (w), 1039 (w), 1027 (w), 1007 (m), 965
(w), 935 (w), 886 (w), 836 (w), 822 (w), 802 (w), 751 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 274 (3.8) nm.
Syntheses 267
1H NMR (600 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 6 H, CH3), 1.04 (t, J = 7.41Hz, 6
H, CH3), 1.86–1.97 (m, 8 H CH2CH3), 2.71 (m, 4 H, ArCH2CH2), 2.93 (m, 4 H,
PhCH2CH2) 3.09 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 3.76 (t, J = 7.1 Hz, 4 H, OCH2), 3.90
(dd, J = 7.9 Hz, 4 H, OCH2), 4.42 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 6.31 (d, J = 7.5 Hz, 4
H, m-Ar’H), 6.41 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.70 (s, 4 H, m-ArH), 7.03 (td, J = 7.9
Hz, J = 1.6 Hz, 2 H, PhH), 7.06 (dd, J = 7.6 Hz, J = 1.4 Hz, 2 H, PhH), 7.14 (td, J = 7.5
Hz, J = 1.0 Hz, 2 H, PhH), 7.52 (dd, J = 7.9 Hz, J = 0.9 Hz, 2 H, PhH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 10.2 (q, CH3), 10.7 (q, CH3), 23.3 (t, CH2CH3),
23.5 (t, CH2CH3), 31.1 (t, ArCH2Ar), 35.5 (t, ArCH2CH2), 38.7 (t, PhCH2CH2), 76.7 (t,
OCH2), 76.9 (t, OCH2), 122.1 (d, p-Ar’CH), 124.7 (s, PhCBr), 127.3 (d, PhCH), 127.6
(d, PhCH), 127.9 (d, m-Ar’CH), 128.7 (d, m-ArCH), 130.7 (d, PhCH), 132.9 (d, PhCH),
134.3 (s, Ar’CCH2Ar), 134.5 (s, ArC), 135.9 (s, ArCCH2Ar’), 141.3 (s, PhC), 155.7 (s,
ArCO), 156.0 (s, Ar’CO) ppm.
MS (FAB): m/z (%) = 958 (13) M+, 787 (5).
268 Experimental Part
1H NMR (600 MHz, CDCl3): 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137b)
13C NMR (150 MHz, CDCl3): 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene (137b)
Syntheses 269
2.2.19 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and 5,17-Bis-(2-
chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)
Calixarene 138 (1.50 g, 2.00) was dissolved in dry THF (80 mL) and tBuLi (5.4 mL,
15 % in pentane, 8.35 mmol) was added at –78 °C and the solution stirred for 1 h. After
addition of amide 169b (2.44 g, 12.2 mmol) the mixture was warmed to room
temperature and heated to 60 °C for further 17 h. It was hydrolyzed with HCl (2 N,
60 mL) and the aqueous layer was extracted with DCM (2 x 60 mL). The organic layer
was washed with water (100 mL) and brine (60 mL), dried over MgSO4 and the solvent
was removed at a rotary evaporator to yield 3.73 g of a yellow oil, which was purified
by multiple flash chromatography (silica gel, PE/EtOAc 25:1 to 10:1).
1st fraction: Rf (PE/EtOAC 10:1) = 0.29, Chlorobenzoylcalixarene 163 (489 mg, 33 %)
as colorless solid with mp 87 °C.
C47H51ClO5 (731.36)
calcd.: C 77.19, H 7.03
found: C 77.05, H 7.16
IR (KBr): ν~ = 3059 (w), 3014 (w), 2962 (m), 2930 (w), 2873 (w), 2737 (w), 1666 (m),
1590 (w), 1458 (m), 1436 (w), 1384 (w), 1309 (m), 1288 (m), 1246 (w), 1206 (m), 1159
(w), 1119 (w), 1085 (w), 1063 (w), 1038 (w), 1006 (m), 964 (w), 894 (w), 849 (w), 803
(w), 757 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 280 (4.4) nm.
270 Experimental Part
1H NMR (400 MHz, CD2Cl2): δ = 0.99 (t, J = 7.5 Hz, 6 H, CH3), 1.03, 1.04 (both t, J =
7.5 Hz, J = 7.4 Hz, superimposed, 6 H, CH3), 1.89-2.00 (m, 8 H, CH2CH3), 3.17 and
3.18 (both d, superimposed, J =13.4 Hz, J = 13.3 Hz, 4 H, ArCH2Ar), 3.82 (t, J = 7.4
Hz, 2 H, OCH2), 3.86–3.96 (m, 6 H, OCH2), 4.46 and 4.47 (both d, superimposed, J =
13.2 Hz, J = 13.4 Hz, 4 H, ArCH2Ar), 6.48 (“t”, “J” = 7.5 Hz, p-Ar’’H), 6.59 (d, J = 7.5
Hz, 2 H, m-Ar’’H), 6.62 (t, J = 7.3 Hz, p-Ar’H), 6.65 and 6.66 (both d, superimposed, J
= 7.5 Hz, 2 H, m-Ar’H), 6.75 and 6.76 (both d, superimposed, J = 7.0 Hz, m-Ar’H),
6.92 (dd, J = 7.6 Hz, J = 1.0 Hz, 1 H, Ph-6-H), 7.01 (s, 2 H, m-ArH), 7.26 („t“, „J“ =
7.2 Hz, 1 H, PhH), 7.38–7.44 (m, 2 H, PhH) ppm.
13C{
1H} NMR (100 MHz, CD2Cl2): δ = 10.6, 10.78, 10.84 (all q, CH3), 23.8, 23.95,
24.01 (all t, CH2CH3), 31.4, 31.5 (both t, ArCH2Ar), 77.4, 77.6, 77.7 (all t, OCH2),
122.4 (d, p-Ar’’CH ), 122.7 (d, p-Ar’CH ), 126.7 (d, PhCH), 128.6 (d, m-Ar’’CH),
128.8 (d, m-Ar’CH ), 129.2 (d, m-Ar’CH), 130.0 (d, Ph-6-CH), 130.5 (d, PhCH), 130.8
(s, ArC), 131.1 (d, PhCH), 131.3 (d, m-ArCH), 131.7 (s, ArC), 135.4 (s, ArCCH3),
136.0 (s, ArC), 136.3 (s, ArC), 156.9 (s, Ar’’CO), 157.3 (s, Ar’CO), 162.2 (s, ArCO),
194.2 (s, C=O) ppm.
MS (FAB): m/z (%) = 753 (8) [M+Na]+, 731 (38) [M+H]+.
Syntheses 271
1H NMR (400 MHz, CD2Cl2): 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163)
13C NMR (100 MHz, CD2Cl2): 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163)
272 Experimental Part
2nd fraction: Rf (PE/EtOAc 10:1) = 0.10, Bis(chlorobenzoyl)calixarene 166 (481 mg,
28 %) as colorless solid with mp 244 °C.
C54H54Cl2O6 (869.91)
calcd.: C 74.56, H 6.26
found: C 74.51, H 6.34
IR (KBr): ν~ = 3059 (w), 3027 (w), 2961 (w), 2931 (w), 2874 (w), 2740 (w), 1666 (s),
1594 (m), 1462 (m), 1434 (m), 1385 (w), 1316 (m), 1291 (m), 1234 (w), 1208 (m),
1161 (w), 1119 (m), 1079 (w), 1061 (w), 1036 (w), 1008 (w), 961 (w), 892 (w), 852
(w), 837 (w), 809 (w), 758 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 280 (4.3) nm.
1H NMR (400 MHz, CDCl3): δ = 0.99 (t, J = 6.2 Hz, 6 H, CH3), 1.02 (t, J = 6.2 Hz, 6
H, CH3), 1.88 – 1.98 (m, 8 H, CH2CH3), 3.19 (d, J = 13.4 Hz, 4 H, ArCH2Ar), 3.82 (t, J
= 7.4 Hz, 4 H, OCH2), 3.97 (t, J = 7.6 Hz, 4 H, OCH2), 4.46 (d, J = 13.3 Hz, 4 H,
ArCH2Ar), 6.49 (s, 6 H, m-Ar’H, p-Ar’H), 6.99 (d, J = 6.9 Hz, 2 H, Ph-6-H), 7.29 and
7.30 (td, J = 7.1, J = 1.8 Hz, and s, superimposed, 6 H, Ph-5-H and m-ArH), 7.37 and
7.40 (td, J = 8.0 Hz, J = 1.6 Hz, and dd, J = 8.0 Hz, J = 1.6 Hz, superimposed, 4 H, Ph-
3-H and Ph-4-H) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.4, 10.6 (both q, CH3), 23.4, 23.5 (both t,
CH2CH3) , 31.2 (t, ArCH2Ar), 77.0, 77.3 (both t, OCH2), 122.8 (d, p-Ar’CH), 126.6 (d,
Ph-5-CH), 128.4 (d, m-Ar’CH), 129.5 (d, Ph-6-CH), 130.0 (d, Ph-3-CH), 130.5 (d, Ph-
4-CH), 130.8 (s, ArC), 131.3 (d, m-ArCH), 131.4 (s, PhC), 134.1 (s, Ar’CCH3), 136.0
(s, ArCCH3), 138.7 (s, PhC), 156.1 (s, Ar’CO), 162.2 (s, ArCO), 194.3 (s, C=O) ppm.
MS (FAB): m/z (%) = 869 (9) [M+H]+.
Syntheses 273
1H NMR (400 MHz, CDCl3): 5,17-Bis-(2-Chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)
13C NMR (100 MHz, CDCl3): 5,17-Bis-(2-Chlorobenzoyl)-tetra-n-propoxycalix[4]-arene (166)
0102030405060708090100110120130140150160170180190f1 (ppm)
10.3
10.5
23.4
23.5
31.1
122.8
126.6
128.4
134.1
136.0
138.7
156.1
162.2
194.3
77.077.5f1 (ppm)
77.0
77.3
129.5130.0130.5131.0131.5f1 (ppm)
129.5
130.0
130.5
130.8
131.3
131.4
274 Experimental Part
2.2.20 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171) and
5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (172)
Dipropoxycalixarene 131 (2.09 g, 4.11 mmol), aluminium chloride (2.49 g, 18.7 mmol)
and 2-bromobenzoyl chloride (148b) (1.91 g, 8.71 mmol) were dissolved in dry
dichloromethane (45 mL) and stirred for 10 min at room temperature. The mixture was
hydrolyzed with hydrochloric acid (2 N, 45 mL), the layers were separated and the
aqueous layer was extracted with dichloromethane (25 mL). The combined organic
layers were washed with water (25 mL) and brine (25 mL), dried over MgSO4 and the
solvent was removed in vacuo. The crude product (4.99 g) was purified by flash
chromatography (silica gel, PE/EtOAc 8:1 to 2:1) and the products were dried in vacuo
(0.56 mbar, 100 °C, 40 min).
1st Fraction: Rf (5:1 PE/EtOAc) = 0.13, Bis(bromobenzoyl)dipropoxycalixarene 171
(2.00 g, 57 %) as colorless solid with mp 165–169 °C.
C48H42Br2O6 (874.65)
calcd.: C 65.91, H 4.84
found: C 66.02, H 4.86
IR (KBr): ν~ = 3243 (br, m), 3060 (w), 2963 (w), 2929 (m), 2874 (w), 1733 (w), 1659
(s), 1587 (s), 1481 (w), 1459 (s), 1429 (s), 1386 (w), 1317 (s), 1289 (s), 1214 (w), 1160
(w), 1126 (s), 1078 (w), 1056 (w), 1027 (w), 1001 (w), 958 (s), 916 (w), 857 (w), 837
(w), 815 (w), 751 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 303 (4.5) nm.
Syntheses 275
1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.06 (m, 4 H,
CH2CH3), 3.43 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 3.99 (t, J = 6.1 Hz, 4 H, OCH2), 4.27
(d, J = 13.1 Hz, 4 H, ArCH2Ar), 6.81 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.92 (d, J = 7.6 Hz, 4
H, m-Ar’H), 7.29 (d, J = 7.5 Hz, 2 H, PhH), 7.32–7.37 (t, J = 7.4 Hz, 2 H, PhH), 7.41 (t,
J = 7.5 Hz, 2 H, PhH), 7.59 (s, 4 H, m-ArH), 7.66 (d, J = 8.0 Hz, 2 H, PhH), 9.25 (s, 2
H, OH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 11.1 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,
ArCH2Ar), 78.7 (t, OCH2), 119.7 (s, PhCBr), 125.8 (d, p-Ar’CH), 127.2 (d, PhCH),
127.6 (s, p-ArC), 128.3 (s, ArCCH2Ar’), 129.0 (d, PhCH), 129.6 (d, m-Ar’CH), 130.8
(d, PhCH), 131.8 (d, m-ArCH), 132.6 (s, Ar’CCH2Ar), 133.2 (d, PhCH), 141.7 (s, PhC),
151.9 (s, Ar’CO), 159.4 (s, ArCO), 194.6 (s, C=O) ppm.
MS (FAB): m/z (%) = 875 (29) [M+H]+, 183 (100).
276 Experimental Part
1H NMR (600 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-arene (171)
13C NMR (150 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-arene (171)
Syntheses 277
2nd Fraction: Rf (5:1 PE/EtOAc) = 0.04, Tris(bromobenzoyl)dipropoxycalixarene 172
(137 mg, 3 %) as colorless solid with a melting range of 154–162 °C.
IR (KBr): ν~ = 3283 (br, w), 3057 (w), 2963 (w), 2931 (w), 2875 (w), 1661 (s), 1589
(s), 1563 (w), 1481 (w), 1461 (m), 1429 (m), 1387 (w), 1316 (s), 1292 (s), 1249 (w),
1214 (m), 1159 (w), 1128 (m), 1079 (w), 1053 (w), 1026 (w), 1009 (w), 957 (w), 916
(w), 856 (w), 838 (w), 825 (w), 770 (w), 749 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 299 (4.7), 271 (sh, 4.7) nm.
1H NMR (400 MHz, CDCl3): δ = 1.296 and 1.298 (both t, J = 7.4 Hz, superimposed, 6
H, CH3), 2.02–2.11 (m, 4 H, CH2CH3), 3.42 and 3.46 (both d, J = 13.5 Hz, J = 13.4 Hz,
superimposed, 4 H, ArCH2Ar), 4.00 and 4.03 (both t, J = 6.3 Hz, superimposed, 4 H,
OCH2), 4.27 and 4.30 (both d, J = 12.9 Hz, J = 13.0 Hz, superimposed, 4 H, ArCH2Ar),
6.81 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.93 (d, J = 7.5 Hz, 2 H, m-Ar’’H), 7.10–7.13 (m, 1
H, Ph’H), 7.27–7.36 and 7.30 (m and s, 8 H, PhH, Ph’H, m-Ar’H), 7.41 (td, J = 7.4 Hz,
J = 0.9 Hz, 2 H, PhH), 7.48 (d, J = 2.1 Hz, 2 H, m-ArH), 7.52–7.54 (m, 1 H, Ph’H),
7.65 and 7.67 (dd, J = 8.1 Hz, J = 1.0 Hz and d, J = 2.2 Hz, superimposed, 4 H, PhH, m-
ArH), 8.77 (s, 2 H, OH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.9 (q, CH3), 11.0 (q, CH3), 23.6 (t, CH2CH3),
31.3 (t, ArCH2Ar), 31.4 (t, ArCH2Ar), 78.7 (t, OCH2), 78.9 (t, OCH2), 119.7 (s, PhCBr),
120.1 (s, Ph’CBr), 125.7 (p-Ar’’CH), 127.3 (d, PhCH, Ph’CH), 127.7 (s), 127.8 (s),
128.4 (s, ArCCH2Ar), 129.1 (d, PhCH), 129.6 (d, m-Ar’’CH), 129.7 (d, Ph’CH), 130.9
(d, PhCH), 131.5 (d, Ph’CH), 131.8 (d, m-ArCH), 131.96 (d, m-Ar’CH), 132.00 (d, m-
ArCH) , 132.5 (s, Ar’’CCH2Ar), 133.3 (d, PhCH), 133.4 (d, Ph’CH), 140.0 (s, Ph’C),
141.4 (s, PhC), 151.9 (s, Ar’’CO), 156.7 (s, Ar’CO), 159.1 (s, ArCO), 194.4 (s,
ArC=O), 194.6 (s, Ar’C=O) ppm.
MS (FAB): m/z (%) = 1059 (17) [M+3]+, 183 (100).
278 Experimental Part
1H NMR (400 MHz, CDCl3): 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxy-calix[4]arene (172)
13C NMR (100 MHz, CDCl3): 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxy-calix[4]arene (172)
Syntheses 279
2.2.21 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170) and 5,17-Bis(2-
bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171)
Dipropoxycalixarene 131 (1.00 g, 1.97 mmol), aluminium chlorid (1.18 g, 8.85 mmol)
and 2-bromobenzoyl chloride (148b) (0.916 g, 4.17 mmol) were dissolved in dry
dichloromethane (25 mL) and stirred for 35 min at 0 °C. The mixture was hydrolyzed
with hydrochloric acid (2 N, 25 mL), the layers were separated and the aqueous layer
was extracted with dichloromethane (15 mL). The combined organic layers were
washed with water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was
removed in vacuo. The crude product (4.99 g) was purified by flash chromatography
(silica gel, PE/EtOAc 8:1 to 2:1) and the products were dried in vacuo (0.61 mbar,
100 °C, 30 min).
1st Fraction: Rf (5:1 PE/EtOAc) = 0.31, Bromobenzoyldipropoxycalixarene 170
(344 mg, 25 %) as colorless solid with mp 144–146 °C.
IR (KBr): ν~ = 3305 (br w), 3060 (w), 2961 (w), 2927 (w), 2873 (w), 1658 (w), 1589
(w), 1542 (w), 1521 (w), 1461 (m), 1431 (w), 1386 (w), 1317 (m), 1290 (w), 1214 (w),
1160 (w), 1127 (w), 1085 (w), 1058 (w), 1027 (w), 1005 (w), 961 (w), 914 (w), 858
(w), 836 (w), 815 (w), 756 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 302 (4.2), 288 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.03–2.11 (m, 4 H,
CH2CH3), 3.39 and 3.41 (both d, J = 13.0 Hz and J = 13.1 Hz, superimposed, 4 H,
ArCH2Ar), 3.94–4.03 (m, 4 H, OCH2), 4.29 and 4.31 ( both d, J = 13.1 Hz and J = 12.9
Hz, superimposed, 4 H, ArCH2Ar), 6.65 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.77 (t, J = 7.5
280 Experimental Part
Hz, 2 H, p-Ar’H), 6.89 (dd, J = 7.6 Hz, J = 1.4, Hz, 2 H, m-Ar’H), 6.95 (dd, J = 7.5 Hz,
J = 1.4 Hz, 2 H, m-Ar’H), 7.06 (d, J = 7.5 Hz, 2 H, m-Ar’’H), 7.28-7.35 (m, 2 H, PhH),
7.40 (td, J = 7.4 Hz, J = 1.1 Hz, 1 H, PhH), 7.58 (s, 2 H, m-ArH), 7.65 (dd, J = 7.9 Hz, J
= 0.9 Hz, 1 H, PhH)), 8.26 (s, 1 H, OH), 9.28 (s, 1 H, OH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 11.1 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,
ArCH2Ar), 31.6 (t, ArCH2Ar), 78.6 (t, OCH2), 119.2 (d, p-Ar’’CH), 119.7 (s, PhCBr),
125.6 (d, p-Ar’CH), 127.2 (d, PhCH), 127.5 (s, p-ArC), 128.1 (s, Ar’’CCH2Ar’), 128.5
(s, ArCCH2Ar’), 128.6 (d, m-Ar’’CH), 129.1 (d, PhCH), 129.2 (d, m-Ar’CH), 129.5 (d,
m-Ar’CH), 130.8 (d, PhCH), 131.8 (d, m-ArCH), 132.6 (s, Ar’CCH2Ar/Ar’’), 133.2 (d,
PhCH), 133.7 (s, Ar’CCH2Ar/Ar’’), 141.7 (s, PhC), 152.0 (s, Ar’CO), 153.5 (s,
Ar’’CO), 159.6 (s, ArCO), 194.6 (s, C=O) ppm.
MS (FAB): m/z (%) = 715 (14) [M+Na]+, 691 (100) M+, 183 (92).
2nd Fraction: Rf (5:1 PE/EtOAc) = 0.13, Bis(bromobenzoyl)dipropoxycalixarene 171
(973 mg, 58 %) as colorless solid with mp 165–169 °C. NMR data are in accord with
those mentioned before.
Syntheses 281
1H NMR (400 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)
13C NMR (100 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)
282 Experimental Part
2.2.22 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162), 5-(2-Bromo-
benzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179) and paco-5-(2-
Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)
Sodium hydride (60 %, 897 mg, 22.4 mmol, washed with hexane (2 x 10 mL) prior to
use) was suspended in dry DMF (40 mL), calixarene 170 (1.18 g, 1.71 mmol) were
added and the suspension was heated to 80 °C for 30 min before adding propyl iodide
(6.35 mL, 65.1 mmol). The mixture was stirred at 80 °C overnight, cooled to room
temperature and poured into ice water (80 mL). It was extracted with dichloromethane
(3 x 20 mL), the organic layer was washed with aqueous ammonium chloride (1 N,
2 x 20 mL), water (20 mL) and brine (20 mL), dried over magnesium sulfate and the
solvent was removed in vacuo. The brown residue (1.22 g) was submitted to multiple
flash chromatography (silica gel, 1. PE/EtOAc 5:1 to 2:1; 2. PE/EtOAc 12:1 to 10:1;
3. PE/DCM 2:1 to 1:1) to yield:
1st Fraction: (Rf: 0.37 in PE/EtOAc 10:1), After drying in vacuo (75–100 °C, 0.38 mbar,
40 min) 78 mg (6 %) paco-bromobenzoylcalixarene 180 as a colorless solid with
mp 186–189 °C.
C47H51BrO5 (775.81)
calcd.: C 72.76, H 6.63
found: C 72.42, H 6.26
IR (KBr):ν~ = 3061 (w), 3028 (w), 2961 (w), 2930 (w), 2871 (w), 2738 (w), 1666 (m),
1587 (w), 1457 (m), 1429 (w), 1384 (w), 1312 (m), 1289 (w), 1248 (w), 1201 (m), 1160
(w), 1121 (w), 1085 (w), 1068 (w), 1043 (w), 1004 (w), 961 (w), 906 (w), 848 (w), 804
(w), 766 (w) cm-1.
Syntheses 283
UV/Vis (CH3CN): λmax (lg ε) = 278 (4.2) nm.
1H NMR (400 MHz, CDCl3): δ = = 0.76 (t, J = 7.5 Hz, 3 H, CH3), 1.02 and 1.06 (both t,
J = 7.4 Hz, superimposed, 9 H, CH3), 1.36–1.46 (m, 2 H, CH2CH3), 1.74–1.83 (m, 4 H,
CH2CH3), 1.89–1.99 (m, 2 H, CH2CH3), 3.06 (d, J = 13.3 Hz, 4 H, ArCH2Ar), 3.33–
3.37 (m, 2 H, OCH2), 3.49–3.55 (m, 2 H, OCH2), 3.64–3.72 (m, 6 H, OCH2, ArCH2Ar),
3.82 (t, J = 7.3 Hz, 2 H, OCH2), 4.07 (d, J = 13.2 Hz, 4 H, ArCH2Ar), 6.32 (dd, J = 7.6
Hz, J = 0.9 Hz, 2 H, m-Ar’H), 6.45 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.91 (m, 3 H, m-Ar’H,
p-Ar’’H), 7.09 (d, J = 7.4 Hz, 2 H, m-Ar’’H), 7.36 (td, J = 7.6 Hz, J = 1.8 Hz, 1 H, m-
PhH), 7.44 (td, J = 7.5 Hz, J = 1.0 Hz, 1 H, m-PhH), 7.50 (dd, J = 7.5 Hz, J = 1.7 Hz, 1
H, o-PhH), 7.68 (dd, J = 7.9 Hz, J = 0.9 Hz, 1 H, p-PhH), 7.75 (s, 2 H, m-ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.0
(t, CH2CH2), 23.9 (t, CH2CH2), 24.2 (t, CH2CH2), 30.7 (t, ArCH2Ar), 36.2 (t,
ArCH2Ar), 74.8 (t, OCH2), 75.5 (t, OCH2), 76.5 (t, OCH2), 120.0 (s, CBr), 121.7 (d, p-
Ar’CH), 122.5 (d, p-Ar’’CH), 126.9 (d, m-PhH), 128.9 (d, m-Ar’CH), 129.0 (d, o-PhH),
129.1 (d, m-Ar’’CH), 129.4 (d, m-Ar’CH), 129.9 (s, ArC), 130.7 (d, p-PhH), 131.4 (s,
Ar’CCH2Ar), 133.1 (d, m-ArCH), 133.4 (s, m-PhC), 133.7 (s, Ar’CCH2Ar’’), 134.6 (s,
ArCCH2Ar’), 137.1 (s, Ar’’CCH2Ar), 141.9 (s, PhC), 155.7 (s, Ar’CO), 156.9 (s,
Ar’’CO), 163.1 (s, ArCO), 195.1 (s, C=O) ppm.
MS (FAB): m/z (%) = 799 (7) [M+Na]+, 775 (40) [M+H]+, 733 (8), 185 (66).
284 Experimental Part
1H NMR (400 MHz, CDCl3): paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)
13C NMR (100 MHz, CDCl3): paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)
Syntheses 285
2nd fraction: (Rf: 0.31 in PE/EtOAc 10:1) After drying in vacuo (75–100 °C,
0.42–0.86 mbar, 30 min) 433 mg (33 %) of cone-Bromobenzoyltetrapropoxycalixarene
162 as a colorless solid with mp 83–86 °C.
C47H51BrO5 (775.81)
calcd.: C 72.76, H 6.63
found: C 72.91, H 6.77
IR (KBr): ν~ = 3058 (w) , 3014 (w), 2961 (w), 2930 (w), 2873 (w), 1666 (w), 1589 (w),
1560 (w), 1540 (w), 1521 (w), 1507 (w), 1457 (m), 1433 (w), 1384 (w), 1309 (w), 1288
(w), 1246 (w), 1208 (m), 1159 (w), 1115 (w), 1086 (w), 1065 (w), 1037 (w), 1006 (w),
964 (w), 891 (w), 848 (w), 802 (w), 759 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 280 (4.3) nm.
1H NMR (400 MHz, CDCl3): δ = 0.99, 1.00 and 1.01 (each t, J = 7.1, 7.5 and 7.5 Hz,
superimposed, 12 H, CH3), 1.87–1.98 (m, 8 H, CH2CH3), 3.16 and 3.17 (both d, J =
13.5 and 13.3 Hz, superimposed, 4 H, ArCH2Ar), 3.81–3.87 (m, 4 H, OCH2), 3.89–3.94
(m, 4 H, OCH2), 4.45 (d, J = 13.3 Hz, 4 H, ArCH2Ar), 6.52–6.59 (m, 5 H, p-ArH, m-
ArH), 6.63–6.68 (m, 4 H, m-ArH), 6.95 (m, 1 H, PhH), 7.11 (s, 2 H, m-ArH), 7.27–7.31
(m, 2 H, PhH), 7.61 (m, 1 H, PhH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.4 (q, CH3),10.47 (q, CH3),10.51 (q, CH3),
23.37 (t, CH2CH3), 23.44 (t, CH2CH3), 23.5 (t, CH2CH3), 31.08 (t, ArCH2Ar), 31.13 (t,
ArCH2Ar), 77.0 (t, OCH2), 120.1 (s, PhCBr), 122.1 (d, p-Ar’’CH), 122.5 (d, p-Ar’CH),
126.7 (d, m-ArCH), 128.3 (d, m-ArCH), 128.4 (d, m-ArCH), 128.7 (d, m-ArCH), 129.7
(d, PhCH), 130.1 (s, ArC), 130.8 (d, PhCH), 131.2 (d, m-ArCH), 133.3 (d, PhCH),
134.6 (s, ArCCH2Ar), 135.1 (s, ArCCH2Ar), 135.5 (s, ArCCH2Ar), 135.6 (s,
ArCCH2Ar), 140.8 (s, PhC), 156.58 (s, Ar’CO), 156.64 (s, Ar’’CO), 161.9 (s, ArCO),
194.8 (s, C=O) ppm.
MS (FAB): m/z (%) = 799 (7) [M+Na]+, 775 (36) [M+H]+, 183 (100), 149 (32), 119
(58).
286 Experimental Part
1H NMR (400 MHz, CDCl3): cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162)
13C NMR (100 MHz, CDCl3): cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162)
Syntheses 287
3rd fraction: (Rf: 0.18 in PE/EtOAc 10:1). Bromobenzoyltripropoxycalixarene 179
(344 mg, 27 %) was obtained as a colorless solid with mp 97–103 °C after drying in
vacuo (100 °C, 0.71–0.89 mbar, 1 h 15 min).
C44H45BrO5 (733.73)
calcd.: C 72.03, H 6.18
found: C 71.94, H 5.89
IR (KBr): ν~ = 3522 (w), 3443 (w), 3059 (w), 3016 (w), 2962 (w), 2930 (w), 2873 (w),
1659 (w), 1590 (w), 1560 (w), 1541 (w), 1521 (w), 1507 (w), 1458 (m), 1431 (w), 1386
(w), 1320 (m), 1289 (w), 1248 (w), 1208 (w), 1160 (w), 1127 (w), 1086 (w), 1065 (w),
1042 (w), 1004 (w), 963 (w), 909 (w), 858 (w), 840 (w), 799 (w), 762 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 302 (4.5) nm.
1H NMR (400 MHz, CDCl3): δ = 0.94 (t, J = 7.5 Hz, 3 H, CH3), 1.11 (t, J = 7.4 Hz, 6
H, CH3), 1.83–1.97 (m, 4 H, CH2CH3), 2.21–2.31 (m, 2 H, CH2CH3), 3.22 (d, J = 13.1
Hz, 2 H, ArCH2Ar), 3.35 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 3.70-3.79 (m, 4 H, OCH2),
3.82–3.86 (m, 2 H, OCH2), 4.34 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 4.40 (d, J = 13.1 Hz, 2
H, ArCH2Ar), 5.99 (s, 1 H, OH), 6.40 (m, 6 H, p-Ar’H, m-Ar’H), 6.97 (t, J = 7.4 Hz, 1
H, p-Ar’’H), 7.18 (d, J = 7.5 Hz, 1 H, m-Ar’’H), 7.32–7.37 (m, 1 H, PhH), 7.40–7.46
(m, 2 H, PhH), 7.60 (s, 2 H, m-ArH), 7.66 (d, J = 7.8 Hz, 1 H, PhH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 9.7 (q, CH3), 10.9 (q, CH3), 22.6 (t, CH2CH3),
23.6 (t, CH2CH3), 30.8 (t, ArCH2Ar), 30.9 (t, ArCH2Ar), 76.6 (t, OCH2), 77.8 (t,
OCH2), 119.8 (s, PhCBr), 123.2 (d, p-Ar’’CH), 123.4 (d, p-Ar’CH), 127.3 (d, m-PhCH),
127.5 (s, p-ArCH), 127.8 (d, m-Ar’CH), 128.5 (d, m-Ar’CH), 129.2 (d, o-PhCH), 129.3
(d, m-Ar’’CH), 130.3 (s, ArCCH2Ar), 130.8 (d, p-PhCH), 131.6 (d, m-ArCH), 131.7 (s,
ArCCH2Ar), 133.3 (d, m-PhCh), 133.7 (s, ArCCH2Ar), 137.1 (s, ArCCH2Ar), 141.8 (s,
PhC), 154.4 (s, Ar’CO), 157.0 (s, Ar’’CO), 159.3 (s, ArCOH), 195.1 (s, C=O) ppm.
MS (FAB): m/z (%) = 757 (10) [M+Na]+, 733 (40) [M+H]+, 183 (100), 149 (21), 119
(63).
288 Experimental Part
1H NMR (400 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]-arene (179)
13C NMR (100 MHz, CDCl3): 5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]-arene (179)
Syntheses 289
2.2.23 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165),
paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (175) and
5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (176)
Sodium hydride (60 % dispersion in paraffin, 497 mg, 12.4 mmol) was washed with
hexane (2 x 5 mL) under argon and suspended in DMF (32 mL) with calixarene 171
(1.09 g, 1.25 mmol). The suspension was stirred 30 min at 60 °C, 1-iodopropane
(1.85 mL, 19.0 mmol) was added at room temperature and the mixture was stirred 10
min at room temperature and further 2 h at 70–80 °C. After cooling to room temperature
ice water (60 mL) was added and the mixture was extracted with dichloromethane
(3 x 20 mL), the organic layer was washed with aqueous ammonium chloride (1 N,
15 mL), water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was
removed in vacuo. The residue was purified by flash chromatography (silica gel,
1. PE/EtOAc 6:1 to 2:1; 2. PE/DCM 2:1) and the products were dried in vacuo
(0.6 mbar, 100 °C).
1st fraction: Rf (4:1 PE/EtOAc) = 0.38, Rf (2:1 DCM/PE) = 0.15. 252 mg (21 %) of
cone-Bis(bromobenzoyl)calixarene 165 were obtained as colorless crystals with
mp 273–276 °C after crystallization from DCM/MeOH.
C54H54Br2O6 (958.81)
calcd.: C 67.64, H 5.68
found: C 67.59, H 5.88
IR (KBr): ν~ = 2961 (w), 2930 (w), 2873 (w), 1664 (s), 1592 (w), 1461 (w), 1430 (w),
1384 (w), 1316 (m), 1291 (m), 1237 (w), 1207 (m), 1161 (w), 1118 (w), 1078 (w), 1036
(w), 1007 (m), 961 (w), 894 (w), 836 (w), 808 (w), 756 (w) cm-1.
290 Experimental Part
UV/Vis (CH3CN): λmax (lg ε) = 279 (4.1) nm.
1H NMR (400 MHz, CDCl3): δ = 0.99 (t, J = 7.4 Hz, 6 H, CH3), 1.02 (t, J = 7.4 Hz, 6
H, CH3), 1.88–198 (m, 8 H, CH2CH3), 3.19 (d, J = 13.4 Hz, 4 H, ArCH2Ar), 3.82 (t, J =
7.4 Hz, 4 H, OCH2), 3.97 (t, J = 7.5, 4 H, OCH2), 4.45 (d, J = 13.3 Hz, 4 H, ArCH2Ar),
6.49 (m, 6 H, m-Ar’H, p-Ar’H), 6.97 (dd, J = 7.31 Hz, J = 1.13 Hz, 2 H, PhH), 7.29,
7.30 and 7.35 (td, J = 7.6 Hz, J = 1.90 Hz, s and td, J = 7.5 Hz, J = 1.1 Hz,
superimposed, 8 H, PhH, m-ArH), 7.59 (dd, J = 7.9 Hz, J = 1.0 Hz, 2 H, PhH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.3 (q, CH3), 10.5 (q, CH3), 23.4 (t, CH2CH3),
23.5 (t, CH2CH3), 31.1 (t, ArCH2Ar), 77.0 (t, OCH2), 77.3 (t, OCH2), 119.7 (s, PhCBr),
122.8 (d, p-Ar’CH), 127.2 (d, PhCH), 128.4 (d, m-Ar’CH), 129.4 (d, PhCH), 130.2 (s,
p-ArC), 130.9 (d, PhCH), 131.4 (d, m-ArCH), 133.1 (d, PhCH), 134.1 (s, Ar’CCH2Ar),
136.1 (s, ArCCH2Ar’), 140.8 (s, PhC), 156.1 (s, Ar’CO), 162.3 (s, ArCO), 195.0 (s,
C=O) ppm.
MS (FAB): m/z (%) = 959 (14) [M+H]+, 185 (54).
2nd fraction: Rf (2:1 DCM/PE) = 0.40, 431 mg (34 %) of paco-Bis(bromobenzoyl)-
calixarene 175 were obtained as colorless solid with mp 125–127 °C.
C54H54Br2O6 (958.81)
calcd.: C 67.64, H 5.68
found: C 67.84, H 5.78
IR (KBr): ν~ = 3062 (w), 3027 (w), 2960 (m), 2931 (m), 2873 (m), 1664 (s), 1559 (m),
1456 (m), 1429 (w), 1385 (w), 1313 (s), 1248 (w), 1208 (m), 1198 (m), 1160 (w), 1122
(m), 1082 (w), 1065 (w), 1049 (w), 1040 (w), 1028 (w), 1003 (m), 961 (w), 907 (w),
889 (w), 867 (w), 850 (w), 802 (w), 752 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 282 (4.5) nm.
Syntheses 291
1H NMR (400 MHz, CDCl3): δ = 0.77 (t, J = 7.5 Hz, 3 H, CH2CH3), 1.01 (t, J = 7.4 Hz,
6 H, CH2CH3), 1.08 (t, J = 7.5 Hz, 3 H, CH2CH3), 1.38-1.48 (m, 2 H, CH2CH3), 1.73–
1.82 (m, 4 H, CH2CH3), 1.91–2.01 (m, 2 H, CH2CH3), 3.10 (d, J = 13.5 Hz, 2 H,
ArCH2Ar), 3.41–3.45 (m, 2 H, OCH2), 3.47–3.53 (m, 2 H, OCH2), 3.64–3.72 and 3.67
(m and s, superimposed, 6 H, OCH2, ArCH2Ar), 3.84 (t, J = 7.3 Hz, 2 H, OCH2), 4.09
(d, J = 13.4 Hz, ArCH2Ar), 6.28 (dd, J = 7.7 Hz, J = 1.1 Hz, 2 H, m-Ar’H), 6.47 (t, J =
7.6 Hz, 2 H, p-Ar’H), 6.94 (dd, J = 7.5 Hz, J = 1.5 Hz, 2 H, m-Ar’H), 7.33–7.38 (m, 2
H, PhH), 7.40–7.48 (m, 4 H, PhH), 7.57 (s, 2 H, m-Ar’’H), 7.66-7.69 (m, 2 H, PhH),
7.75 (s, 2 H, m-ArH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH2CH3), 10.7 (q, CH2CH3), 10.9 (q,
CH2CH3), 22.1 (t, CH2CH3), 23.9 (t, CH2CH3), 24.2 (t, CH2CH3), 30.7 (t, ArCH2Ar),
36.0 (t, ArCH2Ar), 75.0 (t, OCH2), 75.6 (t, OCH2), 76.5 (t, OCH2), 119.8 (s, PhCBr),
120.0 (s, PhCBr), 121.9 (d, p-Ar’CH), 126.9 (d, PhCH), 127.3 (d, PhCH), 128.9 (d, m-
Ar’CH), 129.0 (d, PhCH), 129.2 (d, PhCH), 129.7 (d, m-Ar’CH), 130.0 (s, ArC), 130.6
(s, ArC), 130.8 (d, PhCH), 131.0 (d, PhCH), 131.5 (d, m-Ar’’CH, ArCCH2Ar)), 132.8
(s, ArCCH2Ar), 133.0 (s, m-ArCH), 133.3 (d, PhCH), 133.4 (d, PhCH), 134.5 (s,
ArCCH2Ar), 137.6 (s, ArCCH2Ar), 141.5 (s, PhC), 141.8 (s, PhC), 155.7 (s, Ar’CO),
162.3 (s, Ar’’CO), 163.0 (s, ArCO), 195.1 (s, C=O), 195.5 (s, C=O) ppm.
MS (FAB): m/z (%) = 959 (12) [M+H]+, 183 (100).
3rd fraction: Rf (4:1 PE/EtOAc) = 0.27, Rf (2:1 DCM/PE) = 0.24.140 mg (12 %)
Bis(bromobenzoyl)tripropoxycalixarene 176 according to NMR. Data were collected
from another experiment, where 176 was obtained as colorless solid with mp 142 °C.
C51H48Br2O6 (916.73)
calcd.: C 66.82, H 5.28
found: C 66.54, H 5.26
IR (KBr): ν~ = 3521 (w), 3442 (w), 2962 (w), 2930 (w), 2873 (w), 1662 (s), 1589 (m),
1458 (m), 1430 (w), 1386 (w), 1319 (s), 1249 (w), 1208 (m), 1161 (w), 1125 (m), 1081
(w), 1028 (w), 999 (w), 962 (w), 909 (w), 854 (w), 804 (w), 753 (w) cm-1.
292 Experimental Part
UV/Vis (CH3CN): λmax (lg ε) = 293 (4.7) nm.
1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 3 H, CH3), 1.10 (t, J = 7.4 Hz, 6
H, CH3), 1.82–1.97 (m, 4 H, CH2CH3), 2.19–2.29 (m, 2 H, CH2CH3), 3.26 (d, J = 13.3
Hz, 2 H, ArCH2Ar), 3.36 (d, J = 14.0 Hz, 2 H, ArCH2Ar), 3.74 (t, J = 6.7 Hz, 4 H,
OCH2), 3.91–3.95 (m, 2 H, OCH2), 4.32 (d, J = 13.9 Hz, 2 H, ArCH2Ar), 4.41 (d, J =
13.2 Hz, 2 H, ArCH2Ar), 6.07 (s, 1 H, OH), 6.37–6.45 (m, 6 H, m-Ar’H, p-Ar’H), 7.33–
7.48 (m, 6 H, PhH), 7.60 (s, 2 H, m-ArH), 7.65 (s, 2 H, m-Ar’’H), 7.66 and 7.68 (two d,
J = 8.6 and 8.0 Hz, 2 H, PhH) ppm
13
C{1H} NMR (100 MHz, CDCl3): δ = 9.7 (q, CH3), 10.9 (q, CH3), 22.7 (t, CH2CH3),
23.6 (t, CH2CH3), 30.8 (t, ArCH2Ar), 30.9 (t, ArCH2Ar), 76.7 (t, OCH2), 77.9 (t,
OCH2), 119.8 (s, PhCBr), 123.6 (s, p-Ar’CH), 127.3 (d, PhCH), 127.4 (d, PhCH), 127.6
(s, p-ArC), 128.2 (d, m-Ar’CH), 128.5 (d, m-Ar’CH), 129.15 (d, PhCH), 129.23 (d,
PhCH), 130.1 (s, ArCCH2Ar’), 130.8 (d, PhCH), 131.2 (d, PhCH), 131.3 (s, p-Ar’’C),
131.6 (d, m-ArCH), 131.7 (d, m-Ar’CH), 131.9 and 132.8 (both s Ar’CCH2Ar,
Ar’CCH2Ar’’), 133.3 (d, PhCH), 133.4 (d, PhCH), 137.7 (s, Ar’’CCH2Ar’), 141.4 (s,
PhC), 141.7 (s, PhC), 154.4 (s, Ar’CO), 159.2 (s, ArCO), 162.3 (s Ar’’CO), , 195.1(s,
C=O), 195.4 (s, C=O) ppm.
MS (FAB): m/z (%) = 917 (26) [M+H]+, 183 (100).
Syntheses 293
1H NMR (400 MHz, CDCl3): cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (165)
13C NMR (100 MHz, CDCl3): cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (165)
294 Experimental Part
1H NMR (400 MHz, CDCl3): paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (175)
13C NMR (100 MHz, CDCl3): paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-arene (175)
Syntheses 295
1H NMR (400 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxy-calix[4]arene (176)
13C NMR (100 MHz, CDCl3): 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-propoxy-calix[4]arene (176)
296 Experimental Part
2.2.24 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene (165)
To a mixture of calixarene 171 (460 mg, 0.53 mmol and sodium carbonate (1.46 g, 13.8
mmol) in acetonitrile (23 mL), 1-iodopropane (1.43 mL, 14.7 mmol) was added and the
suspension was refluxed for 3 d. The mixture war poured into cold HCl (2 N, 50 mL),
extracted with dichloromethane (3 x 15 mL) and dried over MgSO4. The solvent was
removed at a rotary evaporator and the resulting crystalline solid (468 mg), which was
treated with methanol in an ultrasonic bath. After drying in vacuo (1.1 mbar, 100 °C,
30 min) 386 mg (77 %) of 165 were obtained as colorless solid with mp 273–276 °C.
NMR data are in accord with those mentioned above (2.2.21).
Syntheses 297
2.2.25 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and 5,17-Bis(2-
chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174)
Dipropoxycalixarene 131 (1.40 g, 2.76 mmol), aluminium chloride (1.66 g, 12.4 mmol)
and 2-chlorobenzoyl chloride 148a (1.02 g, 5.81 mmol) were dissolved in dry
dichloromethane (30 mL) and stirred for 35 min at 0 °C. The mixture was hydrolyzed
with hydrochloric acid (2 N, 30 mL), the layers were separated and the aqueous layer
was extracted with dichloromethane (15 mL). The combined organic layers were
washed with water (15 mL) and brine (15 mL), dried over MgSO4 and the solvent was
removed in vacuo. The crude product was purified by flash chromatography (silica gel,
PE/EtOAc 6:1 to 2:1) and the products were dried in vacuo (1 mbar, 100 °C, 30 min).
1st Fraction: Rf (2:1 PE/EtOAc) = 0.63, Chlorobenzoyldipropoxycalixarene 173 (616
mg, 35 %) as colorless solid with mp 134–136 °C.
C41H39ClO5 (647.20)
calcd.: C 76.09, H 6.09
found: C 75.77, H 5.97
IR (KBr): ν~ = 3322 (br w), 3061 (w), 2962 (w), 2927 (w), 2873 (w), 1657 (w), 1591
(w), 1541 (w), 1461 (m), 1433 (w), 1385 (w), 1317 (m), 1290 (w), 1214 (w), 1160 (w),
1127 (w), 1085 (w), 1060 (w), 1036 (w), 1003 (w), 961 (w), 915 (w), 859 (w), 836 (w),
815 (w), 757 (w), 702 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 300 (4.3), 287 (4.3) nm.
298 Experimental Part
1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.04–2.10 (m, 4 H,
CH2CH3), 3.39 and 4.41 (both, d, J = 12.3 Hz, and J = 11.7 Hz, 4 H, ArCH2Ar),
3.95–4.02 (m, 4 H, OCH2), 4.29 and 4.31 (both d, J = 13.0 Hz and J = 12.9 Hz, 4 H,
ArCH2Ar), 6.65 (t, J = 7.5 Hz, 1 H, p-Ar’’H), 6.78 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.88 (d,
J = 7.4 Hz, 2 H, m-Ar’H), 6.95 (d, J = 7.4 Hz, 2 H, m-Ar’H), 7.06 (d, J = 7.5 Hz, 2 H,
m-Ar’’H), 7.32 (d, J = 7.3 Hz, 1 H, PhH), 7.35 (d, J = 7.4 Hz, 1 H, PhH), 7.41 (t, J = 7.5
Hz, 1 H, PhH), 7.47 (d, J = 8.0 Hz, 1 H, PhH), 7.59 (s, 2 H, m-ArH), 8.26 (s, 1 H, OH),
9.27 (s, 1 H, OH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 11.1 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,
ArCH2Ar), 31.6 (t, ArCH2Ar), 78.6 (t, OCH2), 119.2 (d, p-Ar’’CH), 125.6 (d, p-
Ar’CH), 126.7 (d, PhCH), 127.8 (s, p-ArC), 128.1 (s, Ar’’CCH2Ar’), 128.5 (s,
ArCCH2Ar’), 128.6 (d, m-Ar’’CH), 129.1 (d, m-Ar’CH), 129.2 (d, PhCH), 129.5 (d, m-
Ar’CH), 130.1 (d, PhCH), 130.7 (d, PhCH), 131.4 (s, PhCCl), 131.7 (d, m-ArCH),
132.6 (s, Ar’CCH2Ar), 133.7 (s, Ar’CCH2Ar’’), 139.6 (s, PhC), 152.0 (s, Ar’CO), 153.5
(s, Ar’’CO), 159.5 (s, ArCO), 194.0 (s, C=O) ppm.
MS (FAB): m/z (%) = 647 (59) [M+H]+, 139 (100).
Syntheses 299
1H NMR (600 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173)
13C NMR (150 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173)
300 Experimental Part
2nd Fraction: Rf (2:1 PE/EtOAc) = 0.46, Bis(chlorobenzoyl)dipropoxycalixarene 174
(1.15 g, 53 %) as colorless solid with mp181-184 °C.
IR (KBr): ν~ = 3322 (br w), 3061 (w), 2962 (w), 2927 (w), 2873 (w), 1657 (w), 1591
(w), 1541 (w), 1461 (m), 1433 (w), 1385 (w), 1317 (m), 1290 (w), 1214 (w), 1160 (w),
1127 (w), 1085 (w), 1060 (w), 1036 (w), 1003 (w), 961 (w), 915 (w), 859 (w), 836 (w),
815 (w), 757 (w), 702 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 301 (4.5) nm.
1H NMR (600 MHz, CDCl3): δ = 1.32 (t, J = 7.4 Hz, 6 H, CH3), 2.05-2.10 (m, 4 H,
CH2CH3), 3.43 (d, J = 13.1 Hz, 4 H, ArCH2Ar), 3.99 (t, J = 6.1 Hz, 4 H, OCH2), 4.28
(d, J = 13.1 Hz, 4 H, ArCH2Ar), 6.81 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.92 (d, J = 7.5 Hz, 4
H, m-Ar’H), 7.32 (d, J = 7.5 Hz, 2 H, PhH), 7.35 (t, J = 7.4 Hz, 2 H, PhH), 7.42 (t, J =
7.6 Hz, 2 H, PhH), 7.48 (d, J = 8.0 Hz, 2 H, PhH), 7.59 (s, 4 H, m-ArH), 9.23 (s, 2 H,
OH) ppm.
13
C{1H} NMR (150 MHz, CDCl3): δ = 11.1 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,
ArCH2Ar), 78.7 (t, OCH2), 125.8 (d, p-ArCH), 126.7 (d, PhCH), 128.0 (s, p-ArC),
128.3 (s, ArCCH2Ar’), 129.1 (d, PhCH), 129.6 (d, m-Ar’CH), 130.1 (d, PhCH), 130.7
(d, PhCH), 131.3 (s, PhCCl), 131.7 (d, m-ArCH), 132.7 (s, Ar’CCH2Ar), 139.6 (s, PhC),
151.9 (s, Ar’CO), 159.4 (s, ArCO), 193.9 (s, C=O) ppm.
MS (FAB): m/z (%) = 785 (31) [M+H]+, 139 (100).
Syntheses 301
1H NMR (600 MHz, CDCl3): 5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]-arene (174)
13C NMR (150 MHz, CDCl3): 5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]-arene (174)
302 Experimental Part
2.2.26 cone-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163),
5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181) and
paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)
Sodium hydride (60 % dispersion in mineral oil, 1.38, 34.5 mmol, washed with hexane
(2 x 15 mL) prior to use) was suspended in dry DMF (60 mL), calixarene 173 (1.69 g,
2.62 mmol) were added and the suspension was heated to 80 °C for 30 min before
adding propyl iodide (10.0 mL, 102 mmol). The mixture was stirred at 80 °C overnight,
cooled to room temperature and poured into ice water (120 mL). It was extracted with
dichloromethane (3 x 20 mL), the organic layer was washed with aqueous ammonium
chloride (1 N, 2 x 20 mL), water (20 mL) and brine (20 mL), dried over magnesium
sulfate and the solvent was removed in vacuo. The brown residue (1.31 g) was
submitted to multiple flash chromatography (silica gel, 1. PE/EtOAc 6:1 to 2:1; 2.
PE/EtOAc15:1; 3. PE/DCM 2:1) to yield:
1st Fraction: Rf (10:1 PE/EtOAc): 0.29, Rf (2:1 PE/EtOAc): 0.83. After drying in vacuo
(1.1 mbar, 50–75 °C, 40 min) 454 mg (24 %) of cone-Chlorobenzoylcalixarene 163 as a
colorless solid with mp 87 °C.
NMR data are in accord with those mentioned above (2.2.19).
2nd Fraction: Rf (2:1 PE/EtOAc): 0.80. According to NMR about 293 mg (16 %) of
Chlorobenzoyltripropoxycalixarene 181 were formed. The compound was not further
characterized.
1H NMR (200 MHz, CDCl3): δ = 0.93 (t, J = 7.6 Hz, 3 H, CH3), 1.11 (t, J = 7.4 Hz, 6
H, CH3), 1.84–1.96 (m, 4 H, CH2CH3), 2.20–2.32 (m, 2 H, CH2CH3), 3.22 (d, J = 13.1
Hz, 2 H, ArCH2Ar), 3.35 (d, J = 14.0 Hz, 2 H, ArCH2Ar), 4.33 and 4.40 (both d,
Syntheses 303
superimposed, J = 12.5 Hz and J = 12.8 Hz, 4 H, ArCH2Ar), 5.99 (s, 1 H, OH), 6.40 (m,
6 H, m-ArH, p-ArH), 6.97 (t, J = 7.4 Hz, 1 H, p-ArH), 7.18 (d, J = 7.3 Hz, 2 H, m-ArH),
7.36–7.47 (m, 4 H, PhH), 7.61 (s, 2 H, m-ArH) ppm.
3rd Fraction: Rf (10:1 PE/EtOAc): 0.42. 46 mg (2 %) of paco-Chlorobenzoylcalixarene
182 as a colorless solid with mp 168–171 °C after drying in vacuo (0.71 mbar, 50–75
°C, 30 min).
C47H51ClO5·1/16 CH2Cl2 (736.67)
calcd.: C 76.73, H 7.00
found: C 76.63, H 7.00
IR (KBr): ν~ = 3063 (w), 3028 (w), 2961 (w), 2931 (w), 2873 (w), 2742 (w), 1665 (w),
1590 (w), 1457 (m), 1431 (w), 1384 (w), 1312 (m), 1293 (w), 1248 (w), 1200 (m), 1150
(w), 1121 (w), 1086 (w), 1064 (w), 1040 (w), 1005 (w), 962 (w), 907 (w), 888 (w), 849
(w), 804 (w), 758 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 278 (4.8) nm.
1H NMR (400 MHz, CDCl3): δ = 0.75 (t, J = 7.5 Hz, 3 H, CH3), 1.02 (t, J = 7.5 Hz, 6
H, CH3), 1.06 (t, J = 7.4 Hz, 3 H, CH3), 1.35- 1.45 (m, 2 H, CH2CH3), 1.73-1.82 (m, 4
H, CH2CH3), 1.90-1.99 (m, 2 H, CH2CH3), 3.05 (d, J = 13.3 Hz, 2 H, ArCH2Ar), 3.33-
3.37 (m, 2 H, OCH2), 3.49-3.55 (m, 2 H, OCH2), 3.64-3.72 (m, 6 H, OCH2, ArCH2Ar),
3.82 (t, J = 7.3 Hz, 2 H, OCH2), 4.07 (d, J = 13.2 Hz, 2 H, ArCH2Ar), 6.32 (d, J = 6.7
Hz, 2 H, m-Ar’H), 6.45 (t, J = 7.5 Hz, 2 H, p-Ar’H), 6.91 (d, J = 6.8 Hz, t, J = 7.3 Hz,
superimposed, 3 H, m-Ar’H and p-Ar’’H), 7.09 (d, J = 7.4 Hz, 2 H, m-Ar’’H), 7.38 (td,
J = 7.3 Hz, J = 1.2 Hz, 1 H, m-PhH), 7.44 (td, J = 7.6 Hz, J = 1.7 Hz, 1 H, p-PhH),
7.48-7.52 (m, 2 H, o-PhH, m-PhH), 7.76 (s, 2 H, m-ArH) ppm.
13C{
1H} NMR 100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.0
(t, CH2CH3), 23.9 (t, CH2CH3), 24.2 (t, CH2CH3) 30.7 (t, ArCH2Ar), 36.2 (t, ArCH2Ar),
74.8 (t, OCH2), 75.5 (t, OCH2), 76.5 (t, OCH2), 121.7 (d, p-Ar’CH), 122.5 (d, p-
304 Experimental Part
Ar’’CH), 126.4 (d, m-PhH), 128.9 (d, m-ArCH), 129.07 (d, m-ArCH), 129.11 (d, PhH),
129.4 (d, m-ArCH), 130.2 (d, PhH), 130.3 (s, PhC), 130.6 (d, p-PhH), 131.4 (s,
ArCCH2Ar), 131.6 (s, ArC), 133.1 (d, m-ArCH), 133.7 (s, ArCCH2Ar), 134.6 (s,
ArCCH2Ar), 137.2 (s, ArCCH2Ar), 139.9 (s, PhC), 155.8 (s, Ar’CO), 156.9 (s, Ar’’CO),
163.1 (s, ArCO), 194.5 (s, C=O) ppm.
MS (FAB): m/z (%) = 731 (21) [M+H]+, 139 (100).
1H NMR (200 MHz, CDCl3): 5-(2-Chlorobenzoyl)-25,26,27-tri-n-propoxcalix[4]arene (181)
Syntheses 305
1H NMR (400 MHz, CDCl3): paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)
13C NMR (100 MHz, CDCl3): paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)
306 Experimental Part
2.2.27 cone-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (166), paco-
5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177) and 5,17-Bis(2-
chloro-benzoyl)-25,26,27-tri-n-propoxcalix[4]arene (178)
Sodium hydride (60 %, 600 mg, 15.0 mmol) was wahed with hexane (2 x 5 mL) under
argon and suspended in DMF (25 mL) with calixarene 174 (896 mg, 1.14 mmol). The
suspension was stirred 30 min at 80 °C, 1-iodopropane (4.30 mL, 44.1 mmol) was
added at room temperature and the mixture was stirred at 80 °C overnight. After cooling
to room temperature ice water (50 mL) was added and the mixture was extracted with
dichloromethane (3 x 20 mL), the organic layer was washed with aqueous ammonium
chloride (1 N, 20 mL), water (20 mL) and brine (20 mL), dried over MgSO4 and the
solvent was removed in vacuo. The obtained solid was crystallized from DCM/MeOH
and dried in vacuo (0.91 mbar, 125 °C, 30 min) to yield 394 mg (40 %) of calixarene
166 as colorless crystals with mp 247 °C. The remaining residue was submitted to flash
chromatography (silica gel, PE/EtOAc 5:1, Rf in PE/EtOAc 5:1: 0.54 (177), 0.42 (178).
The first fraction was treated with methanol in an ultrasonic bath, filtrated and dried in
vacuo (0.35 mbar, 100 °C, 30–45 min). paco-Bis(chlorobenzoyl)calixarene 177 283 mg
(29 %) was isolated as a colorless solid with mp 184 °C. The second fraction contained
traces of still impure trialkylated calixarene 178.
Data for 166 are in accord with those mentioned above (2.2.19).
1st Fraction: Rf (5:1 PE/EtOAc): 0.54. paco-Bis(chlorobenzoyl)calixarene 177.
C54H54Cl2O6 (869.91)
calcd.: C 74.56, H 6.26
found: C 74.61, H 6.46
Syntheses 307
IR (KBr): ν~ = 3062 (w), 3025 (w), 2961 (w), 1932 (w), 1874 (w), 1663 (s), 1591 (w),
1456 (m), 1432 (w), 1286 (w), 1314 (s), 1292 (w), 1247 (w), 1207 (m), 1199 (m), 1160
(w), 1121 (m), 1083 (w), 1061 (w), 1038 (w), 1004 (w), 962 (w), 908 (w), 889 (w), 867
(w), 852 (w), 803 (w), 756 (m) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 282 (4.5) nm.
1H NMR (400 MHz, CDCl3): δ = 0.76 (t, J = 7.5 Hz, 3 H, CH3), 1.01 (d, J = 7.5 Hz, 6
H, CH3), 1.08 (t, J = 7.5 Hz, 3 H, CH3), 1.37–1.47 (m, 2 H, CH2CH3), 1.72–1.81 (m, 4
H, CH2CH3), 1.91–2.01 (m, 2 H, CH2CH3), 3.10 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 3.42
(„t“, J = 8.3 Hz, 2 H, OCH2), 3.49 (t, J = 7.2 Hz, 2 H, OCH2), 3.51 (t, J = 7.2 Hz, 2 H,
OCH2), 3.63-3.73 (m with s at 3.67, superimposed, 6 H, OCH2, ArCH2Ar), 3.84 (t, J =
7.3 Hz, 2 H, OCH2), 4.08 (d, J = 13.4 Hz, 2 H, ArCH2Ar), 6.27 (dd, J = 7.7 Hz, J = 1.0
Hz, 2 H, m-Ar’H), 6.47 (t, J = 7.6 Hz, 2 H, p-Ar’H), 6.94 (dd, J = 7.4 Hz, J = 1.5 Hz, 2
H, m-Ar’H), 7.36-7.50 (m, 8 H, PhH), 7.57 (s, 1 H, m-Ar’’H), 7.75 (s, 1 H, m-ArH)
ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.1 (q, CH3), 10.7 (q, CH3), 11.0 (q, CH3), 22.1
(t, CH2CH3), 23.8 (t, CH2CH3), 24.3 (t, CH2CH3), 30.8 (t, ArCH2Ar), 36.0 (t,
ArCH2Ar), 75.0 (t, OCH2), 75.6 (t, OCH2), 76.5 (t, OCH2), 122.0 (d, p-Ar’CH), 126.4,
126.8, 128.9 (d, m-ArCH), 129.12, 129.31, 129.7 (d, m-Ar’CH), 130.21, 130.24, 130.3,
130.7, 130.9, 130.97, 131.4 (d, m-ArCH), 131.5, 131.57 (s, ArCCH2Ar), 131.64, 132.8
(s, ArCCH2Ar), 133.0 (d, m-ArCH), 134.5 (s, ArCCH2Ar), 137.6 (s, ArCCH2Ar), 139.4
(s, PhC), 139.8 (s, PhC), 155.7 (s, Ar’CO), 162.3 (s, Ar’’CO), 163.0 (s, ArCO), 194.5
(s, C=O), 194.9 (s, C=O) ppm.
MS (FAB): m/z (%) = 869 (10) [M+H]+, 139 (100).
308 Experimental Part
1H NMR (400 MHz, CDCl3): paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]-arene (177)
13C NMR (100 MHz, CDCl3): paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]-arene (177)
Syntheses 309
2.2.28 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184)
Calixarene 165 (253 mg, 264 µmol), pivalic acid (53 mg, 461 µmol) and potassium
carbonate (429 mg, 3.10 mmol) were suspended in DMA (5 ml) in a screw-cap flask.
Bedford catalyst 150 (28 mg, 17 µmol) was added under argon and the mixture was
heated to 120 °C for 10 h. After cooling to room temperature it was quenched with HCl
(2 N, 15 ml) and extracted with DCM (3 x 10 ml). The organic layer was washed with
water (10 ml) and dried over MgSO4. The solvent was removed in vacuo and the
residue was submitted to flash chromatography (silica gel, PE/toluene 50:1, Rf = 0.27)
and subsequently crystallized from DCM/EtOH to yield 184 (119 mg, 57 %) as a
yellow crystalline solid with mp > 300 °C after drying in vacuo (100 °C, 0.57 mbar,
20 min).
Mixture of steroisomers:
IR (KBr): ν~ = 3061 (w), 3017 (w), 2961 (w), 2932 (w), 2874 (w), 1707 (s), 1666 (w),
1572 (w), 1453 (w), 1435 (w), 1417 (w), 1382 (w), 1363 (w), 1307 (w), 1244 (w), 1187
(m), 1111 (w), 1087 (w), 1064 (w), 1038 (w), 1001 (w), 965 (w), 947 (w), 909 (w), 892
(w), 863 (w), 757 (w), 722 (w) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 349 (3.5), 302 (3.9), 273 (sh, 4.5), 263 (4.6) nm.
1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.12, 1.15 and 1.17
(three t, J = 7.4, superimposed, 6 H, CH3), 1.86–2.13 (m, 8 H, CH2CH3), 3.19, 3.24 and
3.26 (three d, J = 13.7, 13.7, 13.6 Hz, superimposed, 4 H, ArCH2Ar), 3.65–3.84 (m, 4
H, OCH2), 3.95–4.08 (m, 4 H, OCH2, ArCH2Ar), 4.20–4.30 (m, 2 H, OCH2), 4.41, 4.43,
4.45, 4.49 and 4.50 (five d, J = 13.5, 13.5, 13.3, 14.0, 13.9 Hz, superimposed, 4 H,
310 Experimental Part
ArCH2Ar), 6.15–6.26 (m, 6 H, m-Ar’H, m-Ar’’H, p-Ar’H, p-Ar’’H), 7.25–7.30 (m, 2
H, fluorenoneH), 7.40–7.45 (m, 2 H, fluorenoneH), 7.56 (2 s, 2 H, fluorenoneH), 7.70
(d, J = 7.3 Hz, 2 H, fluorenoneH), 7.83 and 7.85 (two d, J = 8.1, J = 7.9 Hz,
superimposed, 2 H, fluorenoneH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.0 and11.0 (both q, CH3), 23.4, 23.71, 23.74,
23.8 (all t, CH2CH3), 25.5, 25.6, 31.2, 31.3 (all t, ArCH2Ar), 77.2 and77.3 (both t,
OCH2), 122.6 and 122.7 (both d, fluorenoneCH), 122.8, 122.9, 123.0 (all, d, p-Ar’CH,
p-Ar’’CH), 124.2 and 124.3 (both d, fluorenoneCH), 125.6 and 125.7 (both d,
fluorenoneCH), 127.3, 127.5, 127.8, 128.0 (all d, m-Ar’CH, m-Ar’’CH), 128.5 (d,
fluorenoneCH), 129.27, 129.29 (both s, fluorenoneC), 131.8, 131.9, 132.3, 132.5 (all s,
Ar’CCH2Ar, Ar’’CCH2Ar), 134.27 and 134.30 (both s, ArCCH2Ar’), 134.56 and 134.58
(both d, fluorenoneCH), 135.95 and 135.99 (both s, fluorenoneC), 137.3 (s,
ArCCH2Ar’’), 142.2 and 142.3 (both s, fluorenoneC), 145.31 and 145.33 (both s,
fluorenoneC), 155.0, 155.3, 155.6 (all s, Ar’CO, Ar’’CO), 165.1 (s, ArCO), 193.6 (s,
C=O) ppm.
MS (FAB): m/z (%) = 819 (26) [M+Na]+, 797 (100) [M+H]+.
Isomer 184a:
1H NMR (400 MHz, CDCl3): δ = 0.95 (t, J = 7.5 Hz, 6 H, CH3), 1.15 (t, J = 7.4 Hz, 6
H, CH3), 1.85–2.30 (m, 8 H, CH2CH3), 3.26 (d, J = 13.6 Hz, 2 H, ArCH2Ar), 3.68–3.79
(m, 4 H, OCH2), 3.98–4.04 and 4.00 (m and d, J = 13.7 Hz, 4 H, ArCH2Ar), 4.27 (m, 2
H, OCH2), 4.43 (d, J = 13.5 Hz, 2 H, ArCH2Ar), 4.49 (d, J = 14.0 Hz, 2 H, ArCH2Ar),
6.18–6.23 (m, 6 H, m-Ar’H, p-Ar’H), 7.26 (t, J = 7.2 Hz, 2 H, fluorenoneH), 7.42 (td, J
= 7.6 Hz, J = 1.2, Hz, 2 H, fluorenoneH), 7.56 (s, 2 H, fluorenoneH), 7.69 (dd, J = 7.3
Hz, J = 0.7 Hz, 2 H, fluorenoneH), 7.83 (d, J = 7.7 Hz, 2 H, fluorenoneH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.0 (q, CH3), 11.0 (q, CH3), 23.4 (t, CH2CH3),
23.7 (t, CH2CH3), 25.5 (t, ArCH2Ar), 31.3 (t, ArCH2Ar), 77.3 (t, OCH2), 122.7(d,
fluorenoneCH), 122.9 (d, p-Ar’CH), 124.2 (d, fluorenoneCH), 125.6 (d, fluorenoneCH),
127.3 (d, m-Ar’CH), 128.0 (d, m-Ar’CH), 128.5 (d, fluorenoneCH), 129.3 (s,
fluorenoneC), 131.8 (s, Ar’CCH2Ar), 132.5 (s, Ar’CCH2Ar), 134.3 (s, ArCCH2Ar’),
Syntheses 311
134.6 (d, fluorenoneCH), 135.9 (s, fluorenoneC), 137.3 (s, ArCCH2Ar’),, 142.3 (s,
fluorenoneC), 145.3 (s, fluorenoneC), 155.3 (s, Ar’CO), 165.1 (s, ArCO), 193.6 (s,
C=O) ppm.
312 Experimental Part
1H NMR (400 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184), mixture of stereoisomers
13C NMR (100 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184), mixture of stereoisomers
Syntheses 313
1H NMR (400 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184a)
13C NMR (100 MHz, CDCl3): 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184a)
314 Experimental Part
2.2.29 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene
(212)
Calixarene 188 (500 mg, 0.66 mmol), boronic acid 190 (327 mg, 1.65 mmol) and
tetrakis(triphenylphosphine)palladium(0) (90 mg, 77 µmol) were suspended in toluene
(11 mL) and methanol (3 mL). The mixture was stirred at 100 °C for 15 min, then 2 M
aqueous Na2CO3 (1.8 mL) was added and it was heated to 100 °C for another 4 h. After
cooling to room temperature, the suspension was diluted with CH2Cl2 (20 mL), washed
with 2 M aqueous Na2CO3 (10 mL) containing ammonia (25 %, 0.6 mL), water (10 mL)
and dried over magnesium sulfate. The solvent was removed at a rotary evaporator and
the residue purified by flash chromatography (silica gel, PE/DCM 2:1, Rf = 0.24).
Recrystallization from DCM/MeOH and subsequent drying in vacuo (0.77 mbar,
100 °C, 1 h) yielded 212 (202 mg, 34 %) as colorless crystals with mp 243–244 °C.
C66H52O4 (909.12)
calcd.: C 87.20, H 5.77
found: C 87.32, H 5.84
IR (KBr): ν~ = 3392 (m), 3056 (w), 3025 (w), 2923 (w), 2861 (w), 1594 (w), 1487 (w),
1467 (s), 1433 (m), 1373 (w), 1320 (w), 1249 (m), 1210 (m), 1184 (m), 1156 (w), 1112
(w), 1082 (w), 1009 (w), 978 (w), 913 (w), 887 (w), 823 (w), 761 (s), 742 (s), 699 (s)
cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 278 (4.4) nm.
1H NMR (400 MHz, CDCl3): δ = 3.16 (d, J = 13.2 Hz, 2 H, ArCH2Ar), 4.23 (d, J =
13.1 Hz, 2 H, ArCH2Ar), 5.00 (s, 2 H, OCH2), 6.50 (d, J = 7.6 Hz, 2 H, m-Ar’H), 6.68
Syntheses 315
(t, J = 7.6 Hz, 1 H, p-Ar’H), 6.87 (s, 2 H, m-ArH), 7.15–7.26 (m, 10 H, biphenyl-H),
7.33–7.45 (m, J = 49.2 Hz, 14 H, m-BnH, p-BnH, biphenyl-H), 7.56 (s, 2 H, OH), 7.62
(dd, J = 7.3 Hz, J = 2.1 Hz, 4 H, o-BnH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 31.4 (t, ArCH2Ar), 78.4 (t, OCH2), 125.3 (d, p-
Ar’CH), 126.2 (d, biphenyl-CH), 127.0 (d, biphenyl-CH), 127.4 (o-BnCH), 127.5 (d,
biphenyl-CH), 127.7 (s, ArCCH2Ar’), 128.1 (d, p-BnCH), 128.2 (d, biphenyl-CH),
128.9 (d, m-BnCH), 129.2 (d, m-Ar’CH), 130.0 (d, biphenyl-CH), 130.3 (d, m-ArCH),
130.6 (d, biphenyl-CH), 130.8 (d, biphenyl-CH), 132.1 (s, p-ArC), 133.0 (s,
Ar’CCH2Ar), 137.0 (s, BnC), 140.6 (s, biphenyl-C), 140.7 (s, biphenyl-C), 142.3 (s,
biphenyl-C), 151.9 (s, ArCO), 152.4 (s, ArCOH) ppm.
MS (FAB): m/z (%) = 908 (36) M+, 817 (9) [M-Bn]+.
316 Experimental Part
1H NMR (400 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyl-oxycalix[4]arene (212)
13C NMR (100 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-dibenzyloxycalix[4]arene (212)
Syntheses 317
2.2.30 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene
(214)
Calixarene 213 (500 mg, 0.75 mmol), boronic acid 190 (371 mg, 1.87 mmol) and
tetrakis(triphenylphosphine)palladium(0) (102 mg, 87 µmol) were suspended in toluene
(11 mL) and methanol (3 mL). The mixture was stirred at 100 °C for 15 min, then 2 M
aqueous Na2CO3 (1.8 mL) was added and it was heated to 100 °C for another 4 h. After
cooling to room temperature, the suspension was diluted with DCM (20 mL), washed
with 2 M aqueous Na2CO3 (10 mL) containing ammonia (25 %, 0.6 mL), water (10 mL)
and dried over magnesium sulfate. The solvent was removed at a rotary evaporator. The
residue was purified by flash chromatography (silica gel, PE/DCM 4:1 to 2:1,
Rf (2:1) = 0.36). Recrystallization from DCM/MeOH and subsequent drying in vacuo
(0.7 mbar, 100 °C, 1.5 h) yielded 214 (467 mg, 77 %) as colorless crystals with
mp 248–249°C.
C58H52O4 · 1/8 CH2Cl2 (823.65)
calcd.: C 84.76, H 6.39
found: C 84.53, H 6.47
IR (KBr): ν~ = 3312 (s br), 3056 (w), 3020 (w), 2961 (m), 2922 (s), 2871 (m), 1594
(w), 1485 (m), 1466 (s), 1432 (s), 1384 (w), 1319 (m), 1251 (m), 1201 (s), 1157 (s),
1109 (m), 1080 (w), 1039 (m), 1002 (m), 963 (s), 911 (w), 886 (w), 830 (w), 762 (s),
744 (s) cm-1.
UV/Vis (CH3CN): λmax (lg ε) = 277 (4.0), 224 (4.6, sh) nm.
318 Experimental Part
1H NMR (400 MHz, CDCl3): δ = 1.27 (t, J = 7.4 Hz, 6 H, CH3), 1.96 – 2.06 (m, 4 H,
CH2CH3), 3.18 (d, J = 13.0 Hz, 4 H, ArCH2Ar), 3.91 (t, J = 6.3 Hz, 4 H, OCH2), 4.21
(d, J = 13.0 Hz, 4 H, ArCH2Ar), 6.54 (d, J = 7.5 Hz, 4 H, m-Ar’H), 6.66 (t, J = 7.5 Hz, 2
H, p-Ar’H), 6.87 (s, 4 H, m-ArH), 7.16–7.25 (m, 10 H, biphenyl-H), 7.36–7.45 (m, 8 H,
biphenyl-H), 8.04 (s, 2 H, OH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 11.0 (q, CH3), 23.6 (t, CH2CH3), 31.5 (t,
ArCH2Ar), 78.3 (t, OCH2), 125.2 (d, p-Ar’CH), 126.2 (d, biphenyl-CH), 126.9 (d,
biphenyl-CH), 127.5 (d, biphenyl-CH), 127.8 (s, ArCCH2Ar’), 128.2 (d, biphenyl-CH),
129.1 (d, m-Ar’CH), 130.0 (d, biphenyl-CH), 130.2 (d, m-ArCH), 130.7 (d, biphenyl-
CH), 130.9 (d, biphenyl-CH), 132.0 (s, p-ArC), 133.2 (s, Ar’CCH2Ar), 140.6 (s,
biphenyl-C), 140.7 (s, biphenyl-C), 142.3 (s, biphenyl-C), 152.0 (s, ArCO), 152.5 (s,
ArCOH) ppm.
MS (FAB): m/z (%) = 812.3 (100) M+.
Syntheses 319
1H NMR (400 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene (214)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.0f1 (ppm)
*
*
13C NMR (100 MHz, CDCl3): 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-propoycalix[4]arene (214)
320 Experimental Part
2.2.31 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218)
Dibromocalixarene 138 (1.10 g, 1.47 mmol) was dissolved in dry THF (35 mL) and
cooled to –78 °C. After addition of nBuLi (6.40 mL, 10.2 mmol, 1.6 M in hexane) the
solution was stirred for 25 min before addition of trimethyl borate (3.11 mL, 99 %,
27.1 mmol) and the mixture was stirred at room temperature overnight. Hydrochloric
acid (4 N, 8 mL) was added and the solution was stirred for 90 min. It was with water
(2 x 20 mL), the aqueous layer was washed with ethyl acetate (20 mL), dried over
MgSO4 and the solvent removed in vacuo. The viscous residue was treated with hexane
(80 mL), sonicated for 10 min, filtrated and dried in vacuo (1 mbar, 100 °C, 30 min) to
yield 533 mg (53 %) of 218 as a colorless powder with mp 254–256 °C
(lit.85 249–251 °C). The product was used without further purification.
1H NMR data are in accord with those reported in the literature.85 A signal
superimposed by the HDO peak is marked by an asterisk. The signal at 3.97–4.09 ppm
indicates impurity as it should integrate to only 4 H and appear as a triplet.
Syntheses 321
1H NMR (200 MHz, DMSO-d6): 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-diboronic acid (218)
322 Experimental Part
2.2.32 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(220)
Calixarene 218 (360 mg, 529 µmol) and 2,2'-dibromobiphenyl (219) (362 mg,
1.16 mmol) were dissolved in methanol (2.1 ml) and toluene (7.8 ml) and heated to 100
°C. The mixture was degassed with argon for 10 min before addition of Pd(PPh3)4
(84 mg, 72 µmol), stirred for 15 min, then aqueous Na2CO3 (2 M, 1.2 mL) was added
and the mixture was stirred for another 5 h. After cooling to room temperature, the
suspension was diluted with CH2Cl2 (20 mL), washed with aqueous Na2CO3 (2 M,
10 ml) containing ammonia (25 %, 0.6 mL), water (10 ml) and dried over magnesium
sulfate. The solvent was removed at a rotary evaporator. The residue was purified by
flash chromatography (silica gel, PE/DCM 6:1 to 1:1, Rf (3:1) = 0.38). Recrystallization
from DCM/MeOH and subsequent drying in vacuo (1.0 mbar, 100 °C, 30 min) yielded
220 (141 mg, 25 %) as colorless crystalline solid with mp 136 °C.
1H NMR (400 MHz, CD2Cl2): δ = 0.86 and 0.87 (both t, superimposed, J = 7.5 and 7.4
Hz, 6 H, CH2CH3), 1.07 (t, J = 7.4 Hz, 6 H, CH2CH3), 1.77-1.98 (m, 8 H, CH2CH3),
2.91, 2.97 and 2.98 (three d, superimposed, J = 12.7 Hz, 13.2 Hz and “J” = 14.9 Hz, 4
H, ArCH2Ar), 3.57 (t, J = 6.6. Hz, 4 H, OCH2), 3.93–3.99 (m, 4 H, OCH2), 4.31 and
4.33 (both d, superimposed, J = 13.3 and 13.2 Hz, 4 H, ArCH2Ar), 5.50–5.55 (m, 4 H,
m-Ar’H), 5.97–6.26 (m, 2 H, p-Ar’H), 6.86-6.90 (m, 2 H, m-ArH), 6.96–6.98 (m, 2 H,
m-ArH), 7.19–7.24 (m, 2 H, biphenyl-H), 7.30–7.34 (m, 6 H, biphenyl-H), 7.39–7.49
(m, 6 H, biphenyl-H), 7.65 (d, J = 7.9 Hz, biphenylH)
13
C{1H} NMR (100 MHz, CD2Cl2): δ = 10.2 (q, CH2CH3), 11.3 (q, CH2CH3), 23.7 (t,
CH2CH3), 24.1 (t, CH2CH3), 31.4 (t, ArCH2Ar), 77.0 (t, OCH2), 77.4 (t, OCH2), 122.3
(d, p-ArCH), 124.5 (s, CBr), 127.0 (d, biphenylCH), 127.5 (d, biphenylCH), 127.9,
Syntheses 323
127.96, 128.2, 128.3 (all d, m-Ar’CH), 128.5 (d, biphenylCH), 129.0 (d, biphenylCH),
130.6 (d, biphenylCH), 130.7 (d, m-ArCH), 130.8 (d, m-ArCH),, 131.1 (d,
biphenylCH), 133.1 (d, biphenylCH), 133.15 (d, biphenylCH), 133.24, 133.3 (both s),
133.4 (s, ArCCH2Ar), 134.97, 136.97, 137.00 (all s), 137.3 and 137.4 (s, ArCCH2Ar),
140.6, 142.3, 143.8 (all s), 155.5 (s, ArCO), 157.7 (s, ArCO) ppm.
MS (FAB): m/z (%) = 1054 (50) M+, 976 (23) [M-Br]+.
324 Experimental Part
1H NMR (400 MHz, CD2Cl2): 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene (220)
13C NMR (100 MHz, CD2Cl2): 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-propoxycalix[4]arene (220)
Syntheses 325
2.2.33 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes (217a and
217b)
Biphenyldipropoxycalixarene 214 (164 mg, 202 µmol) was dissolved in dry
dichloromethane (2 mL) and 2,2,2-trifluoroethanol (2 mL) and PIFA (200 mg,
456 µmol) was added. The mixture was stirred at room temperature for 15 min and the
solvent was removed at a rotary evaporator. The brown residue (352 mg) was dissolved
in acetic anhydride (1.5 mL) and one drop of concentrated sulfuric acid was added. The
mixture was heated to 100 °C for 30 min and warmed to room temperature. The next
day it was poured onto ice, extracted with dichloromethane (2 x 10 ml), dried over
MgSO4 and the solvent was removed by rotary evaporation. Methanol was added to the
brown liquid residue and the precipitated solid was collected by filtration and washed
with methanol. After purification by flash chromatography (silica gel, toluene,
Rf = 0.29) about 57 % of 216 were obtained according to the NMR spectrum.
Calixarene 216 (50 mg, 56 µmol) was dissolved in THF (3.5 mL) and NaOH (490 mg)
and water (0.3 mL) were added. The mixture was stirred in a screw-capped flask for 3 d
at room temperature. Water (10 mL) and dichloromethane (10 mL) were added, the
layers separated and the aqueous layer was extracted with DCM (10 mL). The organix
layer was wasches with water (10 mL) and HCl (1 N, 10 mL), dried over MgSO4 and
the solvents was removed at a rotary evaporator. The yellow residue was submitted to
flash chromatography (silica gel, PE/EtOAc 10:1, Rf = 0.15) and recrystallized from
326 Experimental Part
DCM/MeOH to yield 217 (18 mg, 40 %) as colorless solid after drying in vacuo
(0.77 mbar, 100 °C, 45 min). According to the NMR spectra it is a 1:1 mixture of both
stereoisomers.
1H NMR (400 MHz, CDCl3): δ = 1.27–1.36 (m, CH2CH3), 2.05–2.15 (m, CH2CH3),
3.64 and 3.68 (both d, “J” = 14.9 and 14.4 Hz, superimposed, ArCH2Ar), 3.99-4.13 (m,
OCH2), 4.46 and 4.49 (both d, “J” = 12.4 and 12.9 Hz, superimposed, ArCH2Ar), 4.75-
4.90 (m, ArCH2Ar), 5.69 (d, J = 7.6 Hz, 2 H, m-ArH (217b)), 5.86–5.89 (m, 2 H, m-
ArH (217a), 1 H, p-ArH (Zb)), 6.24 (t, J = 7.6 Hz, 2 H, p-ArH (217a)), 6.62–6.68 and s
(m and s, 2 H, m-ArH (217a), 1 H, p-ArH (Zb), OH), 6.78 (s, OH), 6.91 (d, J = 7.6 Hz,
2 H, m-ArH (217b)), 7.50–7.66 (m, triphenyleneH), 8.31–8.37 with 8.32 and 8.38 (m
and 2 s, superimposed, triphenyleneH), 8.54-8.61 (m, triphenyleneH) ppm.
13
C{1H} NMR (100 MHz, CDCl3): δ = 10.9, 10.96, 11.03 (all q, CH2CH3), 23.6, 23.7,
23.8 (all t, CH2CH3), 29.0, 29.2, 31.6, 31.7 (all t, ArCH2Ar), 77.8, 78.1, 78.5 (all t,
OCH2), 122.4 (d, triphenyleneH), 122.5 (d, triphenyleneH), 122.9, 123.2 (d,
triphenyleneH), 123.6, 123.66, 123.68, 123.74 (d, p-ArH (217b)), 124.3 (d,
triphenyleneH), 124.9 (d, p-ArH (217b)), 125.3, 125.36, 125.38, 125.40, 126.0 (d,
triphenyleneH), 126.6, 127.4 (d, triphenyleneH), 127.5 (d, triphenyleneH), 127.8 (d, m-
ArH (217b)), 128.0(d, m-ArH (217a)), 128.8 (d, m-ArH (217a)), 128.9 (s), 129.0 (d, m-
ArH (217b)), 129.1 (s), 129.3 (s), 129.5 (d, triphenyleneH), 129.6 (d, triphenyleneH),
129.98 (s), 130.01 (s), 130.78 (s), 130.79 (s), 130.9 (s), 131.3 (s), 131.45 (s), 131.48 (s),
132.4 (s), 133.8 (s), 134.7 (s), 152.8, 153.2, 153.6 (all s, ArCO), 154.90, 154.94 (both s,
triphenyleneCO) ppm.
MS (FAB): m/z (%) = 808 (27) M+.
Syntheses 327
1H NMR (200 MHz, CDCl3): 50,51-Diacteyl-49,51-di-n-propoxycalix[4]di-triphenylenes (216a and 216b)
0.00.51.01.52.02.53.03.54.04.55.05.56.06.57.07.58.08.5f1 (ppm)
0.90
1.19
1.28
1.29
2.03
2.27
2.36
2.38
2.92
3.26
3.42
4.27
4.52
4.74
5.24
5.34
5.67
5.76
6.21
6.34
6.53
7.04
7.16
7.23
7.41
7.70
8.17
8.35
8.36
8.43
8.57
8.63
*
1H NMR (200 MHz, CDCl3): 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]-ditriphenylenes (217a and 217b)
328 Experimental Part
13C NMR (100 MHz, CDCl3): 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]-ditriphenylenes (217a and 217b)
Syntheses 329
2.2.34 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)
Biphenylcalixaren 220 (260 mg, 246 µmol), triphenylphosphine (26 mg, 99 µmol) and
DBU (0.154 mg, 990 µmol, 98 %) were dissolved in DMA (10 mL) in a screw-capped
flask. The mixture was degassed with argon for 10 min, palladium(II) chloride
(9 mg, 51 µmol) was added and the mixture was stirred for 18 h at 160 °C. After
addition of dichloromethane (20 mL), it was washed with water (15 mL), brine (15 mL)
and dried over MgSO4. The solvent was removed in vacuo and the brown residue
(275 mg) was submitted to flash chromatography (silica gel, PE/EtOAc 15:1, Rf = 0.31).
30 mg (ca. 17 %) of slightly impure 221 was isolated as a mixture of both steroisomers
in a ratio of about 1:1.4 221a:221b. Other fractions did also show product signals in the
NMR spectra, but it was not possible to estimate an overall yield due to the complex
mixture obtained.
1H NMR (400 MHz, CDCl3): δ = 1.00 (t, J = 7.5 Hz, CH2CH3), 1.18 (t, J = 7.4 Hz,
CH2CH3), 1.26 (t, J = 7.4 Hz, CH2CH3), 1.33 (t, J = 7.4 Hz, CH2CH3), 1.87–2.24 (m,
CH2CH3), 3.41 and 3.47 (both d, J = 13.5 and 13.3 Hz, superimposed, ArCH2Ar),
3.74–3.84 (m, OCH2), 4.19–4.31 (m , OCH2), 4.41–4.53 and 3.53 (m and d, J = 15.2
Hz, superimposed, OCH2, ArCH2Ar), 4.61, 4.64 and 4.68 (three d, J = 14.3 Hz, J = 13.5
Hz and J = 13.2 Hz, superimposed, ArCH2Ar), 4.85 and 4.87 (both d, J = 14.5 Hz, J =
14.2 Hz, superimposed, ArCH2Ar), 5.04 (d, J = 7.6 Hz, 2 H, m-ArH (221b), 5.28 (d, J =
7.4 Hz, 2 H, m-ArH (221a)), 5.57 (t, J = 7.6 Hz, 1 H, p-Ar’H (221b), 5.91 (t, J = 7.6 Hz,
2 H, p-ArH (221a)), 6.06 (d, J = 7.0 Hz, 2 H, m-ArH (221a), 6.27 („t“, „J“ = 7.5 Hz, 1
H, p-ArH (221b)), 6.38 (d, J = 7.5 Hz, 2 H, m-ArH (221b)), 7.51–7.70 (m,
triphenyleneH), 8.30–8.36 and 8.36 (m and s, triphenylene H), 8.42 (s, triphenylene H),
8.58–8.69 (m, triphenyleneH) ppm.
330 Experimental Part
13C{
1H} NMR (100 MHz, CDCl3): δ = 10.1, 10.2, 11.0, 11.2, 11.3 (all q, CH2CH3),
23.4, 23.5, 23.8, 23.9, 24.0 (all t, CH2CH3), 30.9, 31.0, 31.4, 31.5 (all t, ArCH2Ar), 76.5,
77.7, 78.0 (all t, OCH2), 122.8 (d, p-ArCH (221b)), 122.88 (d, p-ArCH (221a)), 122.91
(d, triphenyleneCH), 123.0 (d, p-ArCH (221b)), 123.2 (d, triphenyleneCH), 123.3,
123.36, 123.38, 123.5, 123.6, 125.49 (d, triphenyleneCH), 125.52 (d, triphenyleneCH),
126.3 (d, m-ArCH (221b), 126.4 (d, triphenyleneCH), 126.5 (d, triphenyleneCH), 126.6
(d, triphenyleneCH), 126.9 (d, m-ArCH (221a)), 127.2 (d, m-ArCH (221a)), 127.5 (d,
triphenyleneCH), 127.7 (d, m-ArCH (221b)), 129.7 (s), 129.8 (d, triphenyleneCH),
129.9 (s), 130.1 (s), 130.8 (s), 131.09 (s), 131.11 (s), 131.90 (s), 131.94 (s), 132.0 (s),
132.5 (s), 134.0 (s), 134.2 (s), 134.6 (s), 134.9 (s), 136.7 (s), 136.8 (s), 154.3, 154.7,
155.4 (all s, ArCO), 160.8, 160.9 (all s, triphenyleneCO) ppm.
MS (FAB): m/z (%) = 892 (29) M+.
Syntheses 331
1H NMR (400 MHz, CDCl3): 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)
13C NMR (100 MHz, CDCl3): 49,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and 221b)
332 Experimental Part
2.2.35 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)
Diformylcalixarene 78 (247 mg, 0.381 mmol) was dissolved in acetone (2 mL) and
chloroform (2 mL). After addition of sulfamic acid (128 mg, 1.32 mmol) in water
(1 mL) a solution of sodium chlorite (106 mg, 0.938 mmol) in water (1 mL) was added
dropwise and the mixture was stirred at room temperature overnight. The reaction was
quenched with hydrochloric acid (1 N, 15 mL), the aqueous layer was extracted with
chloroform (3 x 15 mL) and dried over MgSO4. The solvent was removed in vacuo to
yield (191 mg, 74 %) of 263 as colorless solid with mp > 300 °C (lit. 271–273 °C184, >
280 °C85 (dec)).
1H NMR (200 MHz, CDCl3): δ = 0.87 (t, J = 7.5 Hz, 6 H, CH3), 1.10 (t, J = 7.4 Hz, 6
H, CH3), 1.77–2.02 (m, 8 H, CH2CH3), 3.16 (d, J = 13.7 Hz, 4 H, ArCH2Ar), 3.67 (t, J =
6.6 Hz, 4 H, OCH2), 4.00 (“t”, “J” = 8.2 Hz, 4 H, OCH2), 4.43 (d, J = 13.5 Hz, 4 H,
ArCH2Ar), 6.77 (m, 4 H, m-ArH), 7.04 (t, J = 7.3 Hz, 2 H, p-Ar’H) , 7.18 (d, J = 7.0
Hz, 4 H, m-Ar’H), 12.89 (br s, 2 H, OH) ppm.
13
C{1H} NMR (50 MHz, CDCl3): δ = 9.9, 10.9 (both q, CH3), 23.1, 23.6 (both t,
CH2CH3), 31.1 (t, ArCH2Ar), 77.0 (t, OCH2), 123.0, 123.3, 129.6, 129.9, 133.8, 136.7,
157.7, 159.9, 172.2 (s, C=O) ppm.
NMR data are in accord with those reported in literature.85,184
Syntheses 333
1H NMR (200 MHz, CDCl3): 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)
13C NMR (50 MHz, CDCl3): 5,17-Dicarboxy-25,26,27,28-tetra-n-propoxycalix[4]arene (263)
334 Experimental Part
2.2.36 25,26,27,28-Tetra-n-propoxycalix[4]arene-5,17-dicarbonyl chloride (264)
Carboxycalixarene 263 (1.10 g, 1.61 mmol) was dissolved in anhydrous
dichloromethane (15 mL) and thionyl chloride (5 mL, 65.4 mmol) was added. The
mixture was heated to 50 °C for 3 h, the solvent was removed in vacuo and the residue
was taken up in dichloromethane (15 mL). It was washed with aqueous NaHCO3 (10 %,
2 x 10 mL) and water (15 mL), dried over MgSO4 and the solvent was removed by
rotary evaporation to yield 264 (847 mg, 73 %) as yellow solid. The crude product
contained at least 90 % of the acid chloride according to 1H NMR data, which are in
accord with the literature.187
335
III. Appendix
1 Cross-peak tables
1.1 General Remarks
The numbering of the molecules depicted with each cross-peak table does not follow
official guidelines. However, the numbering of the parent calixarene (see Chapter
I.1.1.4) was adopted for the calixarene framework. Further numbering includes first all
the lower rim substituents then those at the upper rim, always starting from the smallest
number at the calixarene framework. The system was adapted accordingly to
calixarenes with anellated subunits treating the fused rings as part of the parent
skeleton. The same system has been used for the numbering of the crystal structures.
Tentative assignments of peaks to a certain position are marked in italics. The
correlations between proton and carbon signal for these cases were deduced from the
spectra as good as possible. In addition, peak intensities as well as shifts of comparable
structures were considered. If the cross-peaks could not be correlated to a certain carbon
atom or those could not be assigned to a certain position, the respective cells in the table
are marked with ‘n.b.’ for ‘not determinable’.
336 Appendix
1.2 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanone
(118)
1
2
3
4
5
6
O
7 8
10
11
12
O
13
14
15
16
17
9
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
7/8 16.43 2.34
11 45.78 4.40
9 59.81 3.77
13 125.26 -
16 127.63 7.28
15 128.77 7.15
2/6 129.57 7.73
3/5 131.43 -
17 131.80 7.24
1 132.49 -
14 132.92 7.60
12 135.42 -
4 161.61 -
10 195.80 -
Cross-peak tables 337
1.3 2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethanol
(124)
1
2
3
4
5
6
O
7 8
10
11
12
HO
13
14
15
16
17
9
Br18
C atom δ [ppm] HMQC cross peaks
[ppm]
7,8 16.3 2.30
11 46.3 3.05, 3.19
9 59.8 3.72
10 73.3 4.92
13 125.0 -
2,6 126.3 7.06
n.d. 127.5 7.24
n.d. 128.5 7.11
n.d. 131.0 -
n.d. 132.2 7.24
14 133.1 7.58
n.d. 138.1 -
12 139.3 -
4 156.6 -
338 Appendix
1.4 (2-(2-Bromophenyl)-1-(4-methoxy-3,5-dimethylphenyl)ethoxy)-
trimethylsilane (125)
1
2
3
4
5
6
O
7 8
10
11
12
O
13
14
15
16
17
9
Br
Si
18
20
19
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
18,19,20 -0.24 -0.19 -0.19
7,8 16.3 2.28 7.01 (2,6)
11 47.8 2.89, 3.12 4.86 (10), 7.01 (2,6),
7.17 (17), 7.55 (16)
9 59.8 3.72 2.28 (7,8), 7.01 (2,6)
10 73.4 4.86 2.89 (11), 3.12 (11),
7.01 (2,6)
13 124.9 - 2.89 (11), 3.12 (11), 7.08
(15), 7.17 (17), 7.55 (14)
2,6 126.0 7.01 2.28 (7,8), 4.86 (10),
7.01 (2,6)
16 127.0 7.19 7.55 (14)
15 128.1 7.08 7.17 (17)
3,5 130.4 - 2.28 (7,8), 7.01 (2,6)
14 132.6 7.55 7.19 (16)
17 133.2 7.17 2.89 (11), 3.12 (11),
7.08 (15), 7.55 (14)
12 138.8 -
2.89 (11), 3.12 (11), 4.86
(10), 7.08 (15), 7.19 (16),
7.55 (14)
Cross-peak tables 339
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
1 140.3 - 2.89 (11), 3.12 (11),
4.86 (10)
4 156.1 - 2.28 (7,8), 3.72 (9),
7.01 (2,6)
340 Appendix
1.5 (9,10-Dihydrophenanthrene-9,10-diyl)bis((4-methoxy-3,5-
dimethyl-phenyl)methanone) (120a) and Phenanthrene-9,10-
diylbis((4-methoxy-3,5-dimethylphenyl)methanone) (120b)
43
2
1 10a
10 9
8a 8
7
65
4b4a
10'
1'
O6'5' O4'
3' 2'
8'
9'
7'
10'
1'
6' 5'
4'
3'2'
O
8'
9'
7'
O
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7’,8’ 16.4 2.30 7.77 (2’/6’)
9,10 48.9 5.47 5.47 (9/10), 6.95 (1/8)
9’ 59.8 3.77 -
4,5 124.5 7.83 6.95 (1/8), 7.17 (2/7),
7.37 (3/6)
1,8 127.0 6.95 5.47 (9/10)
3,6 127.9 7.37 7.17 (2/7)
2,7 128.2 7.17 6.95 (1/8), 7.83 (4/5)
2’,6’ 130.0 7.77 7.77 (2’/6’)
3’,5’ 131.7 - 2.30 (7’/8’)
1’ 133.8 - -
4a,4b 134.4 - 6.95 (1/8), 7.37 (3/6)
8a,10a 136.4 - 5.47 (9/10), 7.17 (2/7),
7.83 (4/5)
4’ 162.0 - 2.30 (7’/8’), 3.77 (9’),
7.77 (2’/6’)
10’ 201.7 - 5.47 (9/10), 7.77 (2’/6’)
Cross-peak tables 341
43
2
1 10a
10 9
8a 8
7
65
4b4a
10'
1'
O6'5' O4'
3' 2'
8'
9'
7'
10'
1'
6' 5'
4'
3'2'
O
8'
9'
7'
O
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
7’,8’ 16.3 2.18 7.44 (2’/6’)
9’ 59.7 3.72 -
4,5 123.1 8.81 7.53 (2/7)
2,3,6,7 127.5 7.53, 7.69 7.73 (1/8)
1,8 127.9 7.73 7.69 (3/6)
8a,10a 128.9 - 7.53 (2/7), 8.81 (4/5)
4a,4b 130.6 - 7.53 (2/7), 7.69 (3/6),
7.73 (1/8), 8.81 (4/5)
3’/5’ 131.3 - -
2’,6’ 131.4 7.44 2.18 (7’/8’), 7.44 (2’/6’)
1’ 133.6 - -
9,10 135.5 - 7.69 (3/6)
4’ 162.0 - 2.18 (7’/8’), 3.72 (9’),
7.44 (2’/6’)
10’ 197.6 - 7.44 (2’/6’)
342 Appendix
1.6 1-(4-Methoxy-3,5-dimethylphenyl)-2-phenylethanone (127) and
1-(4-Hydroxy-3,5-dimethylphenyl)-2-phenylethanone (128)
1
2
3
4
5
6
O
7 8
10
11
12
O
13
14
15
16
17
9
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7/8 16.4 2.32 7.69 (2/6)
11 45.4 4.23 7.28 (13/17)
9 59.8 3.75 -
15 126.9 7.24 7.28 (13/17)
14,16 128.8 7.32 7.32 (14/16)
13,17 129.6 7.28 4.23 (11), 7.24 (15)
2,6 129.9 7.69 7.69 (2/6)
3,5 131.4 - 2.32 (7/8)
1 132.5 - -
12 135.1 - 4.23 (11), 7.32 (14/16)
4 161.5 - 2.32 (7/8), 3.75 (9),
7.69 (2/6)
10 197.2 - 4.23, 7.69 (2/6)
Cross-peak tables 343
1
2
3
4
5
6
OH
7 8
10
11
12
O
13
14
15
16
17
9
C atom δ [ppm] HMQC cross peaks
[ppm]
7/8 16.0 2.27
11 45.3 4.21
3/5 123.1 -
15 126.8 7.23
14,16 128.7 7.31
1 129.4 -
13,17 129.5 7.27
2/6 130.1 7.69
12 135.3 -
4 156.9 -
10 196.8 -
7/8 16.0 2.27
344 Appendix
1.7 5-(2-Bromophenethyl)-2-methoxy-1,3-dimethylbenzene (129)
1
2
3
4
5
6
O
7 8
10
11
12
14
15
16
17
9
Br
13
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.2 2.29 6.89 (4/6)
10 35.8 2.80 6.89 (4/6)
11 38.7 3.00 7.20 (17)
9 59.9 3.73 -
13 124.6 - 3.00 (11), 7.07 (15),
7.20 (17), 7.56 (14)
16 127.5 7.22 7.56 (14)
15 127.8 7.07 7.20 (17)
4,6 128.9 6.89 2.80 (10), 6.89 (4/6)
17 130.6 7.20 3.00 (11)
1,3 130.7 - 2.29 (7/8)
14 133.0 7.56 7.22 (16)
5 136.9 - 2.80 (10), 3.00 (11)
12 141.3 - 2.80 (10), 3.00 (11),
7.22 (16), 7.56 (14)
2 155.4 - 2.29 (7/8), 3.73 (9),
6.89 (4/6)
Cross-peak tables 345
1.8 3-Methoxy-2,4-dimethyl-9,10-dihydrophenanthrene (130)
1
2
3
4
4a
10a
4b
8a
9
10
5
6
7
8
13
O
11
12
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
13 15.8 2.55 -
11 16.2 2.32 6.95 (1)
9 30.3 2.71 2.71 (10), 7.26 (8)
10 30.4 2.71 2.71 (9), 6.95 (1)
12 59.9 3.79 2.32 (11), 2.55 (13)
6 or 8 125.8 7.28 -
7 126.6 7.20 7.63 (5)
6 or 8 127.6 7.27 -
1 127.9 6.95 2.71 (10)
4 128.0 - 2.55 (13)
5 128.5 7.63 2.32 (11), 7.20 (7)
2 129.4 - -
4a 133.8 - 2.55 (13), 6.95 (1), 7.63 (5)
4b 135.0 - 7.27-7.28 (6/8)
10a 135.3 - 2.71 (9)
-
8a 139.9 - 2.71 (10), 7.20 (7), 7.63 (5)
3 156.9 - 2.32 (11), 2.55 (13), 3.79
(12), 6.95 (1)
346 Appendix
1.9 (2-Chlorophenyl)(4-methoxy-3,5-dimethylphenyl)methanone
(149a)
2
3
4
5
6
1
10
O
O
9
87
11
12
13
14
15
16
Cl
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.4 2.30 7.49 (2/6)
9 59.8 3.78 -
126.7 7.35 7.44
129.0 7.35 -
130.2 7.44 7.42
7.35
13,14,
15,16
131.0 7.42 7.35
2,6 131.3 7.49 2.30 (7/8), 7.49 (2/6)
131.5 - n.d. 1,3,5,11
132.2 - indetetminable
12 139.2 - 7.35, 7.42, 7.44
4 162.1 - 2.30 (7/8), 3.78 (9),
7.49 (2/6)
10 194.7 - 7.35 (16), 7.49 (2/6)
Cross-peak tables 347
1.10 (2-Bromophenyl)(4-methoxy-3,5-dimethylphenyl)methanone
(149b)
2
3
4
5
6
1
10
O
O
9
87
11
12
13
14
15
16
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.38 2.29 7.48 (2,6)
9 59.83 3.77 -
12 119.60 - 7.30 (16), 7.64 (13)
15 127.21 7.40 7.64 (13)
16 128.90 7.30 7.34 (14)
14 131.00 7.34 7.30 (16)
2,6 131.46 7.48 2.29 (7,8), 7.48 (2,6)
3,5 131.55 - -
1 131.81 - -
13 133.28 7.64 7.40 (15)
11 141.20 - 7.40 (15), 7.64 (13)
4 162.12 - 2.29 (7,8), 3.77 (9),
7.48 (2,6)
10 195.31 - 7.30 (16), 7.48 (2,6)
348 Appendix
1.11 (2-Iodophenyl)(4-methoxy-3,5-dimethylphenyl)methanone (149c)
2
3
4
5
6
1
10
O
O
9
87
11
12
13
14
15
16
I
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.4 2.30 7.48 (2,6)
9 59.8 3.78 -
12 92.4 - 7.17 (14),.7.27 (16),
7.43 (15), 7.92 (13)
15 127.8 7.43 7.92 (13)
16 128.4 7.27 7.17 (14)
14 131.0 7.17 7.27 (16), 7.43 (15)
1 131.3 - -
3,5 131.6 - -
2,6 131.7 7.48 2.30 (7,8), 7.48 (2,6)
13 139.8 7.92 7.43 (15)
11 144.9 - 7.43 (15), 7.92 (13)
4 162.1 - 2.30 (7,8), 3.78 (9),
7.48 (2,6)
10 196.8 - 3.78 (9), 7.27 (16),
7.48 (2,6)
Cross-peak tables 349
1.12 3-Methoxy-2,4-dimethyl-9H-fluoren-9-one (151)
1
2
3
4
4a
9a4b
8a9
5
6
78
1012
O
O
11
C atom δ
[ppm]
HMQC cross peaks
[ppm]
10 12.8 2.50
12 16.6 2.29
11 60.3 3.76
8 123.1 7.60
5 124.2 7.63
1 125.0 7.38
n.d. 127.6 -
7 128.3 7.25
n.d. 130.2 -
n.d. 131.7 -
6 134.5 7.45
n.d. 135.1 -
n.d. 142.5 -
n.d. 145.2 -
3 162.8 -
9 193.7 -
350 Appendix
1.13 2-(4-Methoxy-3,5-dimethylbenzoyl)benzoic acid (154)
2
3
4
5
6
1
10
O
O
9
87
11
16
15
14
1312
17HO18
O
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.4 2.27 7.41 (2/6)
9 59.8 3.76 -
16 127.9 7.34 7.56 (14)
12 128.0 - 7.65 (15)
14 129.5 7.56 7.34 (16)
-
2,6 130.9 7.41 2.27 (7/8), 7.41 (2/6)
13 131.1 8.09 7.65 (15)
3,5 131.3 - -
1 132.6 - -
15 133.1 7.65 8.09 (13)
11 142.9 - 7.65 (15), 8.09 (13)
4 161.7 - 2.27 (7/8), 3.76 (9),
7.41 (2/6)
17 169.7 - 8.09 (13)
10 196.6 - 7.34 (16), 7.41 (2/6)
Cross-peak tables 351
1.14 3,3-Bis(4-methoxy-3,5-dimethylphenyl)isobenzofuran-1(3H)-one
(161)
12
1116
15
14
13
17
O10
1
O
23
4
56
7
O
9
8
O
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,8 16.4 2.20 6.94 (2/6)
9 59.8 3.70 -
10 91.8 - 6.94 (2/6), 7.55 (16),
7.68 (15)
16 124.3 7.55 7.54 (14)
12 125.7 - 7.55 (14 and 16), 7.92
(13)
13 126.1 7.92 7.69 (15)
2,6 127.7 6.94 2.20 (7/8), 6.94 (2/6)
14 129.3 7.54 7.55 (16)
3,5 131.0 - 2.20 (7/8), 6.94 (2/6)
15 134.1 7.69 7.92 (13)
1 136.2 - -
11 152.7 - 7.54 (14), 7.69 (15),
7.92 (13)
4 157.2 - 2.20 (7/8), 3.70 (9),
6.94 (2/6)
17 170.1 - 7.54 (14), 7.92 (13)
352 Appendix
1.15 4-(Biphenyl-2-yl)-2,6-dimethylphenol (209)
2
3
4
5
6
1
OH
8 7
9
10
11
12
13
14
15
16
17
18
1920
C atom δ [ppm] HMQC cross peaks
[ppm]
7,8 15.9 2.12
n.d. 122.5 7.20
n.d. 126.4 -
n.d. 127.1 -
n.d. 127.5 7.38
n.d. 127.9 7.22
n.d. 130.0 7.17
3,5 130.3 6.74
n.d. 130.6 7.40
n.d. 130.7 7.40
n.d. 133.6 -
n.d. 140.5 -
n.d. 140.6 -
n.d. 142.0 -
1 151.0 -
Cross-peak tables 353
1.16 3,5-Dimethylspiro[cyclohexa[2,5]diene-1,9'-fluoren]-4-one (210)
3
2 1 6
54
O
8 7
1514
9 20
1312
11
10 19
18
1716
C atom δ [ppm] HMQC cross peaks
[ppm]
7,8 16.4 1.98
1 56.9 -
120.7 7.79
125.0 7.21
128.1 7.30
10,11,12,13,
16,17,18,19
128.7 7.43
n.d. 135.5 -
n.d. 141.6 -
n.d. 143.9 -
2,6 144.6 6.30
6 187.9 -
354 Appendix
1.17 1,3-Dimethyltriphenylen-2-yl acetate (211)
6
1
2
3
4
5
7
1213
18
8
9
10
11
14
15
16
17
1920
O21
22
O
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
20 17.4 2.42 8.37 (6)
19 18.4 2.76 -
22 20.8 2.46 -
6 122.9 8.37 2.42 (20), 2.76 (19)
n.d. 123.2 8.54 7.62
n.d. 123. 5 8.60 7.53
n.d. 123.6 8.54 -
n.d. 125.6 7.54 8.60
n.d. 126.8 - 8.42
n.d. 127.1 - 2.76 (19)
n.d. 127.2 7.61 8.54
n.d. 127.4 - 2.42 (20), 8.57
n.d. 128.9 8.41 7.61
n.d. 129.2 - 2.42 (20)
n.d. 130.0 - -
n.d. 130.1 - -
n.d. 130.3 -
n.d. 130.4 -
2.76, 8.37,
8.41, 8.53
8.60
7.53
n.d. 131.2 - 7.62, 8.42
2 149.0 - 2.42 (20), 2.76 (19), 8.37 (6)
21 169.1 - 2.46 (22)
Cross-peak tables 355
1.18 N'-(4-Methoxy-3,5-dimethylbenzoyl)picolinohydrazide (246)
3
4
56
12
7
10
9
O
NH11
O
8
HN
12
1314
O
N15
16
17
18
C atom δ [ppm] HMQC cross peaks [ppm]
7,9 16.3 2.30
8 59.9 3.74
18 122.6 8.15
16 126.9 7.47
1 127.0 -
2,6 128.2 7.56
3,5 131. 7 -
17 137.5 7.86
14 148.4 -
15 148.8 8.61
4 160.68 -
13 160.70 -
10 164.0 -
356 Appendix
1.19 N'-(Chloro(4-methoxy-3,5-dimethylphenyl)methylene)picolino-
hydrazonoyl chloride (247)
3
4
56
12
7
10
9
O
N
Cl
8
N11
12
Cl
N13
1415
16
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.4 2.36 7.80 (2/6)
8 59.9 3.77 -
16 123.5 8.24 7.43 (14)
14 125.8 7.43 8.24 (16), 8.78 (13)
1 128.9 - -
2,6 129.5 7.80 2.36 (7/9), 7.80 (2/6)
3,5 131.5 - 2.36 (7/9)
15 136.9 7.83 8.78 (13)
11 143.9 - 8.24 (16)
10 144.2 - 7.80 (4/6)
13 149.7 8.78 7.43 (14)
12 150.9 - 7.83 (15), 8.78 (13)
4 160.6 - 2.36 (7/9), 3.77 (8),
7.80 (4/6)
Cross-peak tables 357
1.20 2-(4-Methoxy-3,5-dimethylphenyl)-5-(pyridin-2-yl)-1,3,4-
oxadiazole (253)
3
4
56
12
7
10
9
O
8
O11
NN12
N13
14
1516
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.2 2.36 7.90 (2/6)
8 59.9 3.79 -
1 119.1 - 2.36 (7/9)
16 123.4 8.32 7.47 (14), 7.90 (15),
8.82 (13)
14 125.8 7.47 8.32 (16), 8.82 (13)
2,6 128.2 7.90 2.36 (7/9), 7.90 (2/6)
3,5 132.2 - 2.36 (7/9), 7.90 (2/6)
15 137.3 7.90 8.82 (13)
12 144.0 - 7.90 (15), 8.32 (16),
8.82 (13)
13 150.4 8.82 7.47 (14), 7.90 (15)
4 160.5 - 2.36 (7/9), 3.79 (8),
7.90 (2/6)
11 163.8 - 8.32 (16)
10 165.8 - 7.90 (2/6)
358 Appendix
1.21 3-(4-Methoxy-3,5-dimethylphenyl)-6-(pyridin-2-yl)-1,2,4,5-
tetrazine (249)
N N
11NN
10
1 12
23
4
5 6N
13
14
1516
9
O
8
7
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.5 2.43 8.37 (2/6)
8 59.9 3.83 -
16 123.9 8.67 7.55 (14), 7.98 (15),
8.96 (13)
14 126.3 7.55 8.67 (16), 8.96 (13)
1 126.9 - 8.37 (2/6)
2,6 129.5 8.37 8.37 (2/6)
3,5 132.3 - 8.37 (2/6)
15 137.5 7.98 8.96 (13)
12 150.7 - 7.98 (15), 8.96 (13)
13 151.0 8.96 7.55 (14), 7.98 (15)
4 161.7 - 2.43 (7/9), 3.83 (8),
8.37 (2/6)
11 163.3 - 8.67 (16)
10 164.3 - 8.37(2/6)
Cross-peak tables 359
1.22 N'-Benzoyl-4-methoxy-3,5-dimethylbenzohydrazide (258)
3
4
56
12
7
10
9
O
NH11
O
8
HN
12
1314
O15
16
1718
19
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 15.9 2.28 7.60 (2/6)
8 59.4 3.70 -
15,19 127.3 7.92 7.54 (17), 7.92 (15/19)
2,6 128.1 7.62 2.28 (7/9), 7.62 (2/6)
16,18 128.3 7.48 7.48 (16/18)
1 128.4 - -
3,5 130.3 - 2.28 (7/9)
17 131.4 7.54 7,92 (15/19)
14 133.3 - 7.48 (16/18)
4 159.3 - 2.28 (7/9), 3.70 (8),
7.62 (2/6)
10 165.0 - 7.62 (2/6)
13 165.3 - 7.92 (15/19)
360 Appendix
1.23 N'-(Chloro(phenyl)methylene)-4-methoxy-3,5-dimethylbenzo-
hydrazonoyl chloride (259) and 2-(4-Methoxy-3,5-dimethyl-
phenyl)-5-phenyl-1,3,4-oxadiazole (260)
3
4
56
12
7
10
9
O
N
Cl
8
N11
12
Cl13
14
15
16
17
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.4 2.36 7.80 (2/6)
8 59.9 3.78 -
14,16 128.66 7.48 7.48 (14/16), 7.53 (15)
13,17 128.69 8.13 7.52, 8.13 (13/17)
1 129.1 - -
2,6 129.5 7.80 2.36 (7/9), 7.80 (2/6)
3,5 131.4 - 2.36 (7/9), 7.80 (4/6)
15 131.8 7.53 8.13 (13/17)
12 133.9 - 7.48 (14/16)
11 144.1 - 8.13 (13/17)
10 144.3 - 7.80 (4/6)
4 160.5 - 2.36 (7/9), 3.78 (8),
7.80 (4/6)
Cross-peak tables 361
3
4
56
12
7
10
9
O
8
O11
NN12
13 14
15
1617
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.3 2.38 7.81 (2/6)
8 60.0 3.79 -
1 119.5 - -
12 124.3 - 7.54 (14/16)
13,17 127.1 8.14 7.54 (15), 8.14 (13/17)
2,6 127.8 7.81 2.38 (7/9), 7.81 (2/6)
14,16 129.2 7.54 7.54 (14/16)
15 131.7 7.54 8.14 (13/17)
3,5 132.2 - 2.38 (7/9)
4 160.3 - 2.38 (7/9), 3.79 (8),
7.81 (2/6)
11 164.5 - 8.14 (13/17)
10 164.7 - 7.81 (2/6)
362 Appendix
1.24 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2-dihydro-1,2,4,5-
tetrazine (261)
N N
13NH
12
HN11
10
1 14
23
4
5 6 15 16
17
1819
9
O
8
7
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.3 2.31 7.34 (2/6)
8 59.9 3.74 -
1 125.5 - -
15,19 126.1 7.67 7.45 (17), 7.67 (15/19)
2,6 126.8 7.34 2.31 (7/9), 7.34 (2/6)
16,18 129.0 7.43 7.43 (16/18), 7.45 (17)
14 130.4 - 7.43 (16/18)
17 130.8 7.45 7.67 (15/19)
3,5 131.9 - 2.31 (7/9)
10,13 148.8 - 7.34 (2/6), 7.67 (15/19)
4 159.5 - 2.31 (7/9), 3.74 (8),
7.34 (2/6)
Cross-peak tables 363
1.25 3-(4-Methoxy-3,5-dimethylphenyl)-6-phenyl-1,2,4,5-tetrazine
(262)
N N
11NN
10
1 12
23
4
5 6 13 14
15
1617
9
O
8
7
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7,9 16.5 2.43 8.33 (2/6)
8 60.0 3.83 -
1 127.2 - -
13,17 128.0 8.64 7.63 (15), 8.64 (13/17)
2,6 129.0 8.33 2.43 (7/9), 8.33 (2/6)
14,16 129.4 7.61 7.61 (14/16), 7.63 (15)
12 132.1 - 7.61 (14/16)
3,5 132.4 - 2.43 (7/9)
15 132.6 7.63 8.64 (13/17)
4 161.4 - 2.43 (7/9), 3.83 (8),
8.33 (2/6)
11 163.8 - 8.64 (13/17)
10 163.9 - 8.33 (2/6)
364 Appendix
1.26 Transannular cyclization-product (cone) (60)
20
2119
OO O
17
16
15
23
22 24
26
4
25
1
14
18
5
828
6
7
32 3829
30
31
2
3
O
11
10
9
12
27
13
35
36
37
33
34
39
40
4441
4243
51
45
46
47 48
49
5052
53
54 55
56
C atom1
δ
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.00 31,37
10.02 0.85 1.81 (30/36), 3.90 (29/35)
34,40 11.05 1.12 1.81 (33/39), 3.69 (32/38)
23.24 30,36
23.26 0.85 (31/37), 3.90 (29/35)
33,39 23.72
1.75-1.88 („1.81“)
1.12 (34/40), 3.69 (32/38)
8,14 31.38 3.15, 4.45 5.50 (6/16), 7.13 (10/12)
2,20 31.63 3.21, 4.49 5.86 (4/18), 7.21 (22/24)
42,43 44.97 3.86 3.76 (41/44),
6.89 (46/50/52/56)
41,44 48.69 3.76 3.86 (32/43), 5.50 (6/16),
5.86 (4/18)
76.26 29,35
76.31 3.90 0.85 (31/37), 1.81 (30/36)
32,38 76.34 3.69 1.12 (34/40), 1.81 (33/39)
11,23 121.51 6.94-7.05 7.21 (22/24)
1 For the assignment to the unsubstituted phenyl rings the shift of the bridging methylene groups were
compared with those of other calixarenes, especially tetrapropoxycalixarene, concluding that protons “under” the cyclobutane ring experience a downfield shift.
Cross-peak tables 365
C atom1
δ
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
(„6.98“, „7.02“)
4,18 125.13 5.86 3.21 (2/20), 3.76 (41/44),
4.49 (2/20), 5.50 (6/16)
48/54 125.53 6.98 6.89 (46/50/52/56)
47/49/53/55 127.74 7.04 7.04 (47/49/53/55)
46/50/52/56 128.29 6.89 3.86 (42/43), 6.89
(46/50/52/56), 6.98 (48/54)
6,16 128.74 5.50 3.76 (41/44), 5.86 (4/18)
10,12 129.38 7.13 7.13
(10/12)
22,24 129.63 7.21
3.15 (8/14),
3.21 (2/20),
4.45 (8/14),
4.49 (2/20)
7.21
(22/24)
3,19,5,17 133.92 -
3.21 (2/20), 3.76 (41/44),
3.86 (42/43), 4.49 (2/20),
5.50 (6/16)
7,15 134.27 - 3.15 (8/14), 4.45 (8/14),
5.86 (4/18)
138.03 -
1,9,13,21 138.05 -
3.15 (8/14), 3.21 (2/20),
4.45 (8/14), 4.49 (2/20),
6.94-7.05 (11,23),
7.13 (10/12), 7.21 (22/24)
45,51 141.67 - 3.76 (41/44), 3.86 (42/43),
7.04 (47/49/53/55)
26,28 154.37 -
3.15 (8/14), 3.21 (2/20),
3.69 (32/38),
4.45(8/14), 4.49 (2/20),
5.50 (6/16), 5.86 (4/18)
25 159.44 7.13
(10/12)
27 159.49
-
3.15 (8/14),
3.21 (2/20),
3.90 (29/35),
4.45 (8/14),
4.49 (2/20)
7.21
(22/24)
366 Appendix
1.27 cone-5,11-Bis(2-phenylethenyl)-25,26,27,28-tetra-n-propoxy-
calix[4]arene (65)
22
2125
1
24
23
2
328 7
6
5
4
20
OO
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
1211
O35
36
37
38
39
40
5049 4241
51
52
5354
55
5643
44
4546
47
48
8
E/Z E/Z
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.37
10.46
10.48
10.50
31,34,37,40
10.60
0.96-1.02 1.85-1.96, 4.31-4.47
23.36
23.38 30,33,36,39
23.45
1.85-1.96 0.96-1.02, 4.31-4.47
31.04
31.10
31.21 2,8,14,20
31.27
2.89-3.19, 4.31-4.47 6.27-6.85
29,32,35,48 76.78 3.76-3.93 0.96-1.02, 1.85-1.96
122.04
122.13 17,23
122.15
6.27-6.85
6.27-6.85
n.d. 126.32
n.d. 126.36
6.27-6.85, 7.08-7.23,
7.44
2.89-3.19, 4.31-4.47,
6.27-6.85, 7.08-7.23,
Cross-peak tables 367
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 126.50
n.d. 126.60
n.d. 126.62
n.d. 126.66
n.d. 126.75
n.d. 126.83
n.d. 126.87
n.d. 127.06
n.d. 127.10
n.d. 127.96
n.d. 128.17
n.d. 128.22
n.d. 128.35
n.d. 128.41
n.d. 128.50
n.d. 128.63
n.d. 128.71
n.d. 128.86
n.d. 129.22
n.d. 129.41
n.d. 129.47
n.d. 129.53
6.27-6.85, 7.08-7.23,
7.32
7.32, 7.44
n.d. 130.77
n.d. 130.81
n.d. 130.90
6.27-6.85
n.d. 131.28 -
6.27-6.85
n.d. 134.52 -
n.d. 134.73 -
n.d. 134.78 -
n.d. 134.90 -
2.89-3.19, 4.31-4.47,
6.27-6.85
368 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 135.04 -
n.d. 135.15 -
n.d. 135.26 -
n.d. 135.33 -
n.d. 135.38 -
n.d. 135.41 -
n.d. 135.60 -
n.d. 135.64 -
n.d. 135.71 -
n.d. 135.91 -
n.d. 137.95 -
n.d. 138.00 -
n.d. 138.12 -
n.d. 138.13 -
6.27-6.85, 7.08-7.23,
7.32, 7.44
156.18 -
156.27 -
156.55 -
156.58 -
156.64 -
156.76 -
157.01 -
25,26,27,28
157.18 -
2.89-3.19, 3.76-3.93 ,
4.31-4.47, 6.27-6.85
Cross-peak tables 369
1.28 proximal cone-Calix[4]diphenanthrenes (81a, 81b, 81c)
1.28.1 proximal cone-Calix[4]diphenanthrene (81a)
4
3 44
15
14
5
16
17
43 29
28
27
18
302
OO
1
54
55
56
38
37 41
40
39
O45
46
47
35
32
31 42
34
33
O48
49
50
36
51
52
53
13
87
6
12
11
10
9
26
2524
19
23
22
21
20
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
56 9.77 0.79 1.75 & 2.02 (55), 4.18 & 4.27 (54)
50 10.11 0.94 1.92 & 1.96 (49), 3.96 & 4.24 (48)
47 10.98 1.06 1.81 (46), 3.60 (45)
53 11.34 1.33 2.11 (52), 3.92 & 4.05 (51)
55 22.23 1.75, 2.02 0.79 (56), 4.18 & 4.27 (54)
49 23.13 1.92, 1.96 0.94 (50), 3.96 & 4.24 (48)
46 23.67 1.81 1.06 (47), 3.60 (45)
52 23.94 2.11 1.33 (53), 3.92 & 4.05 (51)
16 30.76 5.76, 5.81 -
30 31.02 3.31, 4.79 6.00 (28), 7.25 (32)
2 31.50 3.04, 4.26 5.30 (40), 7.04 (4)
36 31.61 3.25, 4.49 6.23 (38), 7.29 (34)
45 „76.95“ 3.60 1.06 (47), 1.81 (46)
„77.16“ 3.94, 4.05
„77.16“ 4.18, 4.25 48,51,54
„77.16“ 3.94, 4.25
0.79 (56), 0.94 (50), 1.33 (53),
1.75 & 2.02 (55), 1.92 & 1.96 (49),
2.11 (52)
33 122.11 7.09 -
21 122.51 5.71 7.25 (23)
39 123.29 6.16 -
25 123.90 7.07 -
22 124.31 6.84 7.61 (20)
370 Appendix
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
7 124.56 7.54 -
11 124.88 7.71 8.00 (9)
10 125.83 7.66 8.70 (12)
40 125.86 5.30 3.04 & 4.26 (2), 6.23 (38)
23 126.56 7.25 5.71 (21), 7.07 (25)
6 126.80 7.25 7.04 (4)
38 126.96 6.23 3.25 & 4.49 (36)
20 127.25 7.61 6.84 (22)
5 127.38 - 7.54 (7)
12 127.84 8.70 7.66 (10)
4 127.95 7.04 3.04 & 4.26 (2)
9 128.15 8.00 7.71 (11)
18 128.25 - 6.00 (28), 7.61 (20)
26 128.52 6.80 -
28 128.58 6.00 3.31 & 4.79 (30)
19 129.01 -
34 129.09 7.29
3.25 & 4.49 (36), 5.71 (21),
7.25 (32)
27 129.54 - 7.07 (25)
32 129.76 7.25 3.31 & 4.79 (30), 7.29 (32)
17 130.56 - 5.76 & 5.81 (16), 6.00 (28)
13 131.10 - 7.54 (7), 7.71 (11), 8.00 (9)
15 131.51 - 5.76 (16)
24 131.97 - 6.80 (26), 6.84 (22), 7.61 (20)
1,37 132.87 - 3.04 & 4.26 (2), 3.25 & 4.49 (36),
5.30 (40), 6.16 (39), 6.23 (38)
133.47 -
133.49 - 8,14,29
133.54 -
3.31 & 4.79 (30), 7.04 (4), 7.25
(6), 7.54 (7), 7.66 (10), 8.70 (12)
3 135.65 - 3.04 & 4.26 (2)
31 137.01 - 3.31 & 4.79 (30), 7.09 (33)
35 138.29 - 3.25 & 4.49 (36), 7.09 (33)
41 154.99 - 3.04 & 4.26 (2), 3.25 & 4.49 (36),
3.60 (45), 5.30 (40), 6.16 (39),
Cross-peak tables 371
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
6.23 (38)
43 156.90 - 3.31 & 4.79 (30), 3.92 & 4.05 (51),
5.76 & 5.81 (16), 6.00 (28)
42 158.70 -
3.25 & 4.49 (36), 3.31& 4.79 (30),
3.96 & 4.24 (48),
7.09 (33), 7.25-7.29 (32/34)
44 159.83 - 3.04 & 4.26 (2), 4.18 & 4.27 (54),
7.04 (4), 5.76 & 5.81 (16)
H
atom
δ
[ppm]
H-H COSY
cross peaks
[ppm]
NOESY
cross peaks
[ppm]
ROESY
cross peaks
[ppm]
56 0.79 1.75, 2.02 1.33, 1.75 1.75, 2.20
50 0.94 1.92, 1.96 1.06 1.92, 1.96
47 1.06 1.81 0.94, 1.81 1.81
53 1.33 2.11 0.79, 2.11 2.11
55 1.75 4.27 0.79, 2.02, 4.18,
4.27
2.02, 4.23-4.29
46 1.81 3.60 1.06, 3.60 1.06, 3.60
49 1.92 3.96, 4.24 3.94, 4.24 3.94, 4.23-4.29
49 1.96 3.96, 4.24 3.94, 4.24 3.94, 4.23-4.29
55 2.02 4.18 1.75, 4.25 1.75, 4.23-4.29
52 2.11 3.92, 4.05 1.33, 3.92, 4.05 1.33, 3.94, 4.05, 4.25
2 3.04 4.26 3.31, 4.26, 5.30,
7.04
3.31, 3.60, 4.26, 5.30,
7.04
36 3.25 4.49 4.49, 6.23, 7.29 4.49, 6.23, 7.29
30 3.31 4.79 3.04, 3.94, 4.79,
6.00, 7.25
4.79, 6.00, 7.25
45 3.60 3.60 1.81, 3.94, 4.26 ,
4.49
1.06, 1.81, 3.04, 4.25,
4.49
48,51 3.90-
3.97
4.05, 4.24 2.11, 3.31, 3.60,
4.05, 4.18, 4.25,
0.94, 1.33, 1.92, 1.96,
2.11, 4.25, 4.49, 4.79
372 Appendix
H
atom
δ
[ppm]
H-H COSY
cross peaks
[ppm]
NOESY
cross peaks
[ppm]
ROESY
cross peaks
[ppm]
4.49, 4.79
51 4.05 3.92 2.11, 4.25, 5.80 1.33 (+), 2.11 (+), 3.94,
5.80 (+)
54 4.18 4.27 5.80 0.79, 1.75, 2.02, 5.80
48,54 4.23-
4.29
3.96, 4.18 0.79, 0.94, 1.88-
2.05, 3.94, 4.05
0.79, 1.88-2.05, 3.94
2 4.26 3.04 3.04, 4.23-4.29 3.04
36 4.49 3.25 3.25, 3.94 3.25, 3.60, 3.94, 4.25
30 4.79 3.31 3.31, 4.25 3.31, 3.94
40 5.30 6.16 6.16, 7.04, 7.25 6.16
21 5.71 6.84, 7.61 6.84, 7.61, 7.71 7.61, 6.84
16 5.76 5.81
16 5.81 5.76
4.05, 4.18, 7.61,
8.70
3.94, 4.05, 4.18, 4.25,
7.61, 8.70
28 6.00 - 6.80, 7.04 3.31, 4.79, 6.80
39 6.16 6.23, 5.30 5.30, 6.23, 7.09 5.30
38 6.23 6.16 7.29 3.25 (+), 5.30
26 6.80 7.07 6.00, 7.07, 7.25 6.00, 7.25
22 6.84 5.71, 7.25 5.71, 7.25 5.71, 7.25
4 7.04 - 3.04, 6.00 3.04, 7.25-7.29
25 7.07 6.80 6.80, 7.54 6.80
33 7.09 7.25, 7.29 6.16 6.80, 7.25-7.29
6,32
7.24-
7.26
7.09, 7.54, 3.31, 5.30, 6.80,
6.84, 7.04, 7.07,
7.54, 8.00
3.31, 6.00, 6.84, 7.04,
7.07-7.10, 7.54
34 7.29 7.09 3.25, 6.23 3.25, 7.09
7 7.54 7.25 7.25, 8.00 7.25, 8.00
20 7.61 5.71 5.71, 5.76, 5.81,
8.70
5.71, 5.76, 5.81
10 7.66 7.71, 8.00 8.00 8.00
11 7.71 7.66, 8.70 5.71, 8.70 8.70
9 8.00 7.66 7.25, 7.54, 7.66 7.54, 7.66
12 8.70 7.71 5.76, 5.81, 7.61, 5.76, 5.81, 7.71
Cross-peak tables 373
H
atom
δ
[ppm]
H-H COSY
cross peaks
[ppm]
NOESY
cross peaks
[ppm]
ROESY
cross peaks
[ppm]
7.71
1.28.2 proximal cone-Calix[4]diphenanthrene (81b)
4
3
44 15
14
13
16
17 43
29
28
19
18
302
OO
1
54
55
56
38
37 41
40
39
O45
46
47
35
32
3142
34
33
O48
49
50
36
51
52
53
12
1110
5 27
2221
20
26
25
24
239
8
7
6
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
47,50 10.50 1.02 1.93 (46/49), 3.86 (45/48)
53,56 10.65 1.08 2.03(22/55), 4.06 (51/54)
46,49 23.25 1.93 1.02 (47/50), 3.86 (45/48)
52,55 23.66 2.03 1.08 (53/56), 4.06 (51/54)
16 30.54 3.46, 4.94 -
2/30 30.89 4.73, 4.98 -
36 31.33 2.90, 4.28 -
45,48 76.36 3.86 1.02 (47/50), 1.93 (46/49)
51,54 78.31 4.06, 4.28 1.08 (53/56), 2.03 (52/55)
33,39 121.28 6.07 -
PhenCH 124.31 7.44-7.56 („7.55“)
PhenCH 124.67 7.44-7.56 („7.45“) 7.78 (11/21)
PhenCH 125.64 7.44-7.56 („7.51“) 8.78 (6/26)
32,40;
PhenCH 127.64 5.84, 7.38 2.90 & 4.28 (36)
34,38;
11,21 128.10 6.26, 7.78
4.73 & 4.98 (2/14),
7.55
374 Appendix
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
14,18;
6,26 128.48 7.06, 8.78
3.46 & 4.94 (16),
7.51
129.04 - 7.45
130.45 - 7.55, 7.78
(11/21)
130.70 -
4.73 & 4.98
(2/30) 7.51, 8.78
(6/26)
4,5,10,13,
19,22,27,28
133.03 - 7.51, 8.78 (6/26)
15,17 134.16 - 3.46 & 4.94 (16)
1,3,29,31 134.54 - 4.73 & 4.98
(2/30)
35,37 134.67 - 2.90 & 4.28
(36)
6.07 (33/39)
41,42 156.33 - 2.90 & 4.28 (36), 3.86
(45/48), 4.73 & 4.98 (2/30)
43,44 158.95 - 3.46 & 4.94 (16), 4.06
(51/54), 4.73 & 4.98 (2/30)
Cross-peak tables 375
1.28.3 proximal cone-Calix[4]diphenanthrene (81c)
4
3 44
15
14
5
16
1743
29
28
19
18
302
OO
1
54
55
56
38
37 41
40
39
O45
46
47
35
32
3142
34
33
O48
49
50
36
51
52
53
13
87
6
27
2221
20
12
11
10
9
26
25
24
23
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
CH2CH3 (a) 10.26 0.94 1.90, 3.92
CH2CH3 (b) 10.50 1.00 2.03, 3.80, 3.98, 4.12
CH2CH3 (c) 10.75 1.06
CH2CH3 (d) 10.78 1.11
1.97, 1.99, 3.76-3.86, 3.97-
4.13
CH2CH3 (a) 23.04 0.94, 3.92
CH2CH3 (b) 23.33 1.00,
CH2CH3
(c+d) 23.54
1.87-2.03 1.06, 1.11,
3.80
3.97-4.13
30.04 4.66, 5.31 -
30.67 4.52, 4.94 -
31.42 3.04, 4.38 6.52 2,26,30,36
31.53 3.41, 4.73 -
OCH2 (a) 76.24 3.92 0.94, 1.86-1.95
OCH2 (c) 76.95 3.78, 3.85 1.06, 1.86-1.95
OCH2 (d) 77.37 3.97-4.13 1.11, 1.87-2.03
OCH2 (b) 77.81 3.97-4.13, 4.24 1.00, 1.87-2.03
p-ArCH 120.85 6.18 -
n.d. 122.51 6.39 -
n.d. 123.94 -
n.d. 124.03 7.19 7.61
n.d. 124.75 - 7.73
PhenCH 125.07 7.41, 7.49 n.d.
376 Appendix
C atom δ
[ppm]
HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
n.d. 125.35 - 7.19
n.d. 125.62 - 8.73
n.d. 127.45 - -
n.d. 127.61 -
PhenCH 127.75 7.49
n.d. 127.84 6.88, 7.61
12,26 128.07 8.73
n.d. 128.20 -
n.d. 128.29 7.73
7.38-7.44
n.d. 128.54 6.52
n.d. 128.65 -
n.d. 128.76 -
n.d. 128.83 -
6.18, 6.52
7.18
n.d. 129.24 - 6.88, 7.49
n.d. 129.65* 4.52, 4.94
n.d. 129.82 - n.d.
n.d. 130.39 - 7.19
n.d. 130.50 -
5.31, 7.41,
7.61, 7.73
PhenC 130.60 - 8.73
n.d. 131.40 * 4.66, 5.31
n.d. 132.77 - 6.88, 7.20, 7.38
PhenCH 133.19 - 7.49, 8.73
133.82 - 3.41, 4.73, 4.66, 5.31
134.45 - 4.52, 4.94
134.89* - 3.04, 4.38
6.18 ArCCH2Ar
136.20* 3.41, 4.73
156.42 - 3.04 & 4.38, 3.41 & 4.73
41,42 157.04 -
3.04 & 4.38, 3.92, 4.52 & 4.94,
6.18, 6.51
43,44 157.86 - 3.41 & 4.73, 3.97-4.13 & 4.24
(51/54), 4.52 & 4.94, 4.66 & 5.31
Cross-peak tables 377
1.29 cone-5,17-Bis(2-methyl-2-phenyl-1-ethenyl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (85)
3 28 7
65
4
8
O
13
10
9 27
12
11
O35
36
37
14
38
39
40
4142
43
44
45
46
47
48
49
2
E/Z
C atom δ
1
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
37 10.68 1.03 1.93-2.08 (left) (36), 3.94
(35)
40 10.84 1.05 1.93-2.08 (right) (39),
3.78*,3.87 (38)
49 17.55 1.90, 2.12* 6.53 (41)
36 23.84 1.93-2.08 (left) 3.94 (35)
39 23.98 1.93-2.08 (right)
0.95*, 0.99*,
1.03, 1.05,
3.78* 3.87 (38)
8,14 31.57 2.88, 3.19, 4.32, 4.50
6.24*, 6.41*, 6.53*,
6.64 (11), 6.69 (4/6), 6.76
(10/12), 6.84*
35 77.42 3.78*, 3.94 1.93-2.08
(left) (36)
38 77.69 3.87
0.95*, 0.99*,
1.03, 1.05 1.93-2.08
(right) (39)
11 122.64 6.46*, 6.64, 6.76* 6.24*, 6.41*, 6.46*, 6.84*
1 Minor isomers are marked with an asterisk.
378 Appendix
C atom δ
1
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
44,48 126.27 7.28 7.17
n.d. 126.43 * 7.49* 7.49*
46 127.13 6.24*, 7.23*, 7.17 1.93-2.08* (right), 6.41*, 7.28
41 128.12 6.53 1.90 (49), 2.12*, 6.69 (4/6)
n.d. 128.29* n.d. 6.24*, 6.84*
45,47 128.67 7.17 7.17
n.d. 128.72* 6.24*
10/12 128.78 6.76, 7.11*, 7.33*
PhCH 129.03* 7.28*
6.64 (11), 6.76 (10/12)
m-ArH 129.68 * 6.41* 2.88*, 4.32*, 6.24*, 6.41*
4,6 129.81 6.69 3.19 (8/14), 4.50 (8/14), 6.53
(41), 6.69 (4/6)
4,6* 129.99* 6.84* 3.14* ,4.45*, 6.84*
5 132.42 - 1.90 (49), 6.53 (41)
n.d. 133.02* - n.d.
134.97 - 3,7
135.02* - 6.46*, 6.69 (4/6)
ArCH2Ar 135.91* - 2.88*, 4.32*, 4.45*
135.97 -
42, 9,13 136.00 -
1.90 (49), 2.12*, 3.19 (8/14),
4.50 (8/14), 6.53 (41), 6.64
(11), 6.69 (4/6), 6.76 (10/12),
7.28 (44/48), 7.49*
n.d. 137.22* - 1.93-2.08 (right)
n.d. 143.37* - 1.93-2.08 (right)
43 144.69 - 1.90 (49), 2.12*, 6.53 (41),
7.17, 7.28
n.d. 145.11* - 7.33*
28 155.78 - 3.19 (8/14), 3.87 (35), 4.50
(8/14), 6.69 (4/6)
27/28 156.79* -
2.88*, 3.15*, 3.78*, 4.32*,
4.45*, 6.24*, 6.41*, 6.46*,
6.53*, 6.84*
Cross-peak tables 379
C atom δ
1
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
27 157.24 - 3.19 (8/14), 3.94 (38), 4.50
(8/14), 6.64 (11), 6.76 (10/12)
380 Appendix
1.30 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-
phenanthrene (86a and 86b)
4
3 44
15
14
5
16
17 43 21
20
19
18
OO54
55
56
51
52
53
13
87
6
12
11
10
9
22
57
4
3 44
15
14
5
16
1743
21
20
19
18
222
OO
1
54
55
56
38
37 41
40
39
O45
46
47
35
24
2342
34
33
O48
49
50
36
51
52
53
13
87
6
12
11
10
9
57
2
32
3130
25
29
28
27
26
58a
b
C atom δ
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
50,56a+b 10.11 0.94, 0.95 2.05 (49/55),
4.21& 4.38 (48/54)
47b 11.04 1.16 1.93 (46), 3.74 (45)
53a 11.17 1.24 2.00 (52), 3.77 & 3.82 (51)
53b 11.33 1.32 2.07 (52), 3.86 (51)
57 19.83 2.73, 2.74 7.55 (6)
23.32 49,55a+b
23.36 2.05 (2.05, 2.12)
0.94 & 0.95 (50/56),
4.21 & 4.38 (48/54)
46b 23.76 2.05 (1.93) 1.16 (47), 3.74 (45)
52a 23.90 2.05 (2.00) 1.24 (53), 3.77 & 3.82 (51)
52b 24.02 2.05 (2.07) 1.32 (53), 3.86 (51)
16,22 30.21 4.66, 4.72, 4.87 5.12 (18/20), 5.32 (18)
16,22 31.22 3.35, 3.39, 4.60, 4.62 6.03 (20), 6.27 (38/40),
7.54 & 7.61 (4/34)
Cross-peak tables 381
C atom δ
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
51b 76.50 3.86 1.32 (53), 2.07 (52)
51a 76.73 3.77, 3.82 1.24 (52), 2.00 (53)
45b 77.00 3.74 1.16 (47), 1.93 (46)
77.77 48/54a+b
77.96 4.21, 4.38
0.94 & 0.95 (50/56),
2.05 & 2.12 (49/55)
39b 122.67 6.27 -
19a 122.82 5.94 -
19b 122.90 5.64 -
124.33 9
124.37 8.05 7.57
11 124.51 7.57 8.05
10 125.77 7.57 8.57, 8.60
18,20b 126.32 5.12 4.66, 4.87, 5.12 (18/20),
5.64 (19)
20a 126.84 6.03 3.35, 4.60, 5.33 (18)
18a 127.05 5.33 4.72, 4.87, 5.94 (19), 6.03
(20)
4 127.23 7.57 3.39, 7.57
n.d. 127.43 7.57 n.d.
38,40b 127.57 6.27 4.65, 6.27 (38/40)
n.d. 127.65 - 3.35, 4.60
PhenC 128.42 - -
12 128.50 8.57 7.57
12 128.60 8.60 7.57
7 130.28 - 2.74 (57), 8.05 (9)
PhenC 130.61 - 4.72
130.99 - 7.60, 8.60 PhenC (14)
131.08 - 4.65, 4.87
7.55, 8.57
21a 132.20 - 3.35, 4.65, 5.94 (19)
1,37b 132.67 - 3.39, 4.65, 6.27 (39)
133.27 -
PhenC (8) 133.33 -
4.66, 4.87, 7.55, 7.60
2.74 (57,58), 8.05, 7.57,
8.57 & 8.60 (12/26)
382 Appendix
C atom δ
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
17,21b 134.63 - 5.64 (19)
17a 134.94 - 4.65, 4.87
5.94 (19)
136.91 - 3,15
136.96 - 3.35, 3.39, 4.60, 4.87
43b 154.57 -
3.86 (51),
5.12 (18/20),
5.64 (19)
43a 154.88 -
3.77 & 3.82
(51), 5.33
(18), 5.94
(19), 6.03 (20)
41b
155.32
-
3.35, 3.39,
4.60, 4.62,
4.66, 4.87
3.74 (45),
6.27 (38/40)
159.55 - 3.39, 7.61
(4/34) 44a+b
159.69 -
4.21, 4.38,
4.60, 4.62,
4.66, 4.72,
4.87
3.35, 7.54
(4/34)
Cross-peak tables 383
1.31 cone-5,11,17,23-Tetrakis(2-methyl-2-phenyl-1-ethenyl)-
25,26,27,28-tetra-n-propoxycalix[4]arene (88)
3 28 7
65
4
8
O38
39
40
4142
43
44
45
46
47
48
49
4
E/Z
C atom δ
1
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.35*
10.52 40
10.64*
0.96*, 1.00* 1.02* 1.05 1.88-2.08 (39), 3.94 (38)
3.79* (38), 3.88-4.00* (38)
17.15* 1.83*
17.29 1.88*, 1.96, 2.00* 49
17.68 2.16*
6.53 (41)
6.59 (41)
23.47 39
23.50*
1.88-2.08 0.96* (40), 1.05 (40), 3.79*
(38), 3.94 (38), 3.88-4.00* (38)
31.22* 2.90*, 3.19*,4.34*, 4.49* 8
31.30 3.22, 4.53 6.40, 6.47, 6.79, 6.90
76.96*
38 77.37
3.79*, 3.88-4.00*
3.94
0.96* (40), 1.00* (40),1.05
(40), 1.88-2.08 (39)
125.93
125.98 7.27-7.34, 7.43-7.48
44-48,
4,6
126.07* 6.22, (7.12-7.24)
6.79, 7.12-7.24, 7.43-7.48
1 Minor isomers are marked with an asterisk.
384 Appendix
C atom δ
1
[ppm]
HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
126.69*
126.75
6.47, 7.27-7.34
127.80 4,6, 50
127.90* 6.22-6.90, 6.53, 6.59
1.83 (49), 1.87 (49), 1.96 (49),
2.00 (49), 6.79
128.21*
128.27
128.33*
2.04 (49), 2.16 (49)
6.90, 7.12-7.24 44-48
128.60*
7.12-7.24, 7.27-7.34
6.67, 7.27-7.34
129.19*
4,6
129.47
6.40, 6.47, 6.64, 6.67, 6.79,
6.90
2.90* (2,8),3.22 (2,8), 4.34*
(2,8), 4.53 (2,8), 6.22, 6.47
(4,6), 6.53 (41), 6.59 (41),
6.67(4,6), 6.79 (4,6), 6.90 (4,6)
132.12* - 5
132.36 - 1.96 (49), 6.53 (41), 6.59 (41)
3,7 134.63 - 2.90* (2,8),3.22 (2,8), 4.34*
(2,8), 4.53 (2,8), 6.79 (4,6)
135.57* -
43
135.71 -
1.83 (49), 1.87 (49), 1.96 (49),
2.00 (49), 2.04 (49), 2.16 (49),
6.59 (41), 7.27-7.34 (45-47),
7.43-7.48 (44-48)
42 144.18 -
1.83 (49), 1.87 (49), 1.96 (49),
2.00 (49), 2.04 (49), 2.16 (49),
6.53 (41), 6.59 (41), 6.67, 7.25,
7.27-7.34 (45-47)
154.78* -
2.90* (2,8),3.19* (2,8), 3.79*
(38), 4.34* (2,8), 4.49* (2,8),
6.40 28
155.22 - 3.22 (2,8), 3.94 (38), 4.53
(2,8), 6.47, 6.79, 6.90
Cross-peak tables 385
1.32 5-(2-(2-Bromophenyl)acetyl)-25,26,27,28-tetra-n-propoxy-
calix[4]arene (133)
22
21 25 1
24
23
2
3 28 7
65
4
820
OO
41
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
O 42
43
44
45
46
47
48
Br
38
39
40
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.4 0.98
10.5 1.04 31,34,37,40
10.6 1.02
1.86-1.97 (30/33/36/39),
3.81 & 3.84-3.92
(29/32/35/,38)
23.3 1.86-1.97
23.46 1.86-1.97 30,33,36,39
23.53 1.86-1.97
0.98 &1.02 &1.04
(31/34/37/40), 3.81 & 3.84-
3.92 (29/32/35/38)
31.1 3.16, 3.21, 4.45, 4.48
2,8,14,20
31.2 3.16, 3.21, 4.45, 4.48
6.47(16/18),
6.71-6.74 (10/12/22/24),
7.21 (4/6)
42 45.3 4.14 7.18 (48)
29,32,35,38 77.0 3.81, 3.84-3.92
0.98 & 1.02 & 1.04
(31/34/37/40),
1.86-1.97 (30/33/36/39)
17 122.0 6.39-6.43 -
11,23 122.4 6.65 -
44 125.3 - 4.14 (42),
7.11 (46), 7.18 (48)
47 127.5 7.25 7.57 (45)
16,18 128.1 6.47 6.47(16/18)
386 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
46 128.49 7.11 7.18 (48)
10,12,22,24 128.55 6.71-6.74
3.16 & 3.21 (2/8/14/20),
6.65 (11/23),
6.71-6.74 (10/12/22/24)
128.86 4,6
128.92
7.21
4.45 & 4.48 (2/8),
7.21 (4/6)
5 130.8 - -
48 131.7 7.18 4.14 (42),
7.09-7.14 (46)
45 132.9 7.57 7.25 (47)
134.9 - 1,9,13,21
15,19 135.0 -
4.45 & 4.48 (2/8/14/20),
6.39-6.43 (17),
6.65 (11/23)
3,7 135.5 - 3.21 (2/8), 7.21 (4/6)
43 135.6 - 4.14 (42),
7.25 (47), 7.57 (45)
1,9,13,21
135.8 -
4.45, 4.48 (2,8,14,20), 6.65
(11,23)
26 156.5 -
3.16 & 4.45 (14/20),
3.81 (32),
6.46-6.48 (16/18)
25,27 156.9 -
3.21 (2/8/14/20),
3.84-3.92 (29/35),
4.48 (2/8/14/20),
6.65 (11/23),
6.71-6.74 (10/12/22/24)
28 161.2 -
3.21 (2/8),
3.84-3.92 (38),
4.48 (2/8), 7.21 (4/6)
41 195.6 - 4.14 (42), 7.21 (4/6)
Cross-peak tables 387
1.33 5,11,17,23-Tetra-(2-(2-bromophenyl)acetyl)-25,26,27,28-tetra-n-
propoxycalixarene (136)
3 28 7
65
4
8
O
41O 42
43
44
45
46
47
48
Br
38
39
40
4
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
40 10.4 1.02 1.93 (39), 3.94 (38)
39 23.5 1.93 1.02 (40), 3.94 (38)
2,8 31.3 3.33, 4.50 7.38 (4/6)
42 45.4 4.10 7.21 (48)
38 77.2 3.94 1.02 (40), 1.93 (39)
44 125.0 -
4.10 (42), 7.02 (46),
7.11 (47), 7.21 (48),
7.50 (45)
47 127.6 7.11 7.50 (45)
46 128.5 7.02 7.21 (48)
4,6 129.2 7.38 3.33 (2/8), 4.50 (2/8),
7.38 (4/6)
5 131.2 - -
48 132.4 7.21 4.10 (42), 7.02 (46)
45 132.6 7.50 7.11 (47)
3,7 135.1 - 3.33 (2/8), 4.50 (2/8),
7.38 (4/6)
43 135.7 - 4.10 (42), 7.11 (47),
388 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
7.50 (45)
28 161.1 - 3.33 (2/8), 3.94 (38),
4.50 (2/8), 7.38 (4/6)
41 195.5 - 4.10 (42), 7.38 (4/6)
Cross-peak tables 389
1.34 5-Iodo-25,26,27,28-tetra-n-propoxycalix[4]arene (139a)
22
21 25 1
24
23
2
3 28 7
65
4
820
OO
I
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
38
39
40
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
31,37 10.3 0.95
10.58 34,40
10.64 1.02, 1.03
1.90 (30/36), 3.78 (32),
3.80 (38), 3.88 (29/35)
30,36 23.3 0.95
(31/37)
23.4
33,39 23.5
1.90 1.02 and
1.03
(34/40)
3.78 (32),
3.80 (38),
3.88 (29/35)
2,8 30.9 3.08, 4.37 6.72 (10/24), 6.73 (4/6)
14,20 31.2 3.16, 4.45 6.46 (16/18), 6.77
(12/22)
29,32,35,3
8 77.0 3.78, 3.80, 3.88
0.95 (31/37), 1.02 and
1.03 (34/40), 1.90 (30/36)
5 86.0 - 3.08 (2/8), 4.37 (2/8),
6.73 (4/6)
11,23 122.2
17 122.5 6.69 6.46 (16/18)
16,18 128.0 6.46
3.16 (14/20),
4.45 (14/20),
6.46 (16/18), 6.68 (17)
10,24 128.4 6.72 3.08 (2/8), 4.37 (2/8),
6.68 (11/23),
390 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
6.77 (12/22)
12,22 128.9 6.77
3.16 (14/20), 4.45
(14/20), 6.68 (11/23),
6.72 (10/24)
134.7 -
1,9,13,21 135.0 -
3.08 (2/8), 3.16 (14/20),
4.37 (2/8), 4.45 (14/20),
6.68 (11/23)
15,19 136.0 - 3.16 (14/20), 4.45
(14/20), 6.69 (17)
4,6 136.8 6.73 6.73 (4/6)
3,7 137.6 - 3.08 (2/8), 4.37 (2/8)
26 156.3 - 3.80 (38),
6.46 (16/18)
28 156.5 - 3.78 (32),
6.73 (4/6)
25,27 157.1 -
3.08
(2/8), 4.37
(2/8), 3.16
(14/20),
4.45
(14/20)
3.88
(29/35), 6.72
and 6.77
(10/12/22/24)
Cross-peak tables 391
1.35 5-((2-Bromophenyl)ethynyl)-25,26,27,28-tetra-n-propoxycalix[4]-
arene (141a)
22
21 25 1
24
23
2
3 28 7
65
4
820
OO
41
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
38
39
40
42
43
44
45
46
47
48
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.45 31,34,
37,40 10.53 1.00
1.91 (30,33,36,39),
3.86 (39,32,35,38)
23.40 30,33,
36,39 23.44 1.91
1.00 (31,34,37,40),
3.86 (39,32,35,38)
31.03 2,8,14,20
31.19 3.16, 4.45
6.58 (10/12/16/18/22/24),
6.88 (4/6)
76.7 39,32,
35,38 76.9 3.82-3.87
1.00 (31,34,37,40),
1.91 (30,33,36,39)
42 86.5 - 7.50 (48)
41 95.3 - 6.88 (4/6)
5 116.2 - -
11,23 122.2 (2) 6.58 -
17 122.3 6.70 -
44 125.7 - 7.50 (48)
43 126.2 - 7.26 (47)
47 127.1 7.26 7.59 (45)
10,12,16, 128.3 6.58 3.16 and 4.45 (2/8/14/20),
392 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
128.4 18,22,24
128.5
6.58 (10/12/16/18/22/24)
46 128.9 7.13 7.50 (48)
4,6 131.9 6.88 3.16 and 4.45 (2/8/14/20),
6.88 (4/6)
45 132.5 7.59 7.26 (47)
48 133.1 7.50 7.13 (46)
134.5 - 6.57
(11/23)
135.3 - 6.70 (17)
135.4 - 6.88 (4/6)
1,3,7,9,
13,15,19,
21
136.0 - -
3.16 and
4.45
(2/8/14/20)
25,27 156.6 (2) - 6.58 (10/12/22/24)
26 156.8 - 6.58 (16/18)
28 157.9 - 6.88 (4/6)
Cross-peak tables 393
1.36 5,17-Bis((2-bromophenyl)ethynyl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (141b)
3 28 7
65
4
8
O
41
13
10
9 27
12
11
O
35
36
37
14
38
39
40
42
43
44
45
46
47
48Br
2
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
40 10.1 0.92 1.95 (39), 4.04 (38)
37 10.9 1.09 1.89 (36), 3.71 (35)
39 23.2 1.95 0.92 (40), 4.04 (38)
36 23.6 1.89 1.09 (37), 3.71 (35)
8,14 31.0 3.18, 4.44 6.27 (10/12), 7.31 (4/6)
38 76.8 4.04 0.92 (40), 1.95 (39)
35 77.2 3.71 1.09 (37), 1.89 (36)
42 87.0 - 7.53 (48)
41 95.0 - 7.31 (4/6)
5 116.1 - -
11 122.5 6.33 3.18 (8/14), 4.44 (8/14)
44 125.7 - 7.14 (46), 7.53 (48)
45 126.1 - 7.24 (47), 7.60 (45)
47 127.1 7.24 7.60 (45)
10,12 128.0 6.27 3.18 (8/14), 4.44 (8/14),
6.27 (10/12), 6.33 (11)
46 129.0 7.14 7.53 (46)
394 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
4,6 132.4 7.31 3.18 (8/14), 4.44 (8/14),
7.31 (4/6)
45 132.5 7.60 7.24 (47)
9,13 133.0 - 3.18 (8/14), 4.44 (8/14),
6.33 (11)
48 133.2 7.53 7.14 (46)
3,7 137.2 - 3.18 (8/14), 4.44 (8/14),
7.31 (4/6)
27 155.5 -
3.18 (8/14), 3.71 (35), 4.44
(8/14), 6.27 (10/12), 6.33
(11)
28 158.9 - 3.18 (8/14), 4.04 (38), 4.44
(8/14), 7.31 (4/6)
Cross-peak tables 395
1.37 5-(2-Bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]arene
(137a)
22
21 25 1
24
23
2
3 28 7
65
4
820
OO
41
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
42
43
44
45
46
47
48
Br
38
39
40
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.4
10.47 31,34,
37,40 10.52
0.97-1.02 1.93 (30/33/36/39),
3.85 (29/32/35/38)
23.39 30,33,
36,39 23.42 1.89-1.96
1.00 (31/34/37/40),
3.85 (29/32/35/38)
2,8,24,20 31.2 3.10, 3.15, 4.43, 4.46 6.49 (4/6), 6.53 & 6.57
(10/12/22/24), 6.67 (16/18)
41 35.5 2.60 2.79 (42), 6.49 (4/6)
42 38.6 2.79 2.60 (41), 7.12 (48)
76.83 29,32,
35,38 76.85 3.83-3.87
1.00 (31/34/37/40),
1.93 (30/33/36/39)
17 121.96 -
11,23 122.02 6.55
-
44 124.6 - 2.79 (42), 7.04 (46), 7.12
(48), 7.19 (47), 7.53 (45)
47 127.4 7.19 7.04 (46), 7.53 (45)
46 127.6 7.04 7.12 (48), 7.19 (47)
396 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
128.2 4,6,
10,12,22,24,
16,18 128.3
6.49, 6.52-6.55, 6.56-
6.59, 6.67
2.60 (41), 3.10 (2/8),
3.15 (14/20), 4.43 (2/8),
4.46 (14/20), 6.49 (4/6),
6.53 & 6.57 (10/12/22/24),
6.67 (16/18)
48 130.7 7.12 2.79 (42), 7.04 (46)
45 132.9 7.53 7.19 (47)
5 134.6 - 2.60 (41), 2.79 (42)
3,7 135.07 - 6.49 (4/6)
135.12 - 1,21,9,13
135.2 -
3.10 (2/8),
4.43 (2/8),
6.52-6.55 -
15,19 135.5 -
3.15
(14/20), 4.46
(14/20)
6.56-6.59,
6.67 (16/18)
43 141.6 - 2.60 (41), 2.79 (42),
7.19 (47), 7.53 (45)
28 155.1 - 3.10 (2/8), 3.84 (38),
4.43 (2/8), 6.49 (4/6)
25,27 156.6 -
3.10 (2/8), 3.15 (14/20),
3.85 (29/32/35/38),
4.43 (2/8), 4.46 (14/20),
6.53 & 6.57 (10/12/22/24)
26 156.9 -
3.15 (14/20),
3.85 (29/32/35/38),
4.46 (14/20), 6.67 (16/18)
Cross-peak tables 397
1.38 5,17-Bis(2-bromophenethyl)-25,26,27,28-tetra-n-propoxycalix[4]-
arene (137b)
3 28 7
65
4
8
O
41
13
10
9 27
12
11
O35
36
37
14
42
43
44
45
46
47
48
Br
38
39
40
2
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
40 10.2 0.94 1.94 (39), 3.90 (38)
37 10.7 1.05 1.91 (36), 3.76 (35)
39 23.2 0.94 (40), 3.90 (38)
36 23.5 1.92
1.05 (37), 3.76 (35)
8,14 31.1 3.09, 4.42 6.31 (10/12), 6.70 (4/6)
41 35.5 2.71 2.93 (42), 6.70 (4/6)
42 38.7 2.93 2.71 (41), 7.06 (42)
38 76.7 3.90 0.94 (40), 1.94 (39)
35 76.9 3.76 1.05 (37), 1.91 (36)
11 122.1 6.41 3.09 (8/14), 4.42 (8/14)
44 124.7 - 2.93 (42), 7.03 (46), 7.06
(48), 7.14 (47), 7.52 (45)
47 127.3 7.14 7.52 (45)
46 127.6 7.03 7.06 (38)
10,12 127.9 6.31 3.09 (8/14), 4.42 (8/14),
6.31 (10/12)
4,6 128.7 6.70 2.71 (41), 3.09 (8/14),
4.42 (8/14), 6.70 (4/6)
398 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
48 130.7 7.06 2.93 (42), 7.03 (46)
45 132.9 7.52 7.14 (47)
9,13 134.3 -
3.09 (8/14), 4.42 (8/14),
6.31 (10/12), 6.41 (11),
6.70 (4/6)
5 134.5 - 2.71 (41), 2.93 (42)
3,7 135.9 - 3.09 (8/14), 4.42 (8/14),
6.70 (4/6)
43 141.3 - 2.71 (41), 2.93 (42),
7.14 (47), 7.52 (45)
28 155.7 - 3.09 (8/14), 3.90 (38),
4.42 (8/14), 6.70 (4/6)
27 156.0 -
3.09 (8/14), 3.76 (35), 4.42
(8/14),6.31 (10/12),
6.41 (11)
Cross-peak tables 399
1.39 5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (163) and
5,17-Bis-(2-chlorobenzoyl)-tetra-n-propoxycalix[4]arene (166)
22
21 25 1
24
23
2
3 28 7
6
5
4
820
OO
41
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
O 42
43
44
45
46
47
38
39
40
Cl48
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.6 0.99
10.78 1.03 31,34,
37,40 10.84 1.04
1.89-2.00 (30/33/36/39),
3.82, 3.86-3.96
(29/32/35/38)
23.8
23.95 30,33,
36,39 24.01
1.89-2.00
0.99-1.04 (31/34/37/40),
3.82, 3.86-3.96
(29/32/35/38)
31.4
2,8,14,20 31.5
3.17, 3.18, 4.46, 4.47
6.58-6.67 (2 x)
(10/12/22/24), 6.76
(16/18), 7.01 (4/6)
77.4
77.6 29,32,
35,38 77.7
3.82, 3.86-3.96 0.99-1.04 (31/34/37/40),
1.89-2.00 (30/33/36/39)
17 122.4 6.48 -
11,23 122.7 6.62 -
46 126.7 7.26 7.41
6.48 (17), 6.59 (16/18) 16,18 128.6 6.59
10,12, 128.8 6.65 (2d)
3.17, 3.18, 4.46, 4.47
(2/8/14/20)
400 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
6.76 (10/12/22/24) 22,24
129.2 6.76
3.17, 3.18, 4.46, 4.47
(2/8/14/20);
6.65 (10/12/22/24)
47 130.0 6.92 -
44 130.5 7.42 7.26
5 130.8 - -
45 131.1 7.41 6.92 (47), 7.42
4,6 131.3 7.01 3.17, 3.18, 4.46,
4.47(2/8); 7.01 (4/6)
43 131.7 - -
135.4 - 3.17, 3.18, 4.46, 4.47
(14/20); 6.48 (17)
136.0 - -
1,3,7,9,13,
15,19,21
136.3 - -
(3.83), 6.59 (16/18) 26 156.9 -
3.17, 3.18, 4.46, 4.47
(2/8/14/20);
3.83, 3.86-3.96
(29/32/35/38) 25,27 157.3 -
6.66, 6.75 (10/12/20/24)
28 162.2 -
3.17, 3.18, 4.46, 4.47
(2/8);
3.86-3.96 (38),
7.01 (4/6)
41 194.2 - 6.92 (47), 7.01 (4/6)
Cross-peak tables 401
3 28 7
6
5
4
8
O
41
13
10
927
12
11
O35
36
37
14
O 42
43
44
45
46
47
38
39
40
2
Cl
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
3.97 (38) 40 10.3 0.99
1.88-1.98 (36/39)
37 10.5 1.02 3.82 (35)
36 23.4 1.02 (37), 3.82 (35)
39 23.5 1.88-1.98
0.99 (40), 3.97 (38)
8,14 31.1 3.19, 4.46 6.49 (10/12), 7.30 (4/6)
1.02 (37) 35 77.0 3.82
1.88-1.98 (36/39)
38 77.3 3.97 0.99 (40)
11 122.8 6.49 -
46 126.6 29 7.39 (44)
10,12 128.4 6.49 3.19, 4.46 (8/14),
6.49 (10/12)
47 129.5 6.99 7.37 (45)
44 130.0 7.39 7.29 (46)
45 130.5 7.37 6.99 (47)
5 130.8 - -
4/6 131.3 7.30 (s) 3.19, 4.46 (8/14),
7.30 (4/6)
43 131.4 - 7.39 (44)
402 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
9,13 134.1 - 3.19, 4.46 (8/14),
6.49 (10/12)
3,7 136.0 - 3.19, 4.46 (8/14),
7.30 (4/6)
42 138.7 - 7.29 (46), 7.39 (44)
27 156.1 - 3.19, 4.46 (8/14),
3.82 (35), 6.49 (10/12)
28 162.2 - 3.19, 4.46 (8/14),
3.97 (38), 7.30 (4/6)
41 194.3 - 6.99 (47), 7.30 (4/6)
Cross-peak tables 403
1.40 5,17-Bis(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (171)
and 5,11,17-Tris(2-bromobenzoyl)-25,27-di-n-propoxycalix[4]-
arene (172)
3 28 7
65
4
8
OH36
37
13
10
9 27
12
11
O33
34
35
14
O 38
39
40
41
42
43
2
Br44
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
35 11.1 1.32 2.06 (34), 3.99 (33)
34 23.6 2.06 1.32 (35), 3.99 (33)
8,14 31.5 3.43, 4.27 6.92 (10/12), 7.59 (4/6)
33 78.7 3.99 1.32 (35), 2.06 (34)
39 119.7 - 7.29 (43), 7.34 (41),
7.41 (42), 7.66 (40)
11 125.8 6.81 -
42 127.2 7.41 7.66 (40)
5 127.6 - -
3,7 128.3 - 3.43(8/14), 4.27(8/14),
9.25 (36)
43 129.0 7.29 7.34 (41)
10,12 129.6 6.92 3.43(8/14), 4.27(8/14),
6.81 (11), 6.92 (10/12)
41 130.8 7.34 7.29 (43)
4,6 131.8 7.59 3.43(8/14), 4.27(8/14),
7.59 (4/6)
404 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
9,13 132.6 - 3.43(8/14), 4.27(8/14),
6.81 (11), 6.92 (10/12)
40 133.2 7.66 7.41 (42)
38 141.7 - 7.41 (42), 7.66 (40)
27 151.9 -
3.43 (8/14), 3.99 (33),
4.27(8/14), 6.81 (11),
6.92 (10/12)
28 159.4 - 3.43(8/14), 4.27(8/14),
7.59 (4/6), 9.25 (36)
37 194.6 - 7.29 (43), 7.59 (4/6)
Cross-peak tables 405
22
2125 1
24
23
2
3 28 7
65
4
820
OH36
O
37
19
29
30
31
16
1526
18
17
14
OH32
13
10
927
12
11
O33
34
35
O 38
39
40
41
42
43
51
O52
44
45
53
54
55
5657
O46
47
48
49
50
Br Br Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.9 31,35
11.0 1.30
2.06 (30/34), 4.01
(29/33)
30,34 23.6 2.06 1.30 (31/35), 4.01
(29/33)
8,14 31.2 3.42, 4.30
2,20 31.4 3.46, 4.27
6.93 (22/24), 7.30
(10/12), 7.48 and 7.67
(4/6/16/18)
78.7 29,33
78.9 4.01
1.30 (31/35), 2.06
(30/34)
39,53 119.7 - 7.28 (57), 7.34 (41/55),
7.40 (42/56), 7.65 (54)
46 120.1 - 7.11 (50), 7.34 (48/49),
7.53 (47)
23 125.7 6.81 -
42, 49, 56 127.3 7.34, 7.40 7.53 (47), 7.65 (54)
127.7 - 7,9,13,15,
5,17 127.8 -
3.42 (8/14), 4.30 (8/14)
3,7 128.4 - 8.77 (36)
43, 57 129.1 7.28 7.34 (55)
22,24 129.6 6.93 6.93 (22/24)
50 129.7 7.11 7.34 (48)
41,55 130.9 7.34 7.28 (43/57)
48 131.5 7.34 7.11 (50)
406 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
4,6,16,18 131.8 7.67 7.48
10,12 131.96 7.30 3.42 (8/14), 4.30 (8/14)
7.30 (10/12)
4,6,16,18 132.00 7.48 3.42 (8/14), 4.30(8/14)
7.67
1,21 132.5 - 6.81 (23)
40,54 133.4 7.65 7.40 (56)
47 133.5 7.53 7.34 (49)
45 140.0 - 7.34 (49), 7.53 (47)
38,52 141.4 - 7.40 (42/56), 7.65
(40/54)
25 151.9 -
3.46 (2/20), 4.00 (29),
4.27 (2/20), 6.81 (23), 6.93
(22/24)
27 156.7 - 3.42 (8/14), 4.03 (33),
4.30 (8/14), 7.30 (10/12)
26,28 159.1 -
3.42 (8/14), 3.46 (2/20),
4.27 (2/20), 4.30 (8/14),
7.48 and 7.67 (4/6/16/18),
8.77 (32/36)
37,51 194.4 - 7.11 (50), 7.30 (10/12),
7.48 and 7.67 (4/6/16/18)
Cross-peak tables 407
1.41 5-(2-Bromobenzoyl)-25,27-di-n-propoxycalix[4]arene (170)
22
21 25 1
24
23
2
3 28 7
65
4
820
OH36
O
37
19
29
30
31
16
15 26
18
17
14
OH32
13
10
9 27
12
11
O33
34
35
O 38
39
40
41
42
43
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
31,35 11.0 1.32 2.07 (30/34), 3.98
(29/33)
30,34 23.6 2.07 1.32 (31/35), 3.98
(29/33)
31.5 2,8,14,20
31.6 3.39, 3.41, 4.29, 4.31
6.89 and 6.95
(10/12/22/24), 7.06
(16/18), 7.58 (4/6)
29,33 78.6 3.98 1.32 (31/35), 2.07
(30/34)
17 119.2 6.65 -
39 119.7 - 7.29 (43), 7.32 (41),
7.65 (40)
11,23 125.6 6.77 -
42 127.2 7.40 7.65 (40)
5 127.5 - -
15,19 128.1 -
3.39 (14/20), 4.31
(14/20), 6.65 (17), 8.26
(32)
3,7 128.5 - 9.28 (36)
16,18 128.6 7.06 3.39 (14/20), 4.31
408 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
(14/20), 7.06 (16/18)
43 129.1 7.29 7.32 (41)
129.2 6.89 6.95
10,12,22,2
4 129.5 6.95
3.39 (14/20), 3.41 (2/8),
4.29 (2/8), 4.31 (14/20),
6.89
41 130.8 7.32 7.29 (43)
4,6 131.8 7.58 3.41 (2/8), 4.29 (2/8),
7.58 (4/6)
1,9,13,21 132.6 -
3.39 (14/20), 3.41 (2/8),
4.29 (2/8), 4.31 (14/20),
6.77 (11/23)
40 133.2 7.65 7.40 (42)
1,9,13,21 133.7 -
3.39 (14/20), 3.41 (2/8),
4.29 (2/8), 4.31 (14/20),
6.77 (11/23)
38 141.7 - 7.40 (42), 7.65 (40)
25,27 152.0 -
3.39 (14/20), 3.41 (2/8),
3.98 (29), 4.29 (2/8), 4.31
(14/20), 6.77 (11/23), 6.89
and 6.95 (10/12/22/24)
26 153.5 -
3.39 (14/20), 4.31
(14/20), 6.65 (17), 7.06
(16/18),
8.26 (32)
28 159.6 - 3.41 (2/8), 4.29 (2/8),
7.58 (4/6), 9.28 (36)
37 194.6 - 7.29 (43), 7.58 (4/6)
Cross-peak tables 409
1.42 cone-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (162),
5-(2-Bromobenzoyl)-25,26,27-tri-n-propoxycalix[4]arene (179)
and paco-5-(2-Bromobenzoyl)-tetra-n-propoxycalix[4]arene (180)
22
21 25 1
24
23
2
3 28 7
6
5
4
820
OO
41
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
O 42
43
44
45
46
47
38
39
40
Br48
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
31,37 10.4
10.47 34,40
10.51
0.99 1.93, 3.83, 3.91
29,35 23.37
23.44 33,39
23.5
1.93 0.99, 3.83, 3.91
31.08 2,8,14,20
31.13 3.16, 3.17, 4.45 6.55, 6.65, 7.11 (4/6)
29,32,35,38 77.0 3.83, 3.91 0.99, 1.93
43 120.1 - 6.95 (47), 7.29 (46),
7.61 (44)
17 122.1 6.55 -
11,23 122.5 6.55 -
46 126.7 7.29 7.61 (44)
128.3
128.4 6.55
3.16 (2/8/14/20), 4.45
(2/8/14/20), 6.65 10,12,16,
18,22,24 128.7
6.65
- 6.55
410 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
47 129.7 6.95 7.29 (45)
5 130.1 - -
45 130.8 7.29 6.95 (47)
4,6 131.2 7.11 3.16 (2/8/14/20), 4.45
(2/8/14/20), 7.11 (4/6)
44 133.2 7.61 7.29 (46)
134.6 - 6.55
-
135.1 - 6.55
135.5 -
1,3,7,9,
13,15,19,21
135.6 -
3.16 (2/8/14/20),
4.45 (2/8/14/20)
42 140.8 - 7.29 (46), 7.61 (44)
25,27 156.58 -
26 156.64 -
3.16 (2/8/14/20), 3.83
(29/35), 3.91 (32), 4.45
(2/8/14/20), 6.55, 6.65
28 161.9 - 3.16 (2/8), 3.91 (38),
4.45 (2/8), 7.11 (4/6)
41 194.8 - 6.95 (47), 7.11 (4/6)
Cross-peak tables 411
22
21 25 1
24
23
2
3 28 7
65
4
820
OH38
O
39
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
O 40
41
42
43
44
45
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 9.7 0.94 2.25 (33), 3.84 (32)
31,37 10.9 1.11 1.90 (30/36), 3.74
(29/35)
33 22.6 2.25 0.94 (34), 3.84 (32)
30,36 23.6 1.90 1.11 (31/37), 3.74
(29/35)
2,8 30.8 3.35, 4.34
14,20 30.9 3.22, 4.40
6.40 (10/12/22/24), 7.18
(16/18), 7.60 (4/6)
32 76.6 3.84 0.94 (34), 2.25 (33)
29,35 77.8 3.74 1.11 (31/37), 1.90
(30/36)
41 119.8 - 7.34 (43), 7.43 (45),
7.66 (42)
17 123.2 6.97 7.18 (16/18)
11,23 123.4 6.40 -
44 127.3 7.43 7.66 (42)
5 127.5 - 3.35 (2/8), 4.34 (2/8)
127.8 4.40, (14/20), 6.40
(10/12/22/24) 10,12,22,24
128.5
6.40
-
45 129.2 7.43 7.34 (43)
412 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
16,18 129.3 7.18
3.22 (4/20), 4.40
(14/20), 6.97 (17), 7.18
(16/18)
3,7 130.3 - 5.99 (OH)
43 130.8 7.34 -
4,6 131.6 7.60 3.35 (2/8), 4.34 (2/8),
7.60 (4/6)
1,9 131.7 - -
42 133.3 7.66 6.40, 7.43 (44)
13,21 133.7 - 3.22 (14/20),
4.40 (14/20)
15,19 137.1 -
3.22 (14/20), 4.40
(14/20), 6.97 (17),
7.18 (16/18)
40 141.8 - 7.43 (44), 7.66 (44)
25,27 154.4 -
3.22 (14/20), 3.35 (2/8),
3.74 (29/35), 4.34 (2/8),
4.40 (14/20),
6.40 (10/12/22/24)
26 157.0 - 3.22 (14/20), 3.84 (32),
4.40 (14/20), 7.18 (16/18)
28 159.3 - 3.35 (2/8), 4.34 (2/8),
5.99 (OH), 7.60 (4/6)
39 195.1 - 7.43, (45), 7.60 (4/6)
Cross-peak tables 413
22
21 251
24
23
2
3 7
820
O
19
29
30
31
16
1526
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
28
6
5
4
O
41
O42
38
39
40
47
46
45
44
43
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 10.1 0.76 1.41 (33), 3.35 (32)
40 10.7 1.06 1.94 (39), 3.82 (38)
31,37 11.0 1.02 1.78 (30/36), 3.52
(29/35), 3.68 (29/35)
33 22.0 1.41 0.76 (34), 3.35 (32)
30,36 23.9 1.78 1.02 (31/37), 3.52
(29/35), 3.68 (29,35)
39 24.2 1.94 1.06 (40), 3.82 (38)
14,20 30.7 3.06, 4.07 6.32 (12/22),
7.09 (16/18)
2,8 36.2 3.68 6.91 (10/24), 7.75 (4/6)
38 74.8 3.82 1.06 (40), 1.94 (39)
32 75.5 3.35 0.76 (34), 1.41 (33)
29,35 76.5 3.52, 3.68 1.02 (31/37),
1.78 (30/36)
43 120.0 - 7.36 (45), 7.44 (46),
7.50 (47), 7.68 (44)
11,23 121.7 6.45 -
17 122.5 6.91 7.09 (16/18)
46 126.9 7.44 7.68 (44)
12,22 128.9 6.32 6.91 (10/24)
47 129.0 7.50 7.36 (45)
16,18 129.1 7.09 3.06 (14/20),
414 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
4.07 (14/20), 7.09 (16/18)
10,24 129.4 6.92 6.32 (12/22), 6.45
(11/23)
5 129.9 - -
45 130.7 7.36 7.50 (47)
1,9 131.4 - 3.68 (2/8), 6.45
4,6 133.1 7.75 7.75 (4/6)
44 133.4 7.68 7.44 (46)
13,21 133.7 - 3.06 (14/20), 3.68 (2/8),
4.07 (14/20), 6.45 (11/23)
3,7 134.6 - n.d.
15,19 137.1 - 3.06 (14/20), 4.07
(14/20), 6.91 (10/24)
42 141.9 - 7.44 (46), 7.50 (47),
7.68 (44)
25,27 155.7 -
3.06 (14/20), 3.52
(29/35), 3.68 (29/35), 4.07
(14/20), 6.32 (12/22), 6.45
(11/23), 6.91 (10/24)
26 156.9 -
3.06 (14/20),
4.07 (14/20),
3.35 (32), 7.09 (16/18)
28 163.1 - 3.68 (2/8), 3.82 (38),
7.75 (4/6)
41 195.1 - 7.50 (47), 7.75 (4/6)
Cross-peak tables 415
1.43 cone-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]arene
(165), paco-5,17-Bis(2-bromobenzoyl)-tetra-n-propoxycalix[4]-
arene (175) and 5,17-Bis(2-bromobenzoyl)-25,26,27-tri-n-
propoxycalix[4]arene (176)
3 28 7
6
5
4
8
O
41
13
10
927
12
11
O35
36
37
14
O 42
43
44
45
46
47
38
39
40
2
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.3 0.99 3.97 37,40
10.6 1.02 1.93
3.82
23.4 36,39
23.5 1.93
0.99, 1.03, 3.82 (35),
3.97 (38)
8,13 31.1 3.19, 4.45 6.49 (10/12), 7.30 (4/6)
35 77.0 3.82
38 77.3 3.97 0.99, 1.93
43 119.7 - 6.97 (47), 7.29 (45), 7.59
(44)
11 122.8 6.49 -
46 127.2 7.35 7.59 (44)
10,12 128.4 6.49 3.19 (8/14), 4.45 (8/14),
6.49 (10/12)
47 129.4 6.97 n.d.
5 130.2 - -
45 130.9 7.29 6.97
416 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
4,6 131.4 7.30 3.19 (8/14), 4.45 (8/14),
7.30 (4/6)
44 133.1 7.59 7.35 (46)
9,13 134.1 - 3.19 (8/14), 4.45 (8/14),
6.49 (11)
3,7 136.1 - 3.19 (8/14), 4.45 (8/14)
42 140.8 - 7.35, 7.59
27 156.1 - 3.19 (8/14), 3.82 (35),
4.45 (8/14), 6.49 (10/12)
28 162.3 - 3.19 (8/14), 3.97 (38),
4.45 (8/14), 7.30 (4/6)
41 195.0 - 7.30 (4/6)
Cross-peak tables 417
22
21 251
24
23
2
3 7
820
O
19
29
30
31
16
1526
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
28
6
5
4
O
41
O42
38
39
40
47
46
45
44
43
Br
48
49O50
51
52
53
54
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 10.1 0.77 1.43 (33), 3.43 (32)
40 10.7 1.08 1.95 (39), 3.84 (38)
31,37 10.9 (2) 1.01 1.78 (30/36), 3.50
(29/35), 3.68 (29/35)
33 22.1 1.43 0.77 (34), 3.43 (32)
30,36 23.9 (2) 1.78 1.01 (31/37), 3.50
(29/35), 3.68 (29/35)
39 24.2 1.95 1.08 (40), 3.84 (38)
14,20 30.7 3.10, 4.09 6.28 (12/22),
7.57 (16/18)
2,8 36.0 3.67 6.94 (10/24), 7.75 (4/6)
38 75.0 3.84 1.08 (40), 1.95 (39)
32 75.6 3.43 0.77 (34), 1.43 (33)
29,35 76.5 (2) 3.50, 3.68 1.01 (31/37),
1.78 (30/36)
119.8 - 43,50
120.0 -
7.35 (46/52), 7.43
(47/54), 7.67 (44/51)
11,23 121.9 6.47 6.28 (12/22)
126.9 45,53
127.3 7.43 7.66 (44/51)
12,22 128.9 6.28 6.94 (10/24)
47,54 129.0 7.47 7.35 (46/52)
418 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
129.2 7.42
10,24 129.7 6.94 6.28 (12/22)
130.0 - n.d. 5,7
130.6 - n.d.
46,52 130.8 n.d.
131.0 7.36
n.d.
16,18 131.5 7.57 7.57 (16/18)
1,9,13,21
132.8 - n.d.
4,6 133.0 7.76 7.75 (4/6)
133.3 44,51
133.4 7.67 7.46 (46/53)
3,7 134.5 - 3.67 (2/8)
15,19 137.6 - 3.10 (14/20), 4.09
(14/20), 7.57 (16/18)
141.5 - 42, 49
141.8 -
7.42 (47/54), 7.47
(46/53), 7.67 (44/51)
25,27 155.7 -
3.10 (14/20), 3.50
(29/35), 3.67 (2/8), 4.09
(14/20), 6.28 (12/22), 6.47
(11/23), 6.94 (10/24)
26 162.3 - 3.10 (14/20), 3.43 (32),
4.09 (14/20), 7.57 (16/18)
28 163.0 - 3.67 (2/8), 3.84 (38),
7.75 (4/6)
41 195.1 - 7.47 (47), 7.75 (4/6)
48 195.5 - 7.42 (54), 7.57 (16/18)
Cross-peak tables 419
22
21 25 1
24
23
2
3 28 7
65
4
820
OH38
O
39
19
29
30
31
16
15 26
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
O 40
41
42
43
44
45
46
47O
48
49
50
51
52
Br Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 9.7 0.95 2.23 (33), 3.93 (32)
31,37 10.9 1.10 1.89 (30/36),
3.74 (29/35)
33 22.7 2.23 0.95 (34), 3.93 (32)
30,36 23.6 1.89 1.10 (31/37),
3.74 (29/35)
2,8 30.8 3.36, 4.32 6.38, 7.60
14,20 30.9 3.26, 4.41 7.65
32 76.7 3.93 0.95 (34), 2.23 (33)
29,35 77.9 3.74 1.10 (31/37),
1.89 (30/36)
41,48 119.8 - 7.38, 7.68
11,23 123.6 6.42 -
127.3 44,51
127.4 7.43 7.67 (42/49)
5 127.6 - -
128.2 6.42 - 10,12,22,24
128.5 6.38 6.43, 7.36
4.41
(14/20)
129.15 45,52
129.23 7.43 n.d.
3,7 130.0 - 3.36 (2/8), 4.32 (2/8),
6.07 (38)
420 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
130.8 43,50
131.2 7.37 7.43
17 131.3 - -
4,6 131.6 7.60 7.60
16,18 131.7 7.65 7.65
131.9 - 1,9,13,21
132.8 -
3.26 (14/20),
4.41 (14/20), 6.43
133.3 7.68 42,49
133.4 7.66 7.43
15,19 137.7 - 3.26 (14/20), 4.41
(14/20), 7.65 (16/18)
141.3 - 40,47
141.7 -
7.43, 7.68
25,27 154.4 -
3.26 (14/20), 3.36 (2/8),
3.74 (29/35), 4.32 (2/8),
4.41 (14/20), 6.38
(10/12), 6.43 (11)
28 159.2 - 3.36 (2/8), 4.32 (2/8),
6.07 (38), 7.60 (4/6)
26 162.3 - 3.26 (14/20), 3.93 (32),
4.41 (14/20), 7.65 (16/18)
39 195.1 - 7.60 (4/6)
46 195.4 - 7.65
(16/18)
7.43
Cross-peak tables 421
1.44 5-(2-Chlorobenzoyl)-25,27-di-n-propoxcalix[4]arene (173) and
5,17-Bis(2-chlorobenzoyl)-25,27-di-n-propoxycalix[4]arene (174)
22
21 25 1
24
23
2
3 28 7
65
4
820
OH36
O
37
19
29
30
31
16
15 26
18
17
14
OH32
13
10
9 27
12
11
O33
34
35
O 38
39
40
41
42
43
Cl
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
31,35 11.1 1.32 2.07 (30/34),
3.96 and 4.01 (29/33)
30,34 23.6 2.07 1.32 (31/35),
3.96 and 4.01 (29/33)
31.5 2,8,14,20
31.6 3.39, 3.41, 4.29, 4.31
6.88 (12/22)6.95 (10/24),
7.06 (16/18), 7.59 (4/6)
29,33 78.6 3.99 1.32 (31/35),
2.07 (30/34)
17 119.2 6.65 -
11,23 125.6 6.78 -
42 126.7 7.35 7.47 (40)
5 127.8 - -
15,19 128.1 -
3.40 (2/8/24/20), 4.30
(2/8/24/20), 6.65 (17),
8.26 (32)
3,7 128.5 - 3.41 (2/8), 4.29 (2/8),
9.27 (36)
16,18 128.6 7.06 3.40 (2/8/24/20), 4.30
(2/8/24/20), 7.06 (16/18)
422 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
12,22 129.1 6.88 3.41 (2/8), 4.29 (2/8),
6.95 (10/24)
43 129.2 7.32 7.41 (41), 7.47 (40)
10,24 129.5 6.95
3.39 (14/20), 4.31
(14/20), 6.88 (12/22),
6.78 (11/23)
40 130.1 7.47 7.35 (42)
41 130.7 7.41 n.d.
39 131.4 - 7.32 (43), 7.41 (41),
7.47 (40)
4/6 131.7 7.59 7.59 (4/6)
1,9 132.6 - 3.41 (2/8), 4.29 (2/8),
6.78 (11/23), 6.95 (10/24)
13,21 133.7 -
3.39 (14/20), 4.31
(14/20), 6.88 (12/22), 6.78
(11/23), 7.06 (16/18)
38 139.6 - 7.35 (42), 7.47 (40)
25,27 152.0 -
3.39 (14/20), 3.41 (2/8),
3.96 and 4.01 (29/33), 4.29
(2/8), 4.31 (14/20), 6.78
(11/23), 6.88 (12/22),
6.95 (10/24)
26 153.5 -
3.39 (14/20), 4.31
(14/20), 6.65 (17), 7.06
(16/18), 8.26 (32)
28 159.5 - 3.41 (2/8), 4.29 (2/8),
7.59 (4/6), 9.27 (36)
37 194.0 - 7.32 (43), 7.59 (4/6)
Cross-peak tables 423
3 28 7
65
4
8
OH36
37
13
10
9 27
12
11
O33
34
35
14
O 38
39
40
41
42
43
2
Cl44
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
35 11.1 1.32 2.08 (34), 3.99 (33)
34 23.6 2.08 1.32 (35), 3.99 (33)
8,14 31.5 3.43, 4.28 6.92 (10/12), 7.59 (4/6)
33 78.7 3.99 1.32 (35), 2.08 (34)
11 125.8 6.81 -
42 126.7 7.35 7.48 (40)
5 128.0 - -
3,7 128.3 - 3.43 (8/14), 4.28 (8/14),
9.23 (36)
43 129.1 7.32 7.42 (41)
10,12 129.6 6.92 3.43 (8/14), 4.28 (8/14),
6.92 (10/12)
40 130.1 7.48 7.35 (42)
41 130.7 7.42 n.d.
39 131.3 - 7.32 (43), 7.42 (41),
7.48 (40)
4,6 131.7 7.59 7.59 (4/6)
9,13 132.7 - 3.43 (8/14), 4.28 (8/14),
6.81 (11)
38 139.6 - 7.35 (42), 7.48 (40)
27 151.9 -
3.43 (8/14), 3.99 (33),
4.28 (8/14), 6.81 (11),
6.92 (10/12)
424 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
28 159.4 - 3.43 (8/14), 4.28 (8/14),
7.59 (4/6), 9.23 (36)
37 193.9 - 7.32 (43), 7.59 (4/6)
Cross-peak tables 425
1.45 paco-5-(2-Chlorobenzoyl)-tetra-n-propoxcalix[4]arene (182)
22
21 251
24
23
2
3 7
820
O
19
29
30
31
16
1526
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
28
6
5
4
O
41
O42
38
39
40
47
46
45
44
43
Cl
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 10.1 0.75 1.40 (33), 3.35 (32)
40 10.7 1.06 1.94 (39), 3.82 (38)
31,37 11.0 1.02 1.77 (30/36), 3.52
(29/35), 3.68 (29/35)
33 22.0 1.40 0.75 (34), 3.35 (32)
30,36 23.9 1.77 1.02 (31/37), 3.52
(29/35), 3.68 (29/35)
39 24.2 1.94 1.06 (40), 3.82 (38)
14,20 30.7 3.05, 4.07 6.32 (12/22),
7.09 (16/18)
2,8 36.2 3.68 6.91 (10/24), 7.76 (4/6)
38 74.8 3.82 1.06 (40), 1.94 (39)
32 75.5 3.35 0.75 (34), 1.40 (33)
29,35 76.5 3.52, 3.68 1.02 (31/37),
1.77 (30/36)
11,13 121.7 6.45 -
17 122.5 6.91 7.09 (16/18)
46 126.4 7.38 7.50 (44)
12/22 128.9 6.32 3.05 (14/20), 4.07
(14/20), 6.91
426 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
16/18 129.07 7.09 7.09
47 129.11 7.50
10/24 129.4 6.91 6.32
44 130.2
n.d. 130.3 7.50 7.38, 7.50
45 130.6 7.44 -
1,9 131.4 - 6.45 (11/13)
n.d. 131.6 - 3.68 (2/8)
4,6 133.1 7.76 7.76
13,21 133.7 - 3.05 (14/20), 4.07
(14/20), 6.45 (11/13)
3,7 134.5 - -
15,19 137.2 -
3.05 (14/20), 4.07 3.05
(14/20), 6.91 (17),
7.09 (16/18)
42 139.9 - 7.38 (46), 7.50 (47)
25,27 155.8 -
3.52 (29/35), 3.68
(29/35), 4.07 (14/20), 6.32
(12/22), 6.45 (11/13),
6.91 (10/24)
26 156.9 - 3.05 (14/20), 3.35 (32),
7.09 (16/18)
28 163.1 - 3.68 (2/8), 3.82 (38),
7.76 (4/6)
41 194.5 - 7.50 (47), 7.76 (4/6)
Cross-peak tables 427
1.46 paco-5,17-Bis(2-chlorobenzoyl)-tetra-n-propoxcalix[4]arene (177)
22
21 251
24
23
2
3 7
820
O
19
29
30
31
16
1526
18
17
14
O32
33
34
13
10
9 27
12
11
O35
36
37
28
6
5
4
O
41
O42
38
39
40
47
46
45
44
43
Cl
48
49O50
51
52
53
54
Cl
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
34 10.1 0.76 1.42 (33), 3.42 (32)
40 10.7 1.08 1.96 (39), 3.84 (38)
31,37 11.0 1.01 1.76 (30/36),
3.50 and 3.67 (29/35)
33 22.1 1.42 0.76 (34), 3.42 (32)
30,36 23.8 1.76 1.01 (31/37),
3.50 and 3.67 (29/35)
39 24.3 1.96 1.08 (40), 3.84 (38)
14,20 30.8 3.10, 4.08 6.27 (12/22),
7.57 (16/18)
2,8 36.0 3.67 6.94 (10/24), 7.75 (4/6)
38 75.0 3.84 1.08 (40), 1.96 (39)
32 75.6 3.42 0.76 (34), 1.42 (33)
29,35 76.5 3.50, 3.67 1.01 (31/37),
1.76 (30/36)
11,23 122.0 3.47 6.27 (12/22),
6.94 (10/24)
44-47,
51-54 126.4 7.38 7.43
428 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 126.8 - 7.43
12,22 128.9 6.27 3.10 (14/20), 4.08
(14/20), 6.94 (10/24)
n.d. 129.1 - n.d.
44-47,
51-54 129.3 7.48 n.d.
10,24 129.7 6.94 3.67 (2/8), 6.27 (12/22)
130.21 n.d. 44-47,
51-54 130.24 7.48
n.d.
n.d. 130.3 - n.d.
44-47,
51-54 130.7 7.44 n.d.
n.d. 130.9 - n.d.
n.d. 131.0 - n.d.
16,18 131.4 7.57 3.10 (14/20), 4.08
(14/20), 7.57 (16/18)
n.d. 131.5 - n.d.
1,9 131.57 - 3.67 (2/8), 6.47 (11/23)
n.d. 131.64 - n.d.
13,21 132.8 - 3.10 (14/20), 4.08
(14/20), 6.47 (11/23)
4,6 133.0 7.75 3.10 (14/20), 4.08
(14/20), 7.75 (4/6)
3,7 134.5 - 3.67 (2/8)
15,19 137.6 - 3.10 (14/20), 4.08
(14/20), 7.57 (16/18)
n.d. 139.4 - 7.43
n.d. 139.8 - 7.43
25,27 155.7 -
3.10 (14/20), 3.50
(29/35), 3.67 (29/35/2/8),
4.08 (14/20), 6.27 (12/22),
Cross-peak tables 429
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
6.47 (11/23), 6.94 (10/24)
26 162.3 - 3.10 (14/20), 3.42 (32),
4.08 (14/20), 7.57 (16/18)
28 163.0 - 3.67 (2/8), 3.84 (38),
7.75 (4/6)
41 194.5 - 7.43, 7.75 (4/6)
48 194.9 - 7.43, 7.57 (16/18)
H atom δ [ppm] H-H-Cosy
[ppm] H atom δ [ppm]
H-H-Cosy
[ppm]
34 0.76 3.42 2,8 3.67 -
31,37 1.01 3.50, 3.67 29,35 3.64-3.72 1.01, 1.76,
3.50
40 1.08 3.84 38 3.84 1.08, 1.96
33 1.37-1.47 3.42 14,20 4.08 3.10
30,36 1.72-1.81 3.50, 3.67 12,22 6.27 6.47, 6.94
39 1.91-2.01 3.84 11,23 6.47 6.27, 6.94
14,20 3.10 4.08 10,24 6.94 6.27, 6.47
32 3.42 0.76, 1.42
22/51,
45/52,
36/53,
47/54
7.36-7.50 7.36-7.50
3.49 16,18 7.57 - 29,35
3.51
1.06, 1.76,
3.67 4,6 7.75 -
430 Appendix
1.47 25,26,27,28-Tetra-n-propoxycalixarenedifluorenone (184)
36
35 39 1
38
37
2
3 42 14
13
5
4
1534
OO
33
43
44
45
23
22 40
32
31
21
O46
47
48
20
17
1641
19
18
O49
50
51
52
53
54
12
76
11
10
98
O
3 35 14
13
5
4
15
O
20
17
16 34
19
18
O42
43
44
21
45
46
47
12
76
11
10
98
O 3029
24
2827
26
25
O
2
a b
C atom δ [ppm] HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
48,54 10.0 a+b 0.95 2.06 (47/53),
4.03 and 4.25 (46/52)
45,51 11.0 a+b 1.15 1.92 (44/50),
3.67 and 3.80 (43/49)
47,53 23.4 a+b 2.06 0.95 (48/54),
4.03 and 4.25 (46/52)
23.71 b
23.74 a 44,50
23.8 b
1.92 1.15 (45/51),
3.67 and 3.80 (43/49)
15,34 25.5 a
15,21 25.6 b 4.03, 4.49 6.22 (17/19/36)
2,34 31.2 b
2,21 31.3 a 3.24, 4.43
6.18 (37), 6.22 (19/36/38),
7.56 (4/23/32)
77.2 b 43,46,49,
52 77.3 a 3.67, 3.80, 4.01, 4.25
0.95 (48/54), 1.15 (45/51),
1.92 (44/50), 2.06 (47/53)
11,25 122.6 b
11,30 122.7 a 7.85 7.27 (9/27/28)
18 o. 37 122.8 b -
18,37 122.9 a 6.22
18 o. 37 123.0 b -
-
Cross-peak tables 431
C atom δ [ppm] HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
8,27 124.2 a
8,28 124.3 b 7.70 7.42 (10/26/29)
4,23 125.6 a
4,32 125.7 b 7.56 3.24 and 4.43 (2/21/34)
17,38 127.3 a -
17,19 127.5 b -
36,38 127.8 b 6.17
19,38 128.0 a -
6.22
3.24 and
4.43
(2/21/34),
4.03 and 4.49
(15/21/34),
6.22
(17/19,36/38)
6.18
(36/38)
9,27,28 128.5 7.27 7.83 (11/30), 7.85 (11/25)
5,31 129.27 b -
5,24 129.29 a - -
16,35 131.8 a -
16,20 131.9 b - 4.03 and 4.49 (15/21/34)
1,35 132.3 b -
1,20 132.5 a -
3.24 and 4.43 (2/21/34),
6.22 (18/37)
14,33 134.27 a -
14,22 134.30 b -
4.03 and 4.49 (15/21/34),
7.56 (4/23/32)
10,26 134.56 b
10,29 134.58 a 7.42 7.70 (8/27/28)
7,26 135.95 a -
7,29 135.99 b -
7.27 (9/27/28), 7.83
(11/30), 7.85 (11/25)
3,22,33 137.3 a+b - 3.24 and 4.43 (2/21/34)
13,23 142.2 b -
13,32 142.3 a -
4.03 and 4.49 (15/21/34),
7.56 (4/23/32), 7.83 (11/30),
7.85 (11/25)
12,31 145.31 a -
12,24 145.33 b -
7.27 (9/27/28), 7.42
(10/26/29), 7.70 (8/27/28)
432 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm] HMBC cross peaks [ppm]
155.0 b - 3.67 (43),
6.18 (36/38)
155.3 a -
39,41
155.6 b - 3.80 (49)
3.24 and
4.43
(2/21/34),
4.03 and 4.49
(15/21/34),
6.22
(17/19,36/38)
40,42 165.1 a+b -
3.24 and 4.43 (2/21/34),
4.03 and 4.49 (15/21/34),
7.56 (4/23/32)
6,25,30 193.6 a+b - 7.56 (4/23/32), 7.70
(8/27/28)
Cross-peak tables 433
3 35 14
13
5
4
15
O
20
17
16 34
19
18
O42
43
44
21
45
46
47
12
76
11
10
98
O
2
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
48,54 10.0 0.95 2.04 (47/53),
4.01 and 4.27 (46/52)
45,51 11.0 1.15 1.90 (44/50),
3.69 and 3.77 (43/49)
47,53 23.4 2.04 0.95 (48/54),
4.01 and 4.27 (46/52),
44,50 23.7 1.90 1.15 (45/51),
3.69 and 3.77 (43/49)
15,34 25.5 4.00, 4.49 6.20 (17/36)
2,21 31.3 3.26, 4.43 6.20 (19/38), 7.56 (4/23)
43,46,49,
52 77.3 3.73, 4.01, 4.27
0.95 (48/54), 1.15 (45/51),
1.90 (44/50), 2.04 (47/53)
11,30 122.7 7.83 7.26 (9/28)
18,37 122.9 6.20 -
8,27 124.2 7.69 7.42 (10/29)
4,23 125.6 7.56 3.26 (2/21), 4.43 (2/21)
17,36 127.3 4.00, 4.49
(15/34)
19,38 128.0
6.20 6.20
(17/19/36/38) 3.26, 4.43
(2/21)
9,28 128.5 7.26 7.83 (11/30)
5,24 129.3 - -
16,35 131.8 - 4.00 (15/34), 4.49 15/34)
1,20 132.5 - 3.26 (2/21), 4.43 (2/21),
434 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
6.20 (18/37)
14,33 134.3 - 4.00 (15/34), 4.49 (15/34),
7.56 (4/23)
10,29 134.6 7.42 7.69 (8/27)
7,26 135.9 - 7.26 (9/28), 7.83 (11/30)
3,22 137.3 - 3.26 (2/21), 4.43 (2/21)
13,32 142.3 - 4.00 (15/34), 4.49 (15/34),
7.56 (4/23), 7.83 (11/30)
12,31 145.3 - 7.26 (9/28), 7.42 (10/29),
7.69 (8/27), 7.82 (11/30)
39,41 155.3 -
3.26 (2/21), 3.69 (43/49),
3.77 (43/49), 4.43 (2/21),
4.49 (15/34), 6.20
(17/19/36/38)
40,42 165.1 -
3.26 (2/21), 4.01
(46/52,15/34), 4.27 (46/52),
4.43 (2/21), 4.49 (15/34),
7.56 (4/23)
6,25 193.6 - 7.26 (9/28), 7.56 (4/23),
7.69 (8/27), 7.83 (11/30)
Cross-peak tables 435
1.48 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-
dibenzyloxycalix[4]arene (212)
22
21 25 1
24
23
2
3 28 7
6
5
4
8
OHO
36
2
37
38
39
41
42 42
47
46
45
44
43
29
30
35
34 33
32
31
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
2,20 31.4 3.16, 4.23 6.50 (22/24), 6.87 (4/6)
29 78.4 5.00 7.62 (31/35)
23 125.3 6.68 6.50 (22/24)
biphenyl 126.2 7.25 7.18
biphenyl 127.0 7.39 7.44
31,35 127.4 7.62 7.36 (32/33/34)
biphenyl 127.5 7.39 7.38
3,7 127.7 - 6.87 (4/6), 7.56 (OH)
33 128.1 7.36 7.62 (31/35)
biphenyl 128.2 7.22
7.18, 7.22
32,34 128.9 7.36 7.36 (32/34)
22,24 129.2 6.50 6.50 (22/24)
biphenyl 130.0 7.18 7.18, 7.25
4,6 130.3 6.87 6.87 (4/6)
biphenyl 130.6 7.42 7.38
biphenyl 130.8 7.42 7.38
5 132.1 - -
436 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
1,21 133.0 -
3.16 (2/20), 4.23 (2/20),
6.50 (22/24), 6.68 (23),
6.87 (4/6)
30 137.0 - 5.00 (29), 7.36 (32/34)
37 140.6 - 7.18, 7.42
36 140.7 - 6.87 (4/6), 7.37, 7.41
42 142.3 - 7.18, 7.22, 7.42
25 151.9 - 3.16 (2/20), 4.23 (2/20),
5.00 (29), 6.50 (22/24)
28 152.4 - 3.16 (2/20), 4.23 (2/20),
6.87 (4/6), 7.56 (OH)
Cross-peak tables 437
1.49 5,17-Bis(biphenyl-2-yl)-26,28-dihydroxy-25,27-di-n-
propoycalix[4]arene (214)
22
21 25 1
24
23
2
3 28 7
6
5
4
8
OHO
35
29
30
31
2
36
37
38
39
40 41
46
45
44
43
42
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
31 11.00 1.27 1.97-2.06 (30), 3.91 (29)
30 23.61 1.97-2.06 1.27 (31), 3.91 (29)
2,20 31.49 3.18, 4.21 6.54 (22/24), 6.87(4/6)
29 78.30 3.91 1.27 (31), 1.97-2.06 (30)
23 125.19 6.66 -
biphenyl 126.17 7.25 7.18
biphenyl 126.88 7.16-7.25, 7.36-7.45
biphenyl 127.53
7.16-7.25,
7.36-7.45 6.87, 7.36-7.45
3,7 127.79 - 3.18 (2/8), 4.21 (2/8),
8.04 (OH)
biphenyl 128.19 7.22 7.16-7.25
22,24 129.10 6.54 6.54 (22/24)
biphenyl 129.99 7.18 7.18
4,6 130.25 6.87 3.18 (2/8), 4.21 (2/8),
6.87 (4/6)
bipheny 130.67 7.43 7.36-7.45
biphenyl 130.86 7.40 7.36-7.45
438 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
5 132.00 - 7.36-7.45
1,21 133.16 -
3.18 (2/8), 4.21 (2/8),
6.54 (22/24), 6.66 (23),
6.87 (4/6)
36 140.56 - 7.16-7.25, 7.36-7.45
35 140.69 - 6.87 (4/6), 7.36-7.45
41 142.32 - 7.16-7.25
25 151.99 -
3.18 (2/8), 4.21 (2/8),
3.91 (29), 6.54 (22/24),
6.66 (23)
28 152.52 - 3.18 (2/8), 4.21 (2/8),
6.87 (4/6), 8.04 (OH)
Cross-peak tables 439
1.50 5,17-Bis(2’-bromobiphenyl-2-yl)-25,26,27,28-tetra-n-
propoxycalix[4]arene (220)
2
3 28 7
6
5
4
8
O
13
10
9 27
12
11
O35
36
37
14
38
39
40
41
42
43
44
45
4647
48
49
51
52
53
Br
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
40 10.2 0.86 1.89 (39), 3.96 (38)
37 11.2 1.07 1.81 (36), 3.57 (35)
39 23.7 1.89 0.86 (40), 3.96 (38)
36 24.1 1.81 1.07 (37), 3.57 (35)
8,14 31.4 2.97, 4.31 5.53 (10/12),
6.88 and 6.97 (4/6)
38 77.0 3.96 0.86 (40), 1.89 (39)
35 77.4 3.57, 3.67 1.07 (37), 1.81 (36)
11 122.3 6.12 -
48 124.5 - 7.22, 7.32, 7.66 (49)
n.d. 127.0 7.42 7.45
n.d. 127.5 7.32 7.66
127.9
128.0 5.53, 5.65
128.2 10/12
128.3 5.53, 5.65
2.97 (8/14), 4.31 (8/14),
5.53 (10/12)
n.d. 128.5 7.47 7.32
n.d. 129.0 7.22 7.32
n.d. 130.6 7.45 2.97 (8/14), 4.31 (8/14),
440 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 130.7
n.d. 130.8
6.88
6.97
6.88, 6.97, 7.42
n.d. 131.1 7.34 7.47
n.d. 133.1
n.d. 133.15 7.32, 7.65 7.22, 7.32
n.d. 133.24 - n.d.
n.d. 133.3 - n.d.
6.12
n.d. 133.4 - 2.97 (8/14), 4.31 (8/14)
n.d. 135.0 - -
n.d. 135.7 - -
n.d. 136.97 - -
n.d. 137.00 - -
137.3 - n.d.
137.4 - 2.97 (8/14), 4.31 (8/14)
n.d. 140.6 - 7.31, 7.42, 7.45
n.d. 142.3 - 6.88 and 6.97 (4/6),
7.47 (43)
n.d. 143.7 - 7.22, 7.31, 7.66 (48)
27 155.5 -
2.97 (8/14), 3.57 (35),
4.31 (8/14), 5.53 (10/12),
6.12 (11)
28 157.7 -
2.97 (8/14), 3.96 (38),
4.31 (8/14), 6.88 and 6.97
(4/6)
Cross-peak tables 441
1.51 50,51-Dihydroxy-49,51-di-n-propoxycalix[4]ditriphenylenes
(217a and 217b)
2
4
3 52
19
18
5
20
2151
25
24
23
22
OOH56
57
58
17
1211
6
16
15
14
13
10
9
8
7
26
a
4
3 52
19
18
5
20
2151
25
24
23
22
262
OOH
1
46
45 49
48
47
O53
54
55
43
28
27
50
42
41
OH
44
56
57
58
17
1211
6
16
15
14
13
40
3534
29
33
32
31
30
10
9
8
7 39
38
37
36
b
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
55,58 10.9
58 10.96a
55,58 11.03
1.28 2.10, 4.06
54,57 23.6
57 23.7a
54,57 23.8
2.10 1.28, 4.06
29.0 5.87
29.2 4.82
5.69
31.6
2,20,
26,44
31.7 3.65, 4.47 6.63, 6.91, 8.32, 8.38
53,56 77.8
56 78.1 a+b
53,56 78.5
4.06 1.28, 2.10
122.4 8.38 - - 4,42
122.5 8.32 - -
n.d. 122.9 n.d.
3.66,
4.47 -
tripheny-
lene 123.2 8.58 - -
n.d. 123.6 n.d. - -
7.58
442 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 123.66
n.d. 123.68 n.d. - -
23b 123.74 5.87 - -
tripheny-
lene 124.3 8.24 - - -
47b 124.9 6.66
n.d. 125.3 n.d.
n.d. 125.36
n.d. 125.38
n.d. 125.40
n.d.
4.82 8.60
tripheny-
lene 126.0 7.59
6.67,
6.78
-
n.d. 126.6 n.d. - - 8.32
tripheny-
lene 127.4
tripheny-
lene 127.5
7.59 - -
22,24b 127.8 5.69 -
24a 128.0 6.63 - 5.87
22a 128.8 5.87
n.d. 128.9 -
46,48b 129.0 6.91
n.d. 129.1 -
n.d. 129.3 -
tripheny-
lene 129.5
tripheny-
lene 129.6
8.34
6.63,
6.68,
6.78,
6.91
8.56
n.d. 129.98 -
n.d. 130.01 - - 7.58
n.d. 130.78 -
3.66,
4.47,
4.82
- 8.35
Cross-peak tables 443
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
n.d. 130.79
n.d. 130.9 -
-
n.d. 131.3 - -
n.d. 131.45 - -
n.d. 131.48 - -
6.24
n.d. 132.4 - 6.63 -
n.d. 133.8 -
3.66,
4.47 5.88 -
n.d. 134.7 - 4.83 6.24 -
152.8 -
153.2 - 49,51
153.6 -
4.07, 5.69,
5.88, 6.63,
6.91
50,52 154.90 -
4.47, 4.83 3.65, 6.78,
6.68, 8.32,
8.38
444 Appendix
1.52 29,50,51,52-Tetra-n-propoxycalix[4]ditriphenylenes (221a and
221b)
2
4
3 52
19
18
5
20
2151
25
24
23
22
OO59
60
61
17
1211
6
16
15
14
13
10
9
8
7
62
63
64
26
a
4
3 52
19
18
5
20
2151
25
24
23
22
262
OO
1
46
45 49
48
47
O53
54
55
43
28
27
50
42
41
O
44
59
60
61
17
1211
6
16
15
14
13
40
3534
29
33
32
31
30
10
9
8
7 39
38
37
36
62
63
64
56
57
58
b
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
10.1 „4.26“, „4.43“
10.2 1.00
1.87-
2.24
11.0 1.18
11.2 1.26
55,58,
61,64
11.3 1.33
„3.80“
23.4 1.00,
„4.26“, „4.43“
23.5
1.87-2.24
(2.17)
23.8 1.18
23.9 1.26
54,57,
60,63
24.0
1.87-2.24
(2.04) 1.33
„3.80“
30.9 5.04, 5.28, 6.06, 8.36
31.0 4.53, 4.85, 4.87
31.4
2,20,
26,44
31.5
3.41, 3.47, 4.61, 4.64,
4.68 6.38, 8.42
76.5 3.74-3.84 („3.80“) 1.33, 1.87-2.24 53,56,
59,62 77.7
4.19-4.31 („4.26“),
4.41-4.53 („4.43“) 1.18, 1.25, 1.87-2.24
Cross-peak tables 445
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
78.0 4.51 1.00, 1.87-2.24
47b 122.8 6.27
„3.44
“,
„4.64
“
-
23a 122.88 5.91 -
triphenyle
ne 122.91 8.42 -
23b 123.0 5.57
-
tripheny-
lene 123.2 8.36
„3.44
“,
„4.64
“,
7.51-
7.70
-
n.d. 123.3 n.d. 8.42
n.d. 123.36 n.d. -
n.d. 123.38 n.d. -
n.d. 123.5 n.d. -
n.d. 123.6 n.d.
-
tripheny-
lene 125.49
8.58-
8.69 -
tripheny-
lene 125.52
7.51-7.70 (7.54)
-
22/24b 126.3 5.04 -
tripheny-
lene 126.4 7.51-7.70 (7.61)
4.53,
„4.86“,
8.67
5.04,
5.57
tripheny-
lene 126.54 8.58-8.69 (8.61, 8.67)
3.47, 8.32
446 Appendix
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
tripheny-
lene 126.56
24a 126.9 6.06 5.28
22a 127.2 5.28
6.06
tripheny-
lene 127.5 7.51-7.70 (7.67) -
46/48a 127.7 6.38
„4.64“,
„4.86“
6.38
n.d. 129.7 - 7.61, 8.67
tripheny-
lene 129.8 8.30-8.36 (8.32)
n.d. 129.9 - -
n.d. 130.1 - 7.54
n.d. 130.8 - 7.67, 8.33
n.d. 131.09 - -
n.d. 131.11 - -
n.d. 131.90 - „3.44“, 4.53, „4.64“,
„4.86“, 5.91, 8.36, 8.42
n.d. 131.93 -
n.d. 132.0 -
n.d. 132.5 - „3.44“, „4.64“, „4.86“,
6.27
n.d. 134.0 - -
n.d. 134.2 - -
n.d. 134.6 - 4.53, „4.86“, 5.57
n.d. 134.9 - 5.91
n.d. 136.7 - „3.44“, „4.64“
n.d. 136.8 -
154.3 - - 4.53,
„4.86“ 49,51a+b
154.7 - 5.28,
6.06
5.04 4.67,
6.38
Cross-peak tables 447
C atom δ [ppm] HMQC cross peaks
[ppm]
HMBC cross peaks
[ppm]
155.4 - „3.44“, 6.38
160.8 - „4.86
“, 8.42 50,52a+b
160.9 -
„3.44“, 3.49,
4.21, 4.53, „4.64“ 8.36
448 Appendix
1.53 Structure (157)
C-Atom δ
[ppm]
HMQC-Kreuzsignale
[ppm]
HMBC-Kreuzsignale
[ppm]
16.6 2.27 7.10
126.3 7.10 -
128.9 7.10 7.10
129.7 8.06 7.66
130.0 7.89 2.27
130.7 - 7.10
131.4 - -
131.9
132.0 7.66 7.66, 8.06, 7.89
148.3 - 2.27, 7.10
164.9 - 7.89, 8.06
172.5 - 7.89, 8.06
449
2 Crystal Structure Data
2.1 Transannular cyclization-product (cone) (60)
Table 1. Crystal data and structure refinement for C56H60O4.
Empirical formula C56H60O4 Formula weight 797.04 Temperature 110(2) K Wavelength 0.71073 A Crystal system, space group Monoclinic, P2(1)/c
Unit cell dimensions a = 20.5290(7) Å α = 90° b = 17.7566(6) Å β = 92.535(3)° c = 24.2824(8) Å γ = 90°
Volume 8842.9(5) Å 3
Z, Calculated density 8, 1.197 Mg/m3 Absorption coefficient 0.073 mm-1 F(000) 3424 Crystal size 0.420 x 0.217 x 0.165 mm θ range for data collection 2.47 to 25.00 deg. Limiting indices -24<=h<=24, -21<=k<=21, -28<=l<=28 Reflections collected / unique 61209 / 15535 [R(int) = 0.0963] Completeness to θ = 25.00 99.7 % Absorption correction Semi-empirical from equivalents Max. and min. transmission 0.998 and 0.966 Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 15535 / 0 / 1089 Goodness-of-fit on F2 0.813 Final R indices [I>2σ(I)] R1 = 0.0438, wR2 = 0.0831 [6248 refs] R indices (all data) R1 = 0.1387, wR2 = 0.1085 Largest diff. peak and hole 0.580 and -0.370 e.Å-3
450 Appendix
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C56H60O4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(11) 5005(1) 1782(1) 1098(1) 29(1) O(12) 5407(1) 3652(1) 1426(1) 35(1) O(13) 4829(1) 2370(1) 3230(1) 35(1) O(14) 3790(1) 624(1) 1686(1) 31(1) C(101) 5358(1) 647(2) 683(1) 27(1) C(102) 4840(1) 224(2) 985(1) 31(1) C(103) 4935(1) 361(1) 1603(1) 25(1) C(104) 5557(1) 350(1) 1852(1) 23(1) C(105) 5684(1) 577(1) 2390(1) 22(1) C(106) 5159(1) 832(1) 2686(1) 25(1) C(107) 4526(1) 841(1) 2461(1) 23(1) C(108) 3990(1) 1227(2) 2766(1) 30(1) C(109) 3962(1) 2042(2) 2580(1) 29(1) C(110) 3524(1) 2279(2) 2159(1) 34(1) C(111) 3575(2) 2988(2) 1926(1) 33(1) C(112) 4095(2) 3438(2) 2072(1) 35(1) C(113) 4551(2) 3229(2) 2488(1) 30(1) C(114) 5199(1) 3636(2) 2573(1) 33(1) C(115) 5716(1) 3146(2) 2312(1) 27(1) C(116) 6053(1) 2610(2) 2625(1) 26(1) C(117) 6420(1) 2053(2) 2388(1) 26(1) C(118) 6469(1) 2066(2) 1815(1) 27(1) C(119) 6156(1) 2609(2) 1487(1) 28(1) C(120) 6171(2) 2567(2) 862(1) 34(1) C(121) 6013(2) 1789(2) 639(1) 32(1) C(122) 6441(2) 1406(2) 307(1) 35(1) C(123) 6324(2) 671(2) 150(1) 38(1) C(124) 5796(2) 285(2) 352(1) 35(1) C(125) 5451(1) 1415(2) 788(1) 27(1) C(126) 5781(1) 3145(2) 1746(1) 28(1) C(127) 4431(1) 2555(2) 2760(1) 28(1) C(128) 4420(1) 591(1) 1922(1) 25(1) C(129) 6698(1) 1398(1) 2717(1) 24(1) C(130) 6571(1) 1311(1) 3335(1) 24(1) C(131) 6477(1) 440(1) 3249(1) 24(1) C(132) 6377(1) 592(1) 2619(1) 24(1) C(133) 7045(1) 1598(2) 3778(1) 29(1) C(134) 7526(1) 2121(2) 3669(1) 38(1) C(135) 7945(2) 2388(2) 4091(1) 44(1) C(136) 7894(2) 2133(2) 4620(1) 50(1) C(137) 7421(2) 1617(2) 4737(1) 45(1) C(138) 6996(2) 1359(2) 4323(1) 38(1) C(139) 7037(1) -64(1) 3420(1) 23(1) C(140) 7018(1) -454(2) 3914(1) 27(1) C(141) 7507(1) -948(2) 4082(1) 32(1) C(142) 8029(1) -1061(2) 3754(1) 32(1) C(143) 8061(1) -676(2) 3263(1) 29(1) C(144) 7569(1) -178(2) 3101(1) 26(1)
Crystal Structure Data 451
C(145) 4576(1) 2289(2) 792(1) 34(1) C(146) 3994(2) 1901(2) 526(1) 45(1) C(147) 3539(2) 2469(2) 236(1) 61(1) C(148) 5749(2) 4314(2) 1266(1) 39(1) C(149) 5247(2) 4822(2) 973(2) 73(1) C(150) 4800(2) 4482(2) 576(2) 77(1) C(151) 4635(2) 2783(2) 3712(1) 46(1) C(152) 5176(2) 2699(2) 4169(1) 58(1) C(153) 5217(2) 1910(2) 4365(1) 65(1) C(154) 3471(1) -95(2) 1654(1) 40(1) C(155) 2790(2) 17(2) 1421(2) 55(1) C(156) 2436(2) -727(2) 1346(2) 81(1) O(21) 9854(1) 1620(1) 1044(1) 31(1) O(22) 10098(1) -251(1) 1346(1) 31(1) O(23) 9602(1) 1004(1) 3182(1) 37(1) O(24) 8744(1) 2989(1) 1717(1) 37(1) C(201) 10302(1) 2775(2) 698(1) 29(1) C(202) 9826(2) 3238(2) 1017(1) 33(1) C(203) 9905(1) 3048(1) 1628(1) 26(1) C(204) 10523(1) 2958(1) 1870(1) 26(1) C(205) 10635(1) 2702(1) 2406(1) 24(1) C(206) 10089(1) 2508(1) 2697(1) 25(1) C(207) 9458(1) 2590(2) 2473(1) 27(1) C(208) 8879(1) 2262(2) 2760(1) 35(1) C(209) 8779(1) 1468(2) 2539(1) 35(1) C(210) 8329(1) 1312(2) 2104(1) 40(1) C(211) 8321(2) 616(2) 1845(1) 41(1) C(212) 8801(2) 94(2) 1984(1) 40(1) C(213) 9262(2) 236(2) 2410(1) 35(1) C(214) 9870(2) -249(2) 2496(1) 36(1) C(215) 10433(1) 180(2) 2248(1) 28(1) C(216) 10818(1) 661(2) 2575(1) 28(1) C(217) 11244(1) 1169(2) 2350(1) 24(1) C(218) 11292(1) 1175(2) 1779(1) 28(1) C(219) 10927(1) 693(2) 1437(1) 26(1) C(220) 10945(2) 768(2) 814(1) 34(1) C(221) 10873(2) 1573(2) 627(1) 29(1) C(222) 11351(2) 1937(2) 336(1) 36(1) C(223) 11293(2) 2687(2) 200(1) 38(1) C(224) 10785(2) 3104(2) 393(1) 33(1) C(225) 10331(1) 1993(2) 770(1) 28(1) C(226) 10499(1) 200(2) 1684(1) 26(1) C(227) 9204(1) 896(2) 2707(1) 32(1) C(228) 9376(1) 2887(2) 1942(1) 28(1) C(229) 11587(1) 1771(1) 2693(1) 26(1) C(230) 11493(1) 1820(1) 3319(1) 26(1) C(231) 11446(1) 2705(1) 3264(1) 24(1) C(232) 11323(1) 2607(1) 2627(1) 25(1) C(233) 11961(1) 1424(2) 3715(1) 27(1) C(234) 12635(2) 1520(2) 3706(1) 33(1) C(235) 13049(2) 1129(2) 4071(1) 40(1) C(236) 12802(2) 638(2) 4448(1) 46(1) C(237) 12140(2) 536(2) 4466(1) 45(1) C(238) 11720(2) 929(2) 4103(1) 38(1) C(239) 12031(1) 3175(1) 3450(1) 24(1) C(240) 12050(1) 3457(2) 3985(1) 35(1) C(241) 12565(2) 3902(2) 4177(1) 46(1) C(242) 13071(2) 4068(2) 3842(1) 42(1) C(243) 13059(1) 3787(2) 3316(1) 34(1) C(244) 12543(1) 3347(2) 3120(1) 30(1) C(245) 9208(1) 1605(2) 774(1) 38(1)
452 Appendix
C(246) 9070(2) 853(2) 515(1) 43(1) C(247) 8379(2) 825(2) 256(1) 47(1) C(248) 10395(1) -951(2) 1205(1) 32(1) C(249) 9930(1) -1366(2) 821(1) 29(1) C(250) 10179(2) -2146(2) 693(1) 44(1) C(251) 9260(2) 773(2) 3673(1) 65(1) C(252) 9686(2) 733(2) 4151(2) 70(1) C(253) 9312(2) 562(2) 4657(1) 58(1) C(254) 8503(2) 3738(2) 1834(2) 60(1) C(255) 7787(2) 3763(2) 1762(2) 78(1) C(256) 7511(2) 4507(2) 1933(2) 82(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C56H60O4. _____________________________________________________________ O(11)-C(125) 1.377(3) O(11)-C(145) 1.441(3) O(12)-C(126) 1.398(3) O(12)-C(148) 1.432(3) O(13)-C(127) 1.412(3) O(13)-C(151) 1.451(3) O(14)-C(128) 1.393(3) O(14)-C(154) 1.434(3) C(101)-C(124) 1.390(4) C(101)-C(125) 1.399(4) C(101)-C(102) 1.517(4) C(102)-C(103) 1.523(3) C(103)-C(104) 1.390(3) C(103)-C(128) 1.398(4) C(104)-C(105) 1.381(3) C(105)-C(106) 1.397(4) C(105)-C(132) 1.503(3) C(106)-C(107) 1.387(3) C(107)-C(128) 1.389(3) C(107)-C(108) 1.517(4) C(108)-C(109) 1.517(4) C(109)-C(127) 1.383(4) C(109)-C(110) 1.396(4) C(110)-C(111) 1.386(4) C(111)-C(112) 1.367(4) C(112)-C(113) 1.396(4) C(113)-C(127) 1.394(4) C(113)-C(114) 1.521(4) C(114)-C(115) 1.531(4) C(115)-C(116) 1.384(3) C(115)-C(126) 1.386(4) C(116)-C(117) 1.385(4) C(117)-C(118) 1.400(3) C(117)-C(129) 1.508(3) C(118)-C(119) 1.390(3) C(119)-C(126) 1.392(4) C(119)-C(120) 1.521(4) C(120)-C(121) 1.513(4) C(121)-C(125) 1.394(4)
Crystal Structure Data 453
C(121)-C(122) 1.396(4) C(122)-C(123) 1.377(4) C(123)-C(124) 1.391(4) C(129)-C(130) 1.543(3) C(129)-C(132) 1.590(3) C(130)-C(133) 1.506(4) C(130)-C(131) 1.571(3) C(131)-C(139) 1.501(3) C(131)-C(132) 1.558(3) C(133)-C(134) 1.389(4) C(133)-C(138) 1.398(4) C(134)-C(135) 1.391(4) C(135)-C(136) 1.370(4) C(136)-C(137) 1.374(4) C(137)-C(138) 1.381(4) C(139)-C(144) 1.381(4) C(139)-C(140) 1.388(3) C(140)-C(141) 1.381(3) C(141)-C(142) 1.378(4) C(142)-C(143) 1.379(4) C(143)-C(144) 1.386(3) C(145)-C(146) 1.502(4) C(146)-C(147) 1.525(4) C(148)-C(149) 1.523(4) C(149)-C(150) 1.434(4) C(151)-C(152) 1.543(4) C(152)-C(153) 1.482(4) C(154)-C(155) 1.498(4) C(155)-C(156) 1.515(4) O(21)-C(225) 1.378(3) O(21)-C(245) 1.453(3) O(22)-C(226) 1.390(3) O(22)-C(248) 1.433(3) O(23)-C(227) 1.397(3) O(23)-C(251) 1.469(4) O(24)-C(228) 1.399(3) O(24)-C(254) 1.451(3) C(201)-C(224) 1.392(4) C(201)-C(225) 1.401(4) C(201)-C(202) 1.515(4) C(202)-C(203) 1.525(3) C(203)-C(204) 1.382(4) C(203)-C(228) 1.384(4) C(204)-C(205) 1.389(3) C(205)-C(206) 1.394(4) C(205)-C(232) 1.498(4) C(206)-C(207) 1.392(4) C(207)-C(228) 1.394(4) C(207)-C(208) 1.519(4) C(208)-C(209) 1.519(4) C(209)-C(227) 1.390(4) C(209)-C(210) 1.399(4) C(210)-C(211) 1.387(4) C(211)-C(212) 1.383(4) C(212)-C(213) 1.394(4) C(213)-C(227) 1.382(4) C(213)-C(214) 1.525(4) C(214)-C(215) 1.530(4) C(215)-C(226) 1.382(4) C(215)-C(216) 1.388(4) C(216)-C(217) 1.386(4)
454 Appendix
C(217)-C(218) 1.393(3) C(217)-C(229) 1.510(3) C(218)-C(219) 1.388(3) C(219)-C(226) 1.395(4) C(219)-C(220) 1.521(3) C(220)-C(221) 1.506(4) C(221)-C(222) 1.393(4) C(221)-C(225) 1.395(4) C(222)-C(223) 1.376(4) C(223)-C(224) 1.378(4) C(229)-C(230) 1.543(3) C(229)-C(232) 1.586(3) C(230)-C(233) 1.503(4) C(230)-C(231) 1.579(3) C(231)-C(239) 1.515(3) C(231)-C(232) 1.566(3) C(233)-C(234) 1.395(4) C(233)-C(238) 1.395(4) C(234)-C(235) 1.386(4) C(235)-C(236) 1.377(4) C(236)-C(237) 1.374(4) C(237)-C(238) 1.392(4) C(239)-C(244) 1.384(4) C(239)-C(240) 1.392(3) C(240)-C(241) 1.385(4) C(241)-C(242) 1.379(4) C(242)-C(243) 1.370(4) C(243)-C(244) 1.383(4) C(245)-C(246) 1.497(4) C(246)-C(247) 1.528(4) C(248)-C(249) 1.497(3) C(249)-C(250) 1.513(4) C(251)-C(252) 1.424(4) C(252)-C(253) 1.508(4) C(254)-C(255) 1.473(4) C(255)-C(256) 1.503(5) C(125)-O(11)-C(145) 114.8(2) C(126)-O(12)-C(148) 114.5(2) C(127)-O(13)-C(151) 111.4(2) C(128)-O(14)-C(154) 113.5(2) C(124)-C(101)-C(125) 118.0(3) C(124)-C(101)-C(102) 122.5(3) C(125)-C(101)-C(102) 119.1(3) C(101)-C(102)-C(103) 109.6(2) C(104)-C(103)-C(128) 117.7(2) C(104)-C(103)-C(102) 120.1(3) C(128)-C(103)-C(102) 121.7(3) C(105)-C(104)-C(103) 122.6(3) C(104)-C(105)-C(106) 117.6(2) C(104)-C(105)-C(132) 119.4(2) C(106)-C(105)-C(132) 122.9(2) C(107)-C(106)-C(105) 122.1(3) C(106)-C(107)-C(128) 118.2(3) C(106)-C(107)-C(108) 120.0(2) C(128)-C(107)-C(108) 121.2(2) C(109)-C(108)-C(107) 107.6(2) C(127)-C(109)-C(110) 116.7(3) C(127)-C(109)-C(108) 121.2(2) C(110)-C(109)-C(108) 121.4(3) C(111)-C(110)-C(109) 121.0(3)
Crystal Structure Data 455
C(112)-C(111)-C(110) 119.8(3) C(111)-C(112)-C(113) 121.5(3) C(127)-C(113)-C(112) 116.4(3) C(127)-C(113)-C(114) 121.1(3) C(112)-C(113)-C(114) 121.7(3) C(113)-C(114)-C(115) 107.0(2) C(116)-C(115)-C(126) 118.4(3) C(116)-C(115)-C(114) 120.2(3) C(126)-C(115)-C(114) 120.6(3) C(115)-C(116)-C(117) 122.1(3) C(116)-C(117)-C(118) 117.8(3) C(116)-C(117)-C(129) 122.1(2) C(118)-C(117)-C(129) 119.8(2) C(119)-C(118)-C(117) 122.0(3) C(118)-C(119)-C(126) 117.7(3) C(118)-C(119)-C(120) 120.6(3) C(126)-C(119)-C(120) 121.4(3) C(121)-C(120)-C(119) 112.8(2) C(125)-C(121)-C(122) 117.8(3) C(125)-C(121)-C(120) 120.6(3) C(122)-C(121)-C(120) 121.5(3) C(123)-C(122)-C(121) 121.0(3) C(122)-C(123)-C(124) 119.9(3) C(101)-C(124)-C(123) 120.7(3) O(11)-C(125)-C(121) 119.6(3) O(11)-C(125)-C(101) 118.2(3) C(121)-C(125)-C(101) 121.8(3) C(115)-C(126)-C(119) 122.0(3) C(115)-C(126)-O(12) 118.4(3) C(119)-C(126)-O(12) 119.3(2) C(109)-C(127)-C(113) 123.4(3) C(109)-C(127)-O(13) 118.2(2) C(113)-C(127)-O(13) 118.4(3) C(107)-C(128)-O(14) 118.6(2) C(107)-C(128)-C(103) 121.6(3) O(14)-C(128)-C(103) 119.6(2) C(117)-C(129)-C(130) 121.1(2) C(117)-C(129)-C(132) 118.1(2) C(130)-C(129)-C(132) 88.22(19) C(133)-C(130)-C(129) 121.9(2) C(133)-C(130)-C(131) 120.1(2) C(129)-C(130)-C(131) 89.62(19) C(139)-C(131)-C(132) 116.3(2) C(139)-C(131)-C(130) 117.5(2) C(132)-C(131)-C(130) 88.37(19) C(105)-C(132)-C(131) 116.2(2) C(105)-C(132)-C(129) 116.8(2) C(131)-C(132)-C(129) 88.41(18) C(134)-C(133)-C(138) 117.7(3) C(134)-C(133)-C(130) 122.2(3) C(138)-C(133)-C(130) 120.1(3) C(133)-C(134)-C(135) 120.6(3) C(136)-C(135)-C(134) 120.6(3) C(135)-C(136)-C(137) 119.9(3) C(136)-C(137)-C(138) 120.0(3) C(137)-C(138)-C(133) 121.4(3) C(144)-C(139)-C(140) 117.7(2) C(144)-C(139)-C(131) 123.1(2) C(140)-C(139)-C(131) 119.2(2) C(141)-C(140)-C(139) 121.7(3) C(142)-C(141)-C(140) 119.7(3)
456 Appendix
C(141)-C(142)-C(143) 119.6(3) C(142)-C(143)-C(144) 120.1(3) C(139)-C(144)-C(143) 121.2(3) O(11)-C(145)-C(146) 113.0(2) C(145)-C(146)-C(147) 110.8(3) O(12)-C(148)-C(149) 106.4(2) C(150)-C(149)-C(148) 117.7(3) O(13)-C(151)-C(152) 108.5(2) C(153)-C(152)-C(151) 110.5(3) O(14)-C(154)-C(155) 108.6(2) C(154)-C(155)-C(156) 111.4(3) C(225)-O(21)-C(245) 116.4(2) C(226)-O(22)-C(248) 113.2(2) C(227)-O(23)-C(251) 110.4(2) C(228)-O(24)-C(254) 111.1(2) C(224)-C(201)-C(225) 117.0(3) C(224)-C(201)-C(202) 122.3(3) C(225)-C(201)-C(202) 119.9(3) C(201)-C(202)-C(203) 109.5(2) C(204)-C(203)-C(228) 118.0(3) C(204)-C(203)-C(202) 119.7(3) C(228)-C(203)-C(202) 122.0(3) C(203)-C(204)-C(205) 123.1(3) C(204)-C(205)-C(206) 116.9(3) C(204)-C(205)-C(232) 119.2(3) C(206)-C(205)-C(232) 123.8(2) C(207)-C(206)-C(205) 122.1(3) C(206)-C(207)-C(228) 118.2(3) C(206)-C(207)-C(208) 120.9(2) C(228)-C(207)-C(208) 120.3(3) C(209)-C(208)-C(207) 106.9(2) C(227)-C(209)-C(210) 117.5(3) C(227)-C(209)-C(208) 120.1(3) C(210)-C(209)-C(208) 121.7(3) C(211)-C(210)-C(209) 120.9(3) C(212)-C(211)-C(210) 119.4(3) C(211)-C(212)-C(213) 120.9(3) C(227)-C(213)-C(212) 118.0(3) C(227)-C(213)-C(214) 119.7(3) C(212)-C(213)-C(214) 121.6(3) C(213)-C(214)-C(215) 107.1(2) C(226)-C(215)-C(216) 118.3(3) C(226)-C(215)-C(214) 120.7(3) C(216)-C(215)-C(214) 120.1(3) C(217)-C(216)-C(215) 121.8(3) C(216)-C(217)-C(218) 118.1(3) C(216)-C(217)-C(229) 122.0(2) C(218)-C(217)-C(229) 119.4(2) C(219)-C(218)-C(217) 122.0(3) C(218)-C(219)-C(226) 117.7(3) C(218)-C(219)-C(220) 120.3(3) C(226)-C(219)-C(220) 121.7(2) C(221)-C(220)-C(219) 112.1(2) C(222)-C(221)-C(225) 117.8(3) C(222)-C(221)-C(220) 122.0(3) C(225)-C(221)-C(220) 120.1(3) C(223)-C(222)-C(221) 121.0(3) C(222)-C(223)-C(224) 119.8(3) C(223)-C(224)-C(201) 121.5(3) O(21)-C(225)-C(221) 117.0(3)
Crystal Structure Data 457
O(21)-C(225)-C(201) 120.6(3) C(221)-C(225)-C(201) 121.9(3) C(215)-C(226)-O(22) 119.2(2) C(215)-C(226)-C(219) 122.1(3) O(22)-C(226)-C(219) 118.5(2) C(213)-C(227)-C(209) 122.2(3) C(213)-C(227)-O(23) 119.1(3) C(209)-C(227)-O(23) 118.6(3) C(203)-C(228)-C(207) 121.4(3) C(203)-C(228)-O(24) 119.7(2) C(207)-C(228)-O(24) 118.8(3) C(217)-C(229)-C(230) 120.6(2) C(217)-C(229)-C(232) 117.3(2) C(230)-C(229)-C(232) 89.35(19) C(233)-C(230)-C(229) 120.0(2) C(233)-C(230)-C(231) 123.6(2) C(229)-C(230)-C(231) 89.07(19) C(239)-C(231)-C(232) 116.5(2) C(239)-C(231)-C(230) 118.6(2) C(232)-C(231)-C(230) 88.79(18) C(205)-C(232)-C(231) 116.8(2) C(205)-C(232)-C(229) 117.0(2) C(231)-C(232)-C(229) 88.02(18) C(234)-C(233)-C(238) 118.0(3) C(234)-C(233)-C(230) 122.6(3) C(238)-C(233)-C(230) 119.4(3) C(235)-C(234)-C(233) 120.5(3) C(236)-C(235)-C(234) 120.7(3) C(237)-C(236)-C(235) 119.8(3) C(236)-C(237)-C(238) 120.0(3) C(237)-C(238)-C(233) 121.0(3) C(244)-C(239)-C(240) 118.2(3) C(244)-C(239)-C(231) 124.2(2) C(240)-C(239)-C(231) 117.6(3) C(241)-C(240)-C(239) 120.5(3) C(242)-C(241)-C(240) 120.5(3) C(243)-C(242)-C(241) 119.2(3) C(242)-C(243)-C(244) 120.7(3) C(243)-C(244)-C(239) 120.9(3) O(21)-C(245)-C(246) 111.0(2) C(245)-C(246)-C(247) 110.9(3) O(22)-C(248)-C(249) 108.1(2) C(248)-C(249)-C(250) 111.6(2) C(252)-C(251)-O(23) 112.2(3) C(251)-C(252)-C(253) 110.9(3) O(24)-C(254)-C(255) 110.6(3) C(254)-C(255)-C(256) 112.3(3) _____________________________________________________________
458 Appendix
Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C56H60O4. The anisotropic displacement factor exponent takes the form: -2 pi2 [h2 a*2 U11 + ... + 2 h k a
* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(11) 32(1) 29(1) 26(1) 1(1) 4(1) 7(1) O(12) 41(1) 28(1) 34(1) 12(1) -5(1) -3(1) O(13) 40(1) 38(1) 27(1) 0(1) 1(1) 9(1) O(14) 23(1) 31(1) 37(1) 0(1) -5(1) -1(1) C(101) 26(2) 35(2) 19(2) 0(1) -8(1) 1(2) C(102) 36(2) 28(2) 29(2) -2(1) -5(1) 5(2) C(103) 28(2) 19(2) 27(2) -1(1) -1(1) 0(1) C(104) 24(2) 20(2) 25(2) -1(1) 5(1) 1(1) C(105) 21(2) 21(2) 23(2) 2(1) -2(1) 1(1) C(106) 30(2) 24(2) 21(2) 3(1) 0(1) -4(1) C(107) 22(2) 25(2) 24(2) 3(1) 2(1) 0(1) C(108) 24(2) 35(2) 30(2) 6(1) 2(1) -3(1) C(109) 26(2) 32(2) 29(2) -1(1) 5(1) 5(2) C(110) 31(2) 39(2) 34(2) -4(2) 4(2) 4(2) C(111) 35(2) 38(2) 26(2) 2(2) -2(1) 12(2) C(112) 41(2) 31(2) 33(2) 3(2) 3(2) 11(2) C(113) 39(2) 28(2) 25(2) -2(1) 8(2) 8(2) C(114) 43(2) 23(2) 32(2) 0(1) -4(2) 3(2) C(115) 30(2) 20(2) 30(2) -1(1) -2(1) -1(1) C(116) 29(2) 23(2) 24(2) -2(1) -1(1) 0(1) C(117) 22(2) 27(2) 28(2) 1(1) -3(1) -2(1) C(118) 20(2) 31(2) 31(2) -1(1) 8(1) -2(1) C(119) 31(2) 28(2) 24(2) 4(1) 0(1) -7(2) C(120) 35(2) 33(2) 33(2) 6(2) 6(2) -6(2) C(121) 38(2) 38(2) 19(2) 2(1) 4(1) -1(2) C(122) 35(2) 45(2) 24(2) 2(2) 2(1) -2(2) C(123) 32(2) 53(2) 29(2) -6(2) 4(2) 10(2) C(124) 39(2) 38(2) 26(2) -8(2) -5(2) 9(2) C(125) 32(2) 32(2) 16(2) -1(1) 1(1) 9(2) C(126) 33(2) 20(2) 30(2) 7(1) -5(2) -4(2) C(127) 29(2) 34(2) 20(2) 0(1) 0(1) 11(2) C(128) 25(2) 18(2) 33(2) 4(1) -7(1) 0(1) C(129) 22(2) 28(2) 23(2) 1(1) 3(1) -1(1) C(130) 23(2) 28(2) 23(2) -1(1) 2(1) 5(1) C(131) 21(2) 24(2) 27(2) 0(1) 2(1) 0(1) C(132) 25(2) 23(2) 23(2) -2(1) 2(1) 4(1) C(133) 29(2) 28(2) 30(2) -7(1) -1(1) 8(2) C(134) 31(2) 48(2) 34(2) -3(2) -2(2) -2(2) C(135) 32(2) 50(2) 49(2) -11(2) -2(2) -6(2) C(136) 51(2) 55(2) 42(2) -20(2) -13(2) 10(2) C(137) 61(3) 45(2) 29(2) -9(2) -7(2) 8(2) C(138) 48(2) 38(2) 29(2) -4(2) 0(2) -2(2) C(139) 24(2) 23(2) 22(2) 1(1) -1(1) 0(1) C(140) 22(2) 32(2) 28(2) -1(1) 4(1) 5(1) C(141) 36(2) 32(2) 27(2) 3(1) -4(2) 2(2) C(142) 28(2) 34(2) 33(2) 3(2) -4(2) 7(2) C(143) 23(2) 33(2) 30(2) -1(1) 3(1) 2(2)
Crystal Structure Data 459
C(144) 29(2) 25(2) 23(2) 4(1) 2(1) 0(1) C(145) 38(2) 34(2) 30(2) -1(1) 4(2) 8(2) C(146) 45(2) 42(2) 48(2) 2(2) -5(2) 4(2) C(147) 50(2) 63(3) 66(3) 3(2) -15(2) 15(2) C(148) 48(2) 25(2) 44(2) 12(2) -1(2) -7(2) C(149) 95(3) 48(3) 73(3) 33(2) -26(3) -19(2) C(150) 66(3) 90(3) 73(3) 46(2) -5(2) -1(2) C(151) 54(2) 63(2) 21(2) -2(2) 4(2) 20(2) C(152) 93(3) 51(2) 32(2) -2(2) 6(2) 13(2) C(153) 73(3) 80(3) 43(2) -8(2) 10(2) 3(2) C(154) 30(2) 33(2) 56(2) -1(2) -6(2) -7(2) C(155) 30(2) 50(2) 85(3) -2(2) -14(2) -7(2) C(156) 44(2) 73(3) 125(4) -3(3) -24(2) -23(2) O(21) 30(1) 35(1) 30(1) 6(1) -1(1) -7(1) O(22) 35(1) 24(1) 34(1) -6(1) -6(1) -1(1) O(23) 42(1) 41(1) 28(1) 2(1) 1(1) -11(1) O(24) 28(1) 41(1) 41(1) -2(1) -3(1) 5(1) C(201) 39(2) 28(2) 21(2) 1(1) -5(1) -9(2) C(202) 41(2) 26(2) 31(2) 5(1) -4(2) -4(2) C(203) 32(2) 16(2) 28(2) 0(1) -4(2) -1(1) C(204) 33(2) 23(2) 23(2) -1(1) 5(1) -3(1) C(205) 27(2) 16(2) 30(2) -4(1) 2(1) -1(1) C(206) 29(2) 25(2) 21(2) -2(1) 3(1) 0(1) C(207) 26(2) 24(2) 30(2) -2(1) 4(1) -2(1) C(208) 29(2) 44(2) 32(2) -3(2) 4(2) 2(2) C(209) 27(2) 49(2) 28(2) -1(2) 9(2) -13(2) C(210) 28(2) 59(2) 34(2) 6(2) 10(2) -9(2) C(211) 38(2) 60(2) 27(2) -6(2) 4(2) -21(2) C(212) 43(2) 47(2) 30(2) -6(2) 10(2) -18(2) C(213) 40(2) 38(2) 28(2) 2(2) 7(2) -12(2) C(214) 52(2) 27(2) 29(2) -1(1) 0(2) -13(2) C(215) 36(2) 20(2) 28(2) 1(1) 0(1) 3(2) C(216) 37(2) 24(2) 22(2) 0(1) -1(1) 3(2) C(217) 20(2) 19(2) 33(2) -1(1) 0(1) 4(1) C(218) 28(2) 28(2) 29(2) -1(1) 5(1) 5(1) C(219) 31(2) 25(2) 22(2) -7(1) -2(1) 4(2) C(220) 41(2) 37(2) 24(2) -6(1) 0(1) -1(2) C(221) 37(2) 29(2) 22(2) -3(1) -1(1) -9(2) C(222) 40(2) 43(2) 25(2) -4(2) 3(2) -7(2) C(223) 42(2) 51(2) 22(2) 0(2) 1(2) -19(2) C(224) 41(2) 33(2) 24(2) 4(1) -8(2) -16(2) C(225) 28(2) 32(2) 25(2) -1(1) -1(1) -6(2) C(226) 29(2) 20(2) 28(2) -4(1) -4(1) 0(1) C(227) 30(2) 39(2) 26(2) 2(2) -1(1) -12(2) C(228) 25(2) 24(2) 33(2) -3(1) -4(2) 3(1) C(229) 24(2) 26(2) 27(2) -3(1) 3(1) -1(1) C(230) 27(2) 25(2) 26(2) -3(1) 3(1) -4(1) C(231) 20(2) 28(2) 24(2) -4(1) 4(1) 0(1) C(232) 28(2) 25(2) 22(2) -2(1) 2(1) -4(1) C(233) 33(2) 27(2) 21(2) -8(1) 2(1) 3(2) C(234) 38(2) 35(2) 26(2) 1(1) 0(2) 1(2) C(235) 37(2) 48(2) 35(2) 0(2) -2(2) 5(2) C(236) 48(2) 59(2) 29(2) 3(2) -7(2) 13(2) C(237) 55(3) 48(2) 32(2) 12(2) 3(2) 0(2) C(238) 42(2) 47(2) 26(2) 1(2) 6(2) -3(2) C(239) 26(2) 21(2) 24(2) 2(1) -2(1) 1(1) C(240) 30(2) 49(2) 25(2) -5(2) 3(1) -7(2) C(241) 44(2) 60(2) 32(2) -15(2) 0(2) -15(2) C(242) 33(2) 52(2) 40(2) -12(2) -2(2) -18(2) C(243) 22(2) 40(2) 41(2) 4(2) 4(2) -7(2) C(244) 27(2) 33(2) 28(2) -6(1) 3(1) -2(2)
460 Appendix
C(245) 36(2) 39(2) 38(2) 3(2) 4(2) -4(2) C(246) 48(2) 42(2) 39(2) -3(2) 3(2) -5(2) C(247) 42(2) 50(2) 47(2) -6(2) -5(2) -7(2) C(248) 36(2) 28(2) 31(2) -3(1) -2(2) 1(2) C(249) 32(2) 30(2) 25(2) -1(1) 1(1) -7(2) C(250) 64(2) 33(2) 35(2) -9(2) -8(2) -5(2) C(251) 75(3) 84(3) 36(2) 12(2) -10(2) -46(2) C(252) 90(3) 53(3) 65(3) 10(2) -3(2) -5(2) C(253) 100(3) 47(2) 28(2) 10(2) 12(2) 2(2) C(254) 44(2) 46(2) 89(3) -2(2) -9(2) 15(2) C(255) 50(3) 56(3) 127(4) -11(2) -15(3) 18(2) C(256) 59(3) 86(3) 100(3) 9(3) -2(2) 22(2) ______________________________________________________________________ Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (A2 x 103) for C56H60O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(10A) 4871 -321 907 38 H(10B) 4401 399 856 38 H(104) 5910 179 1644 28 H(106) 5238 1005 3053 30 H(10C) 3567 976 2681 36 H(10D) 4085 1199 3169 36 H(110) 3186 1949 2030 41 H(111) 3250 3161 1666 39 H(112) 4147 3904 1887 42 H(11A) 5306 3707 2971 39 H(11B) 5178 4137 2394 39 H(116) 6030 2624 3015 31 H(118) 6723 1691 1645 33 H(12A) 5852 2931 699 40 H(12B) 6609 2717 747 40 H(122) 6819 1655 188 42 H(123) 6603 429 -97 46 H(124) 5735 -232 263 41 H(129) 7177 1363 2663 29 H(130) 6135 1534 3401 29 H(131) 6064 263 3409 29 H(132) 6662 259 2401 29 H(134) 7571 2297 3303 45 H(135) 8268 2750 4012 53 H(136) 8186 2312 4905 59 H(137) 7386 1438 5103 54 H(138) 6664 1012 4410 46 H(140) 6660 -379 4143 33 H(141) 7484 -1208 4423 38 H(142) 8366 -1403 3866 38 H(143) 8419 -752 3036 35 H(144) 7598 90 2764 31 H(14A) 4824 2540 503 40
Crystal Structure Data 461
H(14B) 4425 2684 1044 40 H(14C) 3755 1628 810 54 H(14D) 4140 1528 255 54 H(14E) 3403 2846 502 91 H(14F) 3154 2208 78 91 H(14G) 3768 2719 -59 91 H(14H) 6099 4181 1016 47 H(14I) 5948 4571 1594 47 H(14J) 4989 5067 1257 87 H(14K) 5485 5225 784 87 H(15A) 5044 4251 282 115 H(15B) 4506 4869 418 115 H(15C) 4544 4096 757 115 H(15D) 4219 2580 3840 55 H(15E) 4570 3321 3618 55 H(15F) 5600 2852 4024 70 H(15G) 5082 3035 4481 70 H(15H) 4799 1761 4512 98 H(15I) 5562 1867 4655 98 H(15J) 5317 1579 4056 98 H(15K) 3461 -322 2025 48 H(15L) 3711 -438 1414 48 H(15M) 2804 276 1060 66 H(15N) 2547 343 1672 66 H(15O) 2676 -1051 1100 122 H(15P) 1996 -636 1186 122 H(15Q) 2405 -974 1705 122 H(20A) 9374 3127 881 39 H(20B) 9910 3781 960 39 H(204) 10888 3078 1659 31 H(206) 10150 2313 3060 30 H(20C) 8969 2251 3163 42 H(20D) 8484 2571 2680 42 H(210) 8026 1688 1984 48 H(211) 7988 498 1574 50 H(212) 8817 -366 1786 47 H(21A) 9807 -741 2310 44 H(21B) 9964 -338 2894 44 H(216) 10789 640 2964 33 H(218) 11584 1519 1619 34 H(22A) 11364 566 691 41 H(22B) 10589 463 639 41 H(222) 11723 1663 230 43 H(223) 11602 2916 -27 46 H(224) 10765 3628 316 39 H(229) 12063 1762 2624 31 H(230) 11046 1628 3388 31 H(231) 11044 2895 3436 28 H(232) 11629 2925 2419 30 H(234) 12812 1857 3447 40 H(235) 13506 1201 4061 48 H(236) 13089 370 4695 55 H(237) 11969 198 4726 54 H(238) 11263 859 4120 46 H(240) 11706 3343 4221 42 H(241) 12570 4095 4542 55 H(242) 13424 4374 3974 50 H(243) 13407 3895 3084 41 H(244) 12540 3161 2753 35 H(24A) 9177 2000 487 45 H(24B) 8877 1714 1047 45
462 Appendix
H(24C) 9122 454 799 51 H(24D) 9388 755 229 51 H(24E) 8065 940 537 70 H(24F) 8292 320 107 70 H(24G) 8337 1196 -42 70 H(24H) 10490 -1254 1541 38 H(24I) 10810 -857 1023 38 H(24J) 9868 -1077 474 35 H(24K) 9502 -1407 990 35 H(25A) 10599 -2106 519 66 H(25B) 9864 -2401 441 66 H(25C) 10233 -2436 1035 66 H(25D) 8908 1138 3739 78 H(25E) 9057 274 3606 78 H(25F) 9919 1218 4202 84 H(25G) 10016 335 4100 84 H(25H) 9061 1006 4758 87 H(25I) 9618 428 4963 87 H(25J) 9015 140 4580 87 H(25K) 8697 4106 1582 72 H(25L) 8636 3879 2217 72 H(25M) 7598 3357 1985 94 H(25N) 7659 3669 1370 94 H(25O) 7653 4615 2316 123 H(25P) 7034 4487 1903 123 H(25Q) 7667 4906 1693 123 ______________________________________________________________________
Crystal Structure Data 463
2.2 proximal cone-Calix[4]diphenanthrenes (81a)
Table 1. Crystal data and structure refinement for C56H56O4. Empirical formula C56H56O4 Formula weight 793.01 Temperature 113(2) K Wavelength 0.71073 A Crystal system, space group Orthorhombic, P2(1)2(1)2(1) Unit cell dimensions a = 11.0221(6) Å α = 90° b = 13.3367(8) Å β = 90° c = 29.6439(15) Å γ = 90° Volume 4357.6(4) A3 Z, Calculated density 4, 1.209 Mg/m3 Absorption coefficient 0.074 mm-1 F(000) 1696 Crystal size 0.22 x 0.20 x 0.10 mm θ range for data collection 3.14 to 26.00 deg. Limiting indices -12<=h<=13, -16<=k<=16, -36<=l<=36 Reflections collected / unique 28159 / 4774 [R(int) = 0.0450] Completeness to θ = 26.00 99.6 % Absorption correction None Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 4774 / 0 / 545 Goodness-of-fit on F2 1.009 Final R indices [I>2σ(I)] R1 = 0.0367, wR2 = 0.0552 [6093 refs] R indices (all data) R1 = 0.0525, wR2 = 0.0567 Absolute structure parameter 0(10) Largest diff. peak and hole 0.198 and -0.156 e.Å-3
464 Appendix
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C56H56O4. U(eq) is defined as one third of the trace of the orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(1) -315(1) 3790(1) 9462(1) 24(1) O(2) -375(1) 3654(1) 8405(1) 21(1) O(3) 1568(1) 1666(1) 7842(1) 20(1) O(4) 1052(1) 1792(1) 8920(1) 20(1) C(11) -1179(2) 3040(2) 9399(1) 21(1) C(12) -941(2) 2080(2) 9569(1) 21(1) C(13) -1807(2) 1336(2) 9495(1) 25(1) C(14) -2861(2) 1543(2) 9261(1) 26(1) C(15) -3049(2) 2493(2) 9084(1) 25(1) C(16) -2214(2) 3257(2) 9151(1) 21(1) C(17) -2392(2) 4276(2) 8923(1) 26(1) C(18) -491(2) 4363(2) 9865(1) 25(1) C(19) 550(2) 5079(2) 9915(1) 26(1) C(21) -1468(2) 3756(2) 8184(1) 19(1) C(22) -2474(2) 4132(2) 8417(1) 23(1) C(23) -3565(2) 4224(2) 8186(1) 27(1) C(24) -3661(2) 3906(2) 7740(1) 29(1) C(25) -2685(2) 3457(2) 7531(1) 26(1) C(26) -1569(2) 3360(2) 7748(1) 21(1) C(27) -574(2) 2704(2) 7570(1) 22(1) C(28) 319(2) 4571(2) 8447(1) 25(1) C(29) 1188(2) 4719(2) 8063(1) 26(1) C(31) 471(2) 1215(2) 7957(1) 17(1) C(32) -591(2) 1702(2) 7820(1) 18(1) C(33) -1663(2) 1279(2) 7951(1) 20(1) C(34) -1719(2) 373(2) 8191(1) 18(1) C(35) -645(2) -124(2) 8330(1) 17(1) C(36) 485(2) 361(2) 8231(1) 16(1) C(37) 1705(2) 59(2) 8427(1) 19(1) C(38) 1970(2) 1384(2) 7394(1) 25(1) C(39) 3148(2) 1912(2) 7302(1) 31(1) C(41) 1251(2) 923(2) 9160(1) 18(1) C(42) 1732(2) 80(2) 8948(1) 18(1) C(43) 2084(2) -749(2) 9224(1) 19(1) C(44) 1659(2) -778(2) 9675(1) 22(1) C(45) 1037(2) 56(2) 9853(1) 23(1) C(46) 867(2) 923(2) 9613(1) 19(1) C(47) 234(2) 1835(2) 9806(1) 24(1) C(48) 2129(2) 2350(2) 8807(1) 23(1) C(49) 2576(2) 3017(2) 9184(1) 25(1) C(110) 368(2) 5750(2) 10325(1) 36(1) C(210) 2023(2) 5608(2) 8156(1) 35(1) C(310) 4150(2) 1640(2) 7628(1) 38(1) C(311) -2891(2) 7(2) 8314(1) 22(1) C(312) -3022(2) -818(2) 8570(1) 24(1) C(313) -1986(2) -1398(2) 8696(1) 19(1) C(314) -2153(2) -2293(2) 8941(1) 25(1) C(315) -1212(2) -2914(2) 9043(1) 26(1)
Crystal Structure Data 465
C(316) -56(2) -2662(2) 8889(1) 25(1) C(317) 126(2) -1783(2) 8653(1) 21(1) C(318) -804(2) -1091(2) 8566(1) 17(1) C(410) 3613(2) 3671(2) 9023(1) 36(1) C(411) 2864(2) -1577(2) 9076(1) 21(1) C(412) 3597(2) -1542(2) 8683(1) 23(1) C(413) 4312(2) -2341(2) 8557(1) 28(1) C(414) 4364(2) -3208(2) 8817(1) 34(1) C(415) 3717(2) -3252(2) 9212(1) 34(1) C(416) 2980(2) -2444(2) 9353(1) 26(1) C(417) 2425(2) -2463(2) 9786(1) 32(1) C(418) 1830(2) -1658(2) 9942(1) 30(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C56H56O4. ______________________________________________________________________ O(1)-C(11) 1.394(2) O(1)-C(18) 1.432(2) O(2)-C(21) 1.379(2) O(2)-C(28) 1.448(2) O(3)-C(31) 1.393(2) O(3)-C(38) 1.449(2) O(4)-C(41) 1.378(2) O(4)-C(48) 1.441(2) C(11)-C(16) 1.388(3) C(11)-C(12) 1.399(3) C(12)-C(13) 1.394(3) C(12)-C(47) 1.511(3) C(13)-C(14) 1.381(3) C(13)-H(13) 0.9500 C(14)-C(15) 1.386(3) C(14)-H(14) 0.9500 C(15)-C(16) 1.387(3) C(15)-H(15) 0.9500 C(16)-C(17) 1.531(3) C(17)-C(22) 1.517(3) C(17)-H(17A) 0.9900 C(17)-H(17B) 0.9900 C(18)-C(19) 1.499(3) C(18)-H(18A) 0.9900 C(18)-H(18B) 0.9900 C(19)-C(110) 1.522(3) C(19)-H(19A) 0.9900 C(19)-H(19B) 0.9900 C(21)-C(22) 1.398(3) C(21)-C(26) 1.401(3) C(22)-C(23) 1.390(3) C(23)-C(24) 1.392(3) C(23)-H(23) 0.9500 C(24)-C(25) 1.379(3) C(24)-H(24) 0.9500 C(25)-C(26) 1.395(3) C(25)-H(25) 0.9500 C(26)-C(27) 1.498(3) C(27)-C(32) 1.527(3)
466 Appendix
C(27)-H(27A) 0.9900 C(27)-H(27B) 0.9900 C(28)-C(29) 1.500(3) C(28)-H(28A) 0.9900 C(28)-H(28B) 0.9900 C(29)-C(210) 1.526(3) C(29)-H(29A) 0.9900 C(29)-H(29B) 0.9900 C(31)-C(36) 1.398(3) C(31)-C(32) 1.399(3) C(32)-C(33) 1.366(3) C(33)-C(34) 1.405(3) C(33)-H(33) 0.9500 C(34)-C(35) 1.417(3) C(34)-C(311) 1.428(3) C(35)-C(36) 1.433(3) C(35)-C(318) 1.479(3) C(36)-C(37) 1.520(3) C(37)-C(42) 1.544(3) C(37)-H(37A) 0.9900 C(37)-H(37B) 0.9900 C(38)-C(39) 1.502(3) C(38)-H(38A) 0.9900 C(38)-H(38B) 0.9900 C(39)-C(310) 1.513(3) C(39)-H(39A) 0.9900 C(39)-H(39B) 0.9900 C(41)-C(42) 1.393(3) C(41)-C(46) 1.408(3) C(42)-C(43) 1.429(3) C(43)-C(44) 1.417(3) C(43)-C(411) 1.466(3) C(44)-C(45) 1.408(3) C(44)-C(418) 1.427(3) C(45)-C(46) 1.371(3) C(45)-H(45) 0.9500 C(46)-C(47) 1.514(3) C(47)-H(47A) 0.9900 C(47)-H(47B) 0.9900 C(48)-C(49) 1.511(3) C(48)-H(48A) 0.9900 C(48)-H(48B) 0.9900 C(49)-C(410) 1.515(3) C(49)-H(49A) 0.9900 C(49)-H(49B) 0.9900 C(110)-H(11A) 0.9800 C(110)-H(11B) 0.9800 C(110)-H(11C) 0.9800 C(210)-H(21A) 0.9800 C(210)-H(21B) 0.9800 C(210)-H(21C) 0.9800 C(310)-H(31A) 0.9800 C(310)-H(31B) 0.9800 C(310)-H(31C) 0.9800 C(311)-C(312) 1.344(3) C(311)-H(311) 0.9500 C(312)-C(313) 1.429(3) C(312)-H(312) 0.9500 C(313)-C(314) 1.409(3) C(313)-C(318) 1.419(3) C(314)-C(315) 1.362(3)
Crystal Structure Data 467
C(314)-H(314) 0.9500 C(315)-C(316) 1.395(3) C(315)-H(315) 0.9500 C(316)-C(317) 1.379(3) C(316)-H(316) 0.9500 C(317)-C(318) 1.404(3) C(317)-H(317) 0.9500 C(410)-H(41A) 0.9800 C(410)-H(41B) 0.9800 C(410)-H(41C) 0.9800 C(411)-C(412) 1.420(3) C(411)-C(416) 1.424(3) C(412)-C(413) 1.378(3) C(412)-H(412) 0.9500 C(413)-C(414) 1.391(3) C(413)-H(413) 0.9500 C(414)-C(415) 1.373(3) C(414)-H(414) 0.9500 C(415)-C(416) 1.413(3) C(415)-H(415) 0.9500 C(416)-C(417) 1.423(3) C(417)-C(418) 1.340(3) C(417)-H(417) 0.9500 C(418)-H(418) 0.9500 C(11)-O(1)-C(18) 113.70(16) C(21)-O(2)-C(28) 114.73(15) C(31)-O(3)-C(38) 112.29(15) C(41)-O(4)-C(48) 115.11(15) C(16)-C(11)-O(1) 118.88(19) C(16)-C(11)-C(12) 122.3(2) O(1)-C(11)-C(12) 118.7(2) C(13)-C(12)-C(11) 117.8(2) C(13)-C(12)-C(47) 120.4(2) C(11)-C(12)-C(47) 121.7(2) C(14)-C(13)-C(12) 120.8(2) C(14)-C(13)-H(13) 119.6 C(12)-C(13)-H(13) 119.6 C(13)-C(14)-C(15) 119.9(2) C(13)-C(14)-H(14) 120.1 C(15)-C(14)-H(14) 120.1 C(14)-C(15)-C(16) 121.2(2) C(14)-C(15)-H(15) 119.4 C(16)-C(15)-H(15) 119.4 C(15)-C(16)-C(11) 117.9(2) C(15)-C(16)-C(17) 120.3(2) C(11)-C(16)-C(17) 121.6(2) C(22)-C(17)-C(16) 109.38(18) C(22)-C(17)-H(17A) 109.8 C(16)-C(17)-H(17A) 109.8 C(22)-C(17)-H(17B) 109.8 C(16)-C(17)-H(17B) 109.8 H(17A)-C(17)-H(17B) 108.2 O(1)-C(18)-C(19) 108.53(17) O(1)-C(18)-H(18A) 110.0 C(19)-C(18)-H(18A) 110.0 O(1)-C(18)-H(18B) 110.0 C(19)-C(18)-H(18B) 110.0 H(18A)-C(18)-H(18B) 108.4 C(18)-C(19)-C(110) 110.60(18) C(18)-C(19)-H(19A) 109.5
468 Appendix
C(110)-C(19)-H(19A) 109.5 C(18)-C(19)-H(19B) 109.5 C(110)-C(19)-H(19B) 109.5 H(19A)-C(19)-H(19B) 108.1 O(2)-C(21)-C(22) 119.57(19) O(2)-C(21)-C(26) 118.07(19) C(22)-C(21)-C(26) 121.9(2) C(23)-C(22)-C(21) 118.3(2) C(23)-C(22)-C(17) 121.9(2) C(21)-C(22)-C(17) 119.1(2) C(22)-C(23)-C(24) 120.4(2) C(22)-C(23)-H(23) 119.8 C(24)-C(23)-H(23) 119.8 C(25)-C(24)-C(23) 120.0(2) C(25)-C(24)-H(24) 120.0 C(23)-C(24)-H(24) 120.0 C(24)-C(25)-C(26) 121.4(2) C(24)-C(25)-H(25) 119.3 C(26)-C(25)-H(25) 119.3 C(25)-C(26)-C(21) 117.4(2) C(25)-C(26)-C(27) 122.48(19) C(21)-C(26)-C(27) 119.2(2) C(26)-C(27)-C(32) 109.36(17) C(26)-C(27)-H(27A) 109.8 C(32)-C(27)-H(27A) 109.8 C(26)-C(27)-H(27B) 109.8 C(32)-C(27)-H(27B) 109.8 H(27A)-C(27)-H(27B) 108.3 O(2)-C(28)-C(29) 112.65(17) O(2)-C(28)-H(28A) 109.1 C(29)-C(28)-H(28A) 109.1 O(2)-C(28)-H(28B) 109.1 C(29)-C(28)-H(28B) 109.1 H(28A)-C(28)-H(28B) 107.8 C(28)-C(29)-C(210) 110.56(19) C(28)-C(29)-H(29A) 109.5 C(210)-C(29)-H(29A) 109.5 C(28)-C(29)-H(29B) 109.5 C(210)-C(29)-H(29B) 109.5 H(29A)-C(29)-H(29B) 108.1 O(3)-C(31)-C(36) 119.00(19) O(3)-C(31)-C(32) 116.99(18) C(36)-C(31)-C(32) 123.8(2) C(33)-C(32)-C(31) 116.71(19) C(33)-C(32)-C(27) 120.6(2) C(31)-C(32)-C(27) 122.48(19) C(32)-C(33)-C(34) 122.5(2) C(32)-C(33)-H(33) 118.7 C(34)-C(33)-H(33) 118.7 C(33)-C(34)-C(35) 120.8(2) C(33)-C(34)-C(311) 117.6(2) C(35)-C(34)-C(311) 121.50(19) C(34)-C(35)-C(36) 117.13(18) C(34)-C(35)-C(318) 116.46(18) C(36)-C(35)-C(318) 126.40(19) C(31)-C(36)-C(35) 118.5(2) C(31)-C(36)-C(37) 116.61(19) C(35)-C(36)-C(37) 124.79(18) C(36)-C(37)-C(42) 113.31(16) C(36)-C(37)-H(37A) 108.9 C(42)-C(37)-H(37A) 108.9
Crystal Structure Data 469
C(36)-C(37)-H(37B) 108.9 C(42)-C(37)-H(37B) 108.9 H(37A)-C(37)-H(37B) 107.7 O(3)-C(38)-C(39) 108.09(17) O(3)-C(38)-H(38A) 110.1 C(39)-C(38)-H(38A) 110.1 O(3)-C(38)-H(38B) 110.1 C(39)-C(38)-H(38B) 110.1 H(38A)-C(38)-H(38B) 108.4 C(38)-C(39)-C(310) 113.67(19) C(38)-C(39)-H(39A) 108.8 C(310)-C(39)-H(39A) 108.8 C(38)-C(39)-H(39B) 108.8 C(310)-C(39)-H(39B) 108.8 H(39A)-C(39)-H(39B) 107.7 O(4)-C(41)-C(42) 120.38(17) O(4)-C(41)-C(46) 116.41(19) C(42)-C(41)-C(46) 123.1(2) C(41)-C(42)-C(43) 117.94(18) C(41)-C(42)-C(37) 117.31(18) C(43)-C(42)-C(37) 124.32(19) C(44)-C(43)-C(42) 118.16(19) C(44)-C(43)-C(411) 117.08(19) C(42)-C(43)-C(411) 124.76(19) C(45)-C(44)-C(43) 119.5(2) C(45)-C(44)-C(418) 120.4(2) C(43)-C(44)-C(418) 120.1(2) C(46)-C(45)-C(44) 122.6(2) C(46)-C(45)-H(45) 118.7 C(44)-C(45)-H(45) 118.7 C(45)-C(46)-C(41) 117.0(2) C(45)-C(46)-C(47) 122.97(19) C(41)-C(46)-C(47) 120.0(2) C(12)-C(47)-C(46) 113.13(18) C(12)-C(47)-H(47A) 109.0 C(46)-C(47)-H(47A) 109.0 C(12)-C(47)-H(47B) 109.0 C(46)-C(47)-H(47B) 109.0 H(47A)-C(47)-H(47B) 107.8 O(4)-C(48)-C(49) 113.60(17) O(4)-C(48)-H(48A) 108.8 C(49)-C(48)-H(48A) 108.8 O(4)-C(48)-H(48B) 108.8 C(49)-C(48)-H(48B) 108.8 H(48A)-C(48)-H(48B) 107.7 C(48)-C(49)-C(410) 110.61(19) C(48)-C(49)-H(49A) 109.5 C(410)-C(49)-H(49A) 109.5 C(48)-C(49)-H(49B) 109.5 C(410)-C(49)-H(49B) 109.5 H(49A)-C(49)-H(49B) 108.1 C(19)-C(110)-H(11A) 109.5 C(19)-C(110)-H(11B) 109.5 H(11A)-C(110)-H(11B) 109.5 C(19)-C(110)-H(11C) 109.5 H(11A)-C(110)-H(11C) 109.5 H(11B)-C(110)-H(11C) 109.5 C(29)-C(210)-H(21A) 109.5 C(29)-C(210)-H(21B) 109.5 H(21A)-C(210)-H(21B) 109.5 C(29)-C(210)-H(21C) 109.5
470 Appendix
H(21A)-C(210)-H(21C) 109.5 H(21B)-C(210)-H(21C) 109.5 C(39)-C(310)-H(31A) 109.5 C(39)-C(310)-H(31B) 109.5 H(31A)-C(310)-H(31B) 109.5 C(39)-C(310)-H(31C) 109.5 H(31A)-C(310)-H(31C) 109.5 H(31B)-C(310)-H(31C) 109.5 C(312)-C(311)-C(34) 121.4(2) C(312)-C(311)-H(311) 119.3 C(34)-C(311)-H(311) 119.3 C(311)-C(312)-C(313) 120.3(2) C(311)-C(312)-H(312) 119.8 C(313)-C(312)-H(312) 119.8 C(314)-C(313)-C(318) 120.3(2) C(314)-C(313)-C(312) 119.2(2) C(318)-C(313)-C(312) 120.44(19) C(315)-C(314)-C(313) 122.1(2) C(315)-C(314)-H(314) 119.0 C(313)-C(314)-H(314) 119.0 C(314)-C(315)-C(316) 118.4(2) C(314)-C(315)-H(315) 120.8 C(316)-C(315)-H(315) 120.8 C(317)-C(316)-C(315) 120.2(2) C(317)-C(316)-H(316) 119.9 C(315)-C(316)-H(316) 119.9 C(316)-C(317)-C(318) 123.1(2) C(316)-C(317)-H(317) 118.4 C(318)-C(317)-H(317) 118.4 C(317)-C(318)-C(313) 115.50(19) C(317)-C(318)-C(35) 125.09(19) C(313)-C(318)-C(35) 119.30(19) C(49)-C(410)-H(41A) 109.5 C(49)-C(410)-H(41B) 109.5 H(41A)-C(410)-H(41B) 109.5 C(49)-C(410)-H(41C) 109.5 H(41A)-C(410)-H(41C) 109.5 H(41B)-C(410)-H(41C) 109.5 C(412)-C(411)-C(416) 116.7(2) C(412)-C(411)-C(43) 123.7(2) C(416)-C(411)-C(43) 119.5(2) C(413)-C(412)-C(411) 121.6(2) C(413)-C(412)-H(412) 119.2 C(411)-C(412)-H(412) 119.2 C(412)-C(413)-C(414) 121.1(2) C(412)-C(413)-H(413) 119.5 C(414)-C(413)-H(413) 119.5 C(415)-C(414)-C(413) 119.2(2) C(415)-C(414)-H(414) 120.4 C(413)-C(414)-H(414) 120.4 C(414)-C(415)-C(416) 121.2(2) C(414)-C(415)-H(415) 119.4 C(416)-C(415)-H(415) 119.4 C(415)-C(416)-C(417) 120.0(2) C(415)-C(416)-C(411) 120.1(2) C(417)-C(416)-C(411) 119.7(2) C(418)-C(417)-C(416) 120.4(2) C(418)-C(417)-H(417) 119.8 C(416)-C(417)-H(417) 119.8 C(417)-C(418)-C(44) 122.2(2)
Crystal Structure Data 471
C(417)-C(418)-H(418) 118.9 C(44)-C(418)-H(418) 118.9 ______________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C56H56O4. The anisotropic displacement factor exponent takes the form: -2 pi² [ h2 a*2 U11 + ... + 2 h k a* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(1) 27(1) 25(1) 22(1) -7(1) 5(1) -4(1) O(2) 19(1) 21(1) 23(1) 1(1) -2(1) 0(1) O(3) 23(1) 23(1) 15(1) -1(1) 4(1) -6(1) O(4) 21(1) 19(1) 19(1) 2(1) 0(1) -1(1) C(11) 17(1) 25(1) 20(1) -4(1) 8(1) -3(1) C(12) 22(1) 23(1) 17(1) -4(1) 6(1) 0(1) C(13) 30(2) 23(1) 23(1) 0(1) 8(1) 1(1) C(14) 22(1) 28(1) 29(1) -2(1) 4(1) -6(1) C(15) 19(1) 30(1) 27(1) 0(1) 2(1) 2(1) C(16) 17(1) 23(1) 24(1) -5(1) 7(1) 3(1) C(17) 25(1) 24(1) 29(1) -1(1) 4(1) 3(1) C(18) 27(1) 25(1) 23(1) -5(1) 4(1) 2(1) C(19) 30(1) 25(1) 23(1) -3(1) -1(1) -1(1) C(21) 19(1) 13(1) 26(1) 4(1) -1(1) 0(1) C(22) 23(1) 15(1) 30(1) 4(1) 3(1) 0(1) C(23) 22(1) 21(1) 38(1) 6(1) 3(1) 2(1) C(24) 26(2) 22(1) 39(2) 8(1) -8(1) 0(1) C(25) 33(2) 20(1) 24(1) 6(1) -5(1) -3(1) C(26) 26(1) 15(1) 21(1) 6(1) -1(1) -4(1) C(27) 27(1) 20(1) 17(1) 3(1) 0(1) -1(1) C(28) 26(1) 23(1) 25(1) -2(1) -2(1) -3(1) C(29) 28(1) 27(1) 23(1) 4(1) -3(1) -2(1) C(31) 16(1) 19(1) 15(1) -4(1) 2(1) -5(1) C(32) 24(1) 18(1) 13(1) -2(1) 0(1) -1(1) C(33) 22(1) 20(1) 18(1) -2(1) -3(1) 5(1) C(34) 21(1) 19(1) 15(1) -2(1) -1(1) -1(1) C(35) 21(1) 19(1) 12(1) -4(1) 2(1) -1(1) C(36) 20(1) 17(1) 12(1) -4(1) 1(1) 0(1) C(37) 22(1) 17(1) 17(1) -2(1) 4(1) -2(1) C(38) 28(1) 30(1) 17(1) -3(1) 3(1) -3(1) C(39) 30(2) 36(2) 29(1) 2(1) 11(1) -5(1) C(41) 17(1) 19(1) 18(1) 3(1) -3(1) -3(1)
472 Appendix
C(42) 14(1) 21(1) 18(1) 0(1) 2(1) -4(1) C(43) 15(1) 20(1) 21(1) 1(1) -2(1) -2(1) C(44) 21(1) 25(1) 20(1) 3(1) -5(1) -1(1) C(45) 24(1) 32(2) 14(1) 3(1) -1(1) -3(1) C(46) 16(1) 26(1) 16(1) -3(1) -1(1) -3(1) C(47) 30(2) 27(1) 14(1) -2(1) 3(1) 0(1) C(48) 26(1) 19(1) 23(1) 0(1) 4(1) 0(1) C(49) 23(1) 25(1) 26(1) -1(1) -3(1) 1(1) C(110) 38(2) 34(2) 35(1) -7(1) 5(1) -4(1) C(210) 35(2) 35(2) 35(1) 8(1) -6(1) -9(1) C(310) 27(2) 41(2) 46(2) -2(1) 5(1) -10(1) C(311) 18(1) 24(1) 25(1) 0(1) 0(1) 1(1) C(312) 18(1) 26(1) 27(1) -5(1) 5(1) -5(1) C(313) 19(1) 20(1) 17(1) -4(1) 2(1) -3(1) C(314) 27(1) 24(1) 22(1) 0(1) 8(1) -6(1) C(315) 36(2) 17(1) 26(1) 3(1) 3(1) -4(1) C(316) 29(1) 19(1) 26(1) -1(1) -4(1) 0(1) C(317) 24(1) 19(1) 20(1) -2(1) 0(1) -3(1) C(318) 18(1) 19(1) 14(1) -3(1) -1(1) -4(1) C(410) 25(1) 33(1) 49(2) 4(1) -8(1) -4(1) C(411) 17(1) 22(1) 24(1) -3(1) -5(1) -2(1) C(412) 16(1) 24(1) 28(1) -3(1) -5(1) 0(1) C(413) 19(1) 33(1) 33(1) -10(1) -4(1) 1(1) C(414) 25(1) 25(1) 51(2) -12(1) -10(1) 7(1) C(415) 32(2) 21(1) 48(2) 1(1) -10(1) 1(1) C(416) 24(1) 24(1) 31(1) 2(1) -8(1) -3(1) C(417) 34(2) 27(1) 36(2) 14(1) -4(1) -2(1) C(418) 33(2) 33(1) 23(1) 11(1) -2(1) 0(1) ______________________________________________________________________
Crystal Structure Data 473
Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103) for C56H56O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(13) -1670 678 9607 30 H(14) -3456 1035 9221 31 H(15) -3763 2623 8914 30 H(17A) -3145 4594 9036 31 H(17B) -1702 4722 8997 31 H(18A) -529 3911 10130 30 H(18B) -1264 4739 9847 30 H(19A) 616 5497 9640 31 H(19B) 1315 4697 9949 31 H(23) -4251 4507 8333 33 H(24) -4399 3999 7579 35 H(25) -2774 3207 7233 31 H(27A) 220 3036 7614 26 H(27B) -691 2590 7243 26 H(28A) 778 4556 8733 30 H(28B) -247 5147 8459 30 H(29A) 729 4839 7781 31 H(29B) 1680 4105 8022 31 H(33) -2400 1610 7876 24 H(37A) 2337 518 8311 22 H(37B) 1907 -627 8323 22 H(38A) 1355 1580 7167 30 H(38B) 2086 648 7377 30 H(39A) 3010 2644 7315 38 H(39B) 3415 1746 6992 38 H(45) 723 15 10151 28 H(47A) 65 1716 10130 28 H(47B) 785 2419 9785 28 H(48A) 1958 2770 8539 27 H(48B) 2781 1873 8724 27 H(49A) 2853 2597 9439 30 H(49B) 1903 3446 9292 30 H(11A) -258 6250 10259 54 H(11B) 1132 6090 10397 54 H(11C) 113 5341 10583 54 H(21A) 1542 6226 8168 52 H(21B) 2626 5661 7914 52 H(21C) 2437 5509 8445 52 H(31A) 3918 1846 7933 57 H(31B) 4899 1983 7540 57 H(31C) 4281 913 7622 57 H(311) -3593 354 8213 27 H(312) -3808 -1017 8667 28 H(314) -2947 -2468 9038 30 H(315) -1340 -3505 9216 31 H(316) 609 -3098 8946 29 H(317) 918 -1640 8545 25 H(41A) 4290 3247 8925 53 H(41B) 3881 4107 9270 53
474 Appendix
H(41C) 3339 4084 8769 53 H(412) 3594 -953 8502 27 H(413) 4776 -2300 8287 34 H(414) 4841 -3762 8722 40 H(415) 3765 -3837 9394 40 H(417) 2477 -3050 9967 39 H(418) 1510 -1673 10239 35 ______________________________________________________________________
Crystal Structure Data 475
2.3 cone-25,26,27,28-Tetra-n-propoxycalix[4]di(9-methyl)-
phenanthrene (86a)
Table 1. Crystal data and structure refinement for C58H60O4. Empirical formula C58H60O4 Formula weight 821.06 Temperature 113(2) K Wavelength 0.71073 A Crystal system, space group Triclinic, P-1 Unit cell dimensions a = 11.1909(4) Å α = 93.885(4°
b = 14.9553(6) Å β = 90.615(3° c = 27.4641(13) Å γ = 93.971(3°
Volume 4574.4(3) Å3 Z, Calculated density 4, 1.192 Mg/m3 Absorption coefficient 0.073 mm-1 F(000) 1760 Crystal size 0.32 x 0.27 x 0.22 mm θ range for data collection 2.85 to 25.25 deg. Limiting indices -13<=h<=13, -17<=k<=17, -32<=l<=32 Reflections collected / unique 68021 / 16546 [R(int) = 0.1126] Completeness to θ = 25.25 99.7 % Absorption correction None Refinement method Full-matrix least-squares on F2 Data / restraints / parameters 16546 / 0 / 1129 Goodness-of-fit on F2 0.829 Final R indices [I>2σ(I)] R1 = 0.0502, wR2 = 0.0892 R indices (all data) R1 = 0.1506, wR2 = 0.0997 Largest diff. peak and hole 0.450 and -0.376 e. Å-3
476 Appendix
Table 2. Atomic coordinates (x 104) and equivalent isotropic displacement parameters (Å2 x 103) for C58H60O4. U(eq) is defined as one third of the trace of the Orthogonalized Uij tensor. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ O(1) 5382(2) -22(1) 3579(1) 25(1) O(2) 6913(2) 2134(1) 3859(1) 23(1) O(3) 9713(2) 2438(1) 3559(1) 22(1) O(4) 8316(2) 320(1) 3495(1) 24(1) C(11) 5953(3) -42(2) 4031(1) 21(1) C(12) 6765(3) -697(2) 4088(1) 22(1) C(13) 7327(3) -715(2) 4541(1) 24(1) C(14) 7096(3) -94(2) 4915(1) 27(1) C(15) 6316(3) 563(2) 4846(1) 28(1) C(16) 5739(3) 601(2) 4398(1) 19(1) C(17) 4932(3) 1354(2) 4318(1) 27(1) C(18) 4212(3) -471(2) 3565(1) 38(1) C(19) 3686(3) -429(3) 3055(1) 42(1) C(21) 6527(3) 2620(2) 4270(1) 21(1) C(22) 5497(3) 2258(2) 4498(1) 22(1) C(23) 5132(3) 2714(2) 4913(1) 25(1) C(24) 5678(3) 3550(2) 5079(1) 24(1) C(25) 6705(3) 3916(2) 4838(1) 20(1) C(26) 7199(3) 3373(2) 4459(1) 21(1) C(27) 8513(3) 3473(2) 4309(1) 22(1) C(28) 6801(3) 2578(2) 3415(1) 27(1) C(29) 5576(3) 2388(2) 3175(1) 34(1) C(31) 9687(3) 2133(2) 4023(1) 18(1) C(32) 9122(3) 2611(2) 4395(1) 19(1) C(33) 9103(3) 2293(2) 4856(1) 23(1) C(34) 9631(3) 1512(2) 4946(1) 24(1) C(35) 10149(3) 1017(2) 4569(1) 21(1) C(36) 10185(2) 1314(2) 4103(1) 18(1) C(37) 10733(3) 757(2) 3689(1) 22(1) C(38) 10812(3) 2964(2) 3485(1) 28(1) C(39) 10834(3) 3229(2) 2973(1) 46(1) C(41) 8995(3) -406(2) 3556(1) 19(1) C(42) 10225(3) -207(2) 3653(1) 21(1) C(43) 10891(3) -909(2) 3745(1) 21(1) C(44) 10415(3) -1806(2) 3707(1) 21(1) C(45) 9187(3) -1990(2) 3587(1) 20(1) C(46) 8439(3) -1258(2) 3572(1) 20(1) C(47) 7083(3) -1349(2) 3671(1) 24(1) C(48) 7788(3) 350(2) 3019(1) 26(1) C(49) 8631(3) 773(2) 2665(1) 32(1) C(110) 4397(3) -925(2) 2670(1) 43(1) C(210) 5501(3) 2879(3) 2708(1) 53(1) C(211) 5236(3) 4041(2) 5501(1) 28(1) C(212) 5715(3) 4852(2) 5674(1) 29(1) C(213) 5198(3) 5325(2) 6120(1) 39(1) C(214) 6665(3) 5290(2) 5406(1) 25(1) C(215) 7105(3) 6181(2) 5540(1) 31(1) C(216) 7910(3) 6641(2) 5262(1) 32(1)
Crystal Structure Data 477
C(217) 8267(3) 6228(2) 4827(1) 31(1) C(218) 7886(3) 5356(2) 4695(1) 25(1) C(219) 7123(3) 4842(2) 4982(1) 25(1) C(310) 12018(3) 3787(2) 2876(1) 60(1) C(410) 7992(3) 878(2) 2178(1) 44(1) C(411) 11139(3) -2520(2) 3814(1) 22(1) C(412) 10722(3) -3382(2) 3794(1) 25(1) C(413) 11482(3) -4105(2) 3959(1) 37(1) C(414) 9531(3) -3616(2) 3600(1) 25(1) C(415) 9101(3) -4527(2) 3503(1) 35(1) C(416) 8011(3) -4752(2) 3285(1) 39(1) C(417) 7299(3) -4086(2) 3141(1) 38(1) C(418) 7673(3) -3200(2) 3238(1) 29(1) C(419) 8766(3) -2930(2) 3490(1) 24(1) O(5) 508(2) 5331(1) 1455(1) 29(1) O(6) 3479(2) 5657(1) 1528(1) 25(1) O(7) 4973(2) 7750(1) 1462(1) 21(1) O(8) 2062(2) 7389(1) 1165(1) 23(1) C(51) 1024(3) 5188(2) 1000(1) 23(1) C(52) 791(3) 5742(2) 629(1) 21(1) C(53) 1310(3) 5574(2) 183(1) 25(1) C(54) 2067(3) 4890(2) 106(1) 28(1) C(55) 2324(3) 4365(2) 482(1) 24(1) C(56) 1820(3) 4514(2) 939(1) 20(1) C(57) 2172(3) 3972(2) 1356(1) 29(1) C(58) -600(3) 4834(3) 1501(1) 69(2) C(59) -843(4) 4744(4) 2035(2) 125(2) C(61) 4114(3) 4905(2) 1450(1) 20(1) C(62) 3531(3) 4047(2) 1441(1) 20(1) C(63) 4236(3) 3298(2) 1420(1) 18(1) C(64) 5454(3) 3422(2) 1289(1) 19(1) C(65) 5952(3) 4303(2) 1235(1) 21(1) C(66) 5333(3) 5043(2) 1338(1) 18(1) C(67) 5867(3) 5990(2) 1300(1) 23(1) C(68) 3045(3) 5808(2) 2013(1) 31(1) C(69) 3982(3) 6271(2) 2359(1) 34(1) C(71) 4843(3) 7336(2) 993(1) 17(1) C(72) 5302(3) 6486(2) 900(1) 18(1) C(73) 5192(3) 6083(2) 432(1) 22(1) C(74) 4642(3) 6499(2) 64(1) 25(1) C(75) 4157(3) 7314(2) 167(1) 21(1) C(76) 4235(3) 7734(2) 635(1) 18(1) C(77) 3633(3) 8611(2) 730(1) 22(1) C(78) 5921(3) 8467(2) 1500(1) 23(1) C(79) 7122(3) 8140(2) 1631(1) 27(1) C(81) 1642(3) 7781(2) 760(1) 19(1) C(82) 2305(3) 8485(2) 579(1) 20(1) C(83) 1782(3) 8953(2) 197(1) 21(1) C(84) 736(3) 8530(2) -43(1) 21(1) C(85) 196(3) 7736(2) 123(1) 24(1) C(86) 589(3) 7383(2) 537(1) 23(1) C(87) 4(3) 6529(2) 713(1) 25(1) C(88) 1996(3) 7937(2) 1618(1) 27(1) C(89) 788(3) 7830(2) 1852(1) 32(1) C(510) -1660(6) 3929(4) 2115(2) 183(3) C(610) 3488(3) 6454(2) 2873(1) 57(1) C(611) 6123(3) 2663(2) 1172(1) 25(1) C(612) 5682(3) 1805(2) 1222(1) 23(1) C(613) 6381(3) 1025(2) 1045(1) 35(1) C(614) 4528(3) 1664(2) 1439(1) 24(1)
478 Appendix
C(615) 4120(3) 810(2) 1580(1) 31(1) C(616) 3065(3) 670(2) 1826(1) 36(1) C(617) 2386(3) 1394(2) 1949(1) 35(1) C(618) 2754(3) 2237(2) 1809(1) 27(1) C(619) 3810(3) 2403(2) 1546(1) 22(1) C(710) 7190(3) 7817(2) 2142(1) 33(1) C(810) 782(3) 8394(3) 2338(1) 60(1) C(811) 261(3) 8923(2) -460(1) 27(1) C(812) 699(3) 9691(2) -625(1) 25(1) C(813) 150(3) 10066(2) -1068(1) 31(1) C(814) 1681(3) 10194(2) -356(1) 23(1) C(815) 2077(3) 11070(2) -481(1) 26(1) C(816) 2917(3) 11597(2) -202(1) 26(1) C(817) 3346(3) 11274(2) 224(1) 28(1) C(818) 2986(3) 10425(2) 353(1) 23(1) C(819) 2191(3) 9844(2) 59(1) 19(1) ______________________________________________________________________ Table 3. Bond lengths [Å] and angles [°] for C58H60O4. ______________________________________________________________________ O(1)-C(11) 1.393(3) O(1)-C(18) 1.428(3) O(2)-C(21) 1.390(3) O(2)-C(28) 1.436(3) O(3)-C(31) 1.382(3) O(3)-C(38) 1.437(3) O(4)-C(41) 1.387(3) O(4)-C(48) 1.432(3) C(11)-C(16) 1.381(4) C(11)-C(12) 1.396(4) C(12)-C(13) 1.392(4) C(12)-C(47) 1.514(4) C(13)-C(14) 1.377(4) C(14)-C(15) 1.380(4) C(15)-C(16) 1.389(4) C(16)-C(17) 1.517(4) C(17)-C(22) 1.502(4) C(18)-C(19) 1.519(4) C(19)-C(110) 1.516(4) C(21)-C(26) 1.377(4) C(21)-C(22) 1.411(4) C(22)-C(23) 1.369(4) C(23)-C(24) 1.398(4) C(24)-C(25) 1.428(4) C(24)-C(211) 1.440(4) C(25)-C(26) 1.416(4) C(25)-C(219) 1.458(4) C(26)-C(27) 1.531(4) C(27)-C(32) 1.530(4) C(28)-C(29) 1.515(4) C(29)-C(210) 1.525(4) C(31)-C(32) 1.390(4) C(31)-C(36) 1.409(4) C(32)-C(33) 1.384(4)
Crystal Structure Data 479
C(33)-C(34) 1.380(4) C(34)-C(35) 1.386(4) C(35)-C(36) 1.385(4) C(36)-C(37) 1.523(4) C(37)-C(42) 1.509(4) C(38)-C(39) 1.487(4) C(39)-C(310) 1.551(4) C(41)-C(46) 1.382(4) C(41)-C(42) 1.407(4) C(42)-C(43) 1.365(4) C(43)-C(44) 1.405(4) C(44)-C(45) 1.414(4) C(44)-C(411) 1.428(4) C(45)-C(46) 1.426(4) C(45)-C(419) 1.458(4) C(46)-C(47) 1.543(4) C(48)-C(49) 1.503(4) C(49)-C(410) 1.531(4) C(211)-C(212) 1.345(4) C(212)-C(214) 1.444(4) C(212)-C(213) 1.515(4) C(214)-C(215) 1.412(4) C(214)-C(219) 1.422(4) C(215)-C(216) 1.367(4) C(216)-C(217) 1.382(4) C(217)-C(218) 1.367(4) C(218)-C(219) 1.397(4) C(411)-C(412) 1.337(4) C(412)-C(414) 1.441(4) C(412)-C(413) 1.513(4) C(414)-C(415) 1.419(4) C(414)-C(419) 1.427(4) C(415)-C(416) 1.362(4) C(416)-C(417) 1.394(4) C(417)-C(418) 1.369(4) C(418)-C(419) 1.420(4) O(5)-C(51) 1.392(3) O(5)-C(58) 1.412(4) O(6)-C(61) 1.378(3) O(6)-C(68) 1.432(3) O(7)-C(71) 1.393(3) O(7)-C(78) 1.453(3) O(8)-C(81) 1.385(3) O(8)-C(88) 1.448(3) C(51)-C(52) 1.390(4) C(51)-C(56) 1.393(4) C(52)-C(53) 1.377(4) C(52)-C(87) 1.524(4) C(53)-C(54) 1.379(4) C(54)-C(55) 1.380(4) C(55)-C(56) 1.392(4) C(56)-C(57) 1.510(4) C(57)-C(62) 1.531(4) C(58)-C(59) 1.507(5) C(59)-C(510) 1.503(6) C(61)-C(62) 1.397(4) C(61)-C(66) 1.406(4) C(62)-C(63) 1.412(4) C(63)-C(64) 1.416(4) C(63)-C(619) 1.455(4) C(64)-C(65) 1.412(4)
480 Appendix
C(64)-C(611) 1.424(4) C(65)-C(66) 1.361(4) C(66)-C(67) 1.510(4) C(67)-C(72) 1.522(4) C(68)-C(69) 1.505(4) C(69)-C(610) 1.536(4) C(71)-C(76) 1.378(4) C(71)-C(72) 1.414(4) C(72)-C(73) 1.382(4) C(73)-C(74) 1.383(4) C(74)-C(75) 1.380(4) C(75)-C(76) 1.393(4) C(76)-C(77) 1.524(4) C(77)-C(82) 1.534(4) C(78)-C(79) 1.510(4) C(79)-C(710) 1.518(4) C(81)-C(82) 1.370(4) C(81)-C(86) 1.399(4) C(82)-C(83) 1.440(4) C(83)-C(84) 1.425(4) C(83)-C(819) 1.456(4) C(84)-C(85) 1.401(4) C(84)-C(811) 1.435(4) C(85)-C(86) 1.367(4) C(86)-C(87) 1.506(4) C(88)-C(89) 1.507(4) C(89)-C(810) 1.528(4) C(611)-C(612) 1.358(4) C(612)-C(614) 1.437(4) C(612)-C(613) 1.507(4) C(614)-C(615) 1.407(4) C(614)-C(619) 1.427(4) C(615)-C(616) 1.377(4) C(616)-C(617) 1.390(4) C(617)-C(618) 1.380(4) C(618)-C(619) 1.408(4) C(811)-C(812) 1.328(4) C(812)-C(814) 1.455(4) C(812)-C(813) 1.514(4) C(814)-C(819) 1.416(4) C(814)-C(815) 1.418(4) C(815)-C(816) 1.375(4) C(816)-C(817) 1.390(4) C(817)-C(818) 1.376(4) C(818)-C(819) 1.407(4) C(11)-O(1)-C(18) 112.6(2) C(21)-O(2)-C(28) 113.9(2) C(31)-O(3)-C(38) 110.8(2) C(41)-O(4)-C(48) 115.4(2) C(16)-C(11)-O(1) 119.4(3) C(16)-C(11)-C(12) 122.3(3) O(1)-C(11)-C(12) 118.2(3) C(13)-C(12)-C(11) 117.8(3) C(13)-C(12)-C(47) 119.8(3) C(11)-C(12)-C(47) 122.3(3) C(14)-C(13)-C(12) 120.4(3) C(13)-C(14)-C(15) 120.7(3) C(14)-C(15)-C(16) 120.4(3) C(11)-C(16)-C(15) 118.3(3)
Crystal Structure Data 481
C(11)-C(16)-C(17) 121.8(3) C(15)-C(16)-C(17) 119.9(3) C(22)-C(17)-C(16) 112.4(3) O(1)-C(18)-C(19) 108.2(3) C(110)-C(19)-C(18) 112.2(3) C(26)-C(21)-O(2) 119.9(3) C(26)-C(21)-C(22) 123.2(3) O(2)-C(21)-C(22) 116.7(3) C(23)-C(22)-C(21) 117.2(3) C(23)-C(22)-C(17) 122.4(3) C(21)-C(22)-C(17) 120.0(3) C(22)-C(23)-C(24) 121.7(3) C(23)-C(24)-C(25) 120.0(3) C(23)-C(24)-C(211) 120.8(3) C(25)-C(24)-C(211) 119.2(3) C(26)-C(25)-C(24) 117.8(3) C(26)-C(25)-C(219) 124.9(3) C(24)-C(25)-C(219) 117.1(3) C(21)-C(26)-C(25) 118.3(3) C(21)-C(26)-C(27) 117.0(3) C(25)-C(26)-C(27) 123.7(3) C(32)-C(27)-C(26) 110.0(2) O(2)-C(28)-C(29) 112.5(3) C(28)-C(29)-C(210) 110.4(3) O(3)-C(31)-C(32) 119.7(3) O(3)-C(31)-C(36) 119.0(3) C(32)-C(31)-C(36) 121.2(3) C(33)-C(32)-C(31) 118.9(3) C(33)-C(32)-C(27) 119.0(3) C(31)-C(32)-C(27) 122.1(3) C(34)-C(33)-C(32) 120.6(3) C(33)-C(34)-C(35) 120.3(3) C(34)-C(35)-C(36) 120.7(3) C(35)-C(36)-C(31) 118.2(3) C(35)-C(36)-C(37) 120.3(3) C(31)-C(36)-C(37) 121.5(3) C(42)-C(37)-C(36) 112.3(2) O(3)-C(38)-C(39) 108.9(2) C(38)-C(39)-C(310) 110.5(3) C(46)-C(41)-O(4) 120.0(3) C(46)-C(41)-C(42) 123.3(3) O(4)-C(41)-C(42) 116.3(3) C(43)-C(42)-C(41) 117.0(3) C(43)-C(42)-C(37) 122.8(3) C(41)-C(42)-C(37) 120.0(3) C(42)-C(43)-C(44) 122.6(3) C(43)-C(44)-C(45) 119.0(3) C(43)-C(44)-C(411) 120.8(3) C(45)-C(44)-C(411) 120.1(3) C(44)-C(45)-C(46) 118.8(3) C(44)-C(45)-C(419) 117.1(3) C(46)-C(45)-C(419) 124.1(3) C(41)-C(46)-C(45) 117.5(3) C(41)-C(46)-C(47) 118.4(3) C(45)-C(46)-C(47) 123.0(3) C(12)-C(47)-C(46) 110.8(2) O(4)-C(48)-C(49) 112.8(2) C(48)-C(49)-C(410) 110.9(3) C(212)-C(211)-C(24) 123.4(3) C(211)-C(212)-C(214) 119.0(3) C(211)-C(212)-C(213) 120.1(3)
482 Appendix
C(214)-C(212)-C(213) 120.7(3) C(215)-C(214)-C(219) 118.8(3) C(215)-C(214)-C(212) 121.2(3) C(219)-C(214)-C(212) 119.9(3) C(216)-C(215)-C(214) 122.1(3) C(215)-C(216)-C(217) 118.6(3) C(218)-C(217)-C(216) 120.7(3) C(217)-C(218)-C(219) 122.6(3) C(218)-C(219)-C(214) 116.7(3) C(218)-C(219)-C(25) 122.6(3) C(214)-C(219)-C(25) 120.3(3) C(412)-C(411)-C(44) 123.1(3) C(411)-C(412)-C(414) 118.6(3) C(411)-C(412)-C(413) 121.4(3) C(414)-C(412)-C(413) 120.1(3) C(415)-C(414)-C(419) 118.4(3) C(415)-C(414)-C(412) 121.3(3) C(419)-C(414)-C(412) 120.3(3) C(416)-C(415)-C(414) 121.6(3) C(415)-C(416)-C(417) 120.3(3) C(418)-C(417)-C(416) 119.7(3) C(417)-C(418)-C(419) 122.1(3) C(418)-C(419)-C(414) 117.5(3) C(418)-C(419)-C(45) 122.6(3) C(414)-C(419)-C(45) 119.5(3) C(51)-O(5)-C(58) 113.5(2) C(61)-O(6)-C(68) 115.2(2) C(71)-O(7)-C(78) 112.8(2) C(81)-O(8)-C(88) 114.1(2) C(52)-C(51)-O(5) 119.9(3) C(52)-C(51)-C(56) 121.7(3) O(5)-C(51)-C(56) 118.2(3) C(53)-C(52)-C(51) 118.2(3) C(53)-C(52)-C(87) 120.4(3) C(51)-C(52)-C(87) 121.4(3) C(52)-C(53)-C(54) 121.4(3) C(55)-C(54)-C(53) 119.8(3) C(54)-C(55)-C(56) 120.7(3) C(55)-C(56)-C(51) 118.1(3) C(55)-C(56)-C(57) 120.0(3) C(51)-C(56)-C(57) 121.9(3) C(56)-C(57)-C(62) 111.4(3) O(5)-C(58)-C(59) 109.0(3) C(510)-C(59)-C(58) 111.8(4) O(6)-C(61)-C(62) 120.5(3) O(6)-C(61)-C(66) 117.2(3) C(62)-C(61)-C(66) 122.1(3) C(61)-C(62)-C(63) 118.4(3) C(61)-C(62)-C(57) 117.2(3) C(63)-C(62)-C(57) 123.4(3) C(64)-C(63)-C(62) 118.7(3) C(64)-C(63)-C(619) 116.9(3) C(62)-C(63)-C(619) 124.3(3) C(65)-C(64)-C(63) 118.9(3) C(65)-C(64)-C(611) 120.9(3) C(63)-C(64)-C(611) 120.0(3) C(66)-C(65)-C(64) 122.5(3) C(65)-C(66)-C(61) 117.6(3) C(65)-C(66)-C(67) 123.1(3) C(61)-C(66)-C(67) 119.1(3) C(66)-C(67)-C(72) 114.0(2)
Crystal Structure Data 483
O(6)-C(68)-C(69) 112.7(2) C(68)-C(69)-C(610) 111.9(3) C(76)-C(71)-O(7) 120.5(3) C(76)-C(71)-C(72) 121.1(3) O(7)-C(71)-C(72) 118.4(3) C(73)-C(72)-C(71) 118.3(3) C(73)-C(72)-C(67) 119.5(3) C(71)-C(72)-C(67) 122.2(3) C(74)-C(73)-C(72) 120.9(3) C(73)-C(74)-C(75) 119.8(3) C(74)-C(75)-C(76) 120.9(3) C(71)-C(76)-C(75) 118.8(3) C(71)-C(76)-C(77) 123.0(3) C(75)-C(76)-C(77) 118.2(3) C(76)-C(77)-C(82) 110.4(2) O(7)-C(78)-C(79) 112.7(2) C(78)-C(79)-C(710) 113.8(3) C(82)-C(81)-O(8) 119.4(3) C(82)-C(81)-C(86) 123.5(3) O(8)-C(81)-C(86) 116.9(3) C(81)-C(82)-C(83) 118.3(3) C(81)-C(82)-C(77) 117.1(3) C(83)-C(82)-C(77) 123.6(3) C(84)-C(83)-C(82) 117.1(3) C(84)-C(83)-C(819) 117.5(3) C(82)-C(83)-C(819) 125.2(3) C(85)-C(84)-C(83) 120.1(3) C(85)-C(84)-C(811) 120.9(3) C(83)-C(84)-C(811) 119.0(3) C(86)-C(85)-C(84) 121.8(3) C(85)-C(86)-C(81) 117.5(3) C(85)-C(86)-C(87) 121.4(3) C(81)-C(86)-C(87) 120.6(3) C(86)-C(87)-C(52) 111.8(3) O(8)-C(88)-C(89) 112.6(2) C(88)-C(89)-C(810) 110.5(3) C(612)-C(611)-C(64) 122.9(3) C(611)-C(612)-C(614) 118.4(3) C(611)-C(612)-C(613) 120.5(3) C(614)-C(612)-C(613) 121.1(3) C(615)-C(614)-C(619) 118.7(3) C(615)-C(614)-C(612) 120.9(3) C(619)-C(614)-C(612) 120.3(3) C(616)-C(615)-C(614) 122.1(3) C(615)-C(616)-C(617) 119.4(3) C(618)-C(617)-C(616) 119.8(3) C(617)-C(618)-C(619) 122.5(3) C(618)-C(619)-C(614) 117.4(3) C(618)-C(619)-C(63) 122.7(3) C(614)-C(619)-C(63) 119.7(3) C(812)-C(811)-C(84) 124.0(3) C(811)-C(812)-C(814) 118.5(3) C(811)-C(812)-C(813) 121.2(3) C(814)-C(812)-C(813) 120.2(3) C(819)-C(814)-C(815) 119.1(3) C(819)-C(814)-C(812) 120.2(3) C(815)-C(814)-C(812) 120.5(3) C(816)-C(815)-C(814) 121.8(3) C(815)-C(816)-C(817) 118.7(3) C(818)-C(817)-C(816) 120.8(3)
484 Appendix
C(817)-C(818)-C(819) 122.0(3) C(818)-C(819)-C(814) 117.4(3) C(818)-C(819)-C(83) 122.5(3) C(814)-C(819)-C(83) 119.8(3) ______________________________________________________________________ Symmetry transformations used to generate equivalent atoms: Table 4. Anisotropic displacement parameters (Å2 x 103) for C58H60O4. The anisotropic displacement factor exponent takes the form: -2 pi2 [h2 a*2 U11 + ... + 2 h k a* b* U12] ______________________________________________________________________ U11 U22 U33 U23 U13 U12 ______________________________________________________________________ O(1) 17(1) 33(2) 23(1) -1(1) -1(1) 1(1) O(2) 25(1) 21(1) 22(1) -4(1) 3(1) 0(1) O(3) 24(1) 22(1) 20(1) 0(1) 1(1) -4(1) O(4) 27(1) 23(1) 22(1) -2(1) -3(1) 1(1) C(11) 15(2) 32(2) 16(2) 6(2) -3(2) -6(2) C(12) 20(2) 22(2) 23(2) 0(2) 1(2) -3(2) C(13) 22(2) 25(2) 25(2) 5(2) 1(2) 0(2) C(14) 26(2) 33(2) 21(2) 5(2) -3(2) -3(2) C(15) 27(2) 34(2) 21(2) -4(2) 2(2) 0(2) C(16) 18(2) 17(2) 22(2) -1(2) 3(2) -4(2) C(17) 17(2) 34(2) 29(2) -5(2) -1(2) 0(2) C(18) 23(2) 54(3) 32(2) -6(2) 0(2) -12(2) C(19) 23(2) 70(3) 31(2) -13(2) -4(2) -1(2) C(21) 19(2) 26(2) 20(2) -4(2) -1(2) 6(2) C(22) 10(2) 25(2) 31(2) -4(2) -5(2) 2(2) C(23) 15(2) 30(2) 29(2) 0(2) 2(2) -4(2) C(24) 20(2) 27(2) 27(2) -3(2) -1(2) 12(2) C(25) 14(2) 25(2) 20(2) -3(2) -3(2) 1(2) C(26) 16(2) 22(2) 24(2) -1(2) -2(2) -1(2) C(27) 25(2) 15(2) 26(2) -4(2) -5(2) -2(2) C(28) 31(2) 28(2) 23(2) -3(2) -2(2) 5(2) C(29) 29(2) 42(3) 29(2) -12(2) -7(2) 8(2) C(31) 15(2) 24(2) 14(2) 1(2) -3(2) -6(2) C(32) 17(2) 19(2) 20(2) -1(2) -1(2) -1(2) C(33) 25(2) 18(2) 23(2) -7(2) 2(2) -1(2) C(34) 27(2) 27(2) 18(2) 4(2) 0(2) -2(2) C(35) 20(2) 16(2) 26(2) -2(2) -5(2) 3(2)
Crystal Structure Data 485
C(36) 6(2) 20(2) 25(2) -6(2) -1(1) -2(2) C(37) 20(2) 24(2) 20(2) -3(2) 1(2) -1(2) C(38) 36(2) 24(2) 22(2) -3(2) 1(2) -2(2) C(39) 72(3) 35(3) 28(2) 2(2) 5(2) -9(2) C(41) 24(2) 16(2) 19(2) 1(2) -1(2) 9(2) C(42) 22(2) 24(2) 15(2) -4(2) 5(2) 1(2) C(43) 17(2) 24(2) 21(2) -3(2) 1(2) 2(2) C(44) 26(2) 22(2) 14(2) -4(2) 2(2) 4(2) C(45) 28(2) 19(2) 12(2) -1(2) 1(2) 1(2) C(46) 20(2) 22(2) 18(2) -2(2) -3(2) -5(2) C(47) 24(2) 20(2) 25(2) 1(2) -1(2) -4(2) C(48) 26(2) 25(2) 28(2) -1(2) -7(2) 4(2) C(49) 42(2) 29(2) 25(2) -4(2) 1(2) -1(2) C(110) 36(2) 55(3) 37(2) -9(2) -7(2) 4(2) C(210) 53(3) 73(3) 33(2) 2(2) -11(2) 22(2) C(211) 21(2) 41(3) 22(2) -3(2) 4(2) 10(2) C(212) 30(2) 33(2) 24(2) -10(2) -5(2) 17(2) C(213) 34(2) 53(3) 29(2) -12(2) 3(2) 10(2) C(214) 17(2) 30(2) 26(2) -5(2) -6(2) 9(2) C(215) 30(2) 35(2) 26(2) -15(2) -6(2) 11(2) C(216) 28(2) 33(2) 32(2) -12(2) -7(2) 7(2) C(217) 26(2) 32(2) 33(2) -7(2) -4(2) 2(2) C(218) 26(2) 26(2) 22(2) -11(2) -1(2) 5(2) C(219) 27(2) 25(2) 22(2) -9(2) -5(2) 5(2) C(310) 92(3) 43(3) 41(3) -6(2) 27(2) -30(2) C(410) 60(3) 41(3) 31(2) -2(2) -4(2) 10(2) C(411) 21(2) 27(2) 19(2) -2(2) 2(2) 7(2) C(412) 35(2) 20(2) 21(2) 2(2) 4(2) 10(2) C(413) 40(2) 32(2) 41(2) 3(2) -3(2) 13(2) C(414) 38(2) 19(2) 19(2) 2(2) 2(2) 7(2) C(415) 46(3) 25(2) 35(2) 7(2) 1(2) 10(2) C(416) 53(3) 13(2) 50(3) 0(2) -11(2) -3(2) C(417) 38(2) 33(3) 42(2) 3(2) -8(2) -9(2) C(418) 36(2) 22(2) 28(2) 2(2) -3(2) -4(2) C(419) 31(2) 22(2) 18(2) 4(2) -2(2) 0(2) O(5) 22(1) 31(2) 32(1) -4(1) 2(1) 1(1) O(6) 28(1) 20(1) 28(1) -1(1) 2(1) 3(1) O(7) 28(1) 17(1) 19(1) -3(1) -2(1) 1(1) O(8) 24(1) 22(1) 24(1) -1(1) -5(1) 3(1) C(51) 17(2) 27(2) 24(2) -6(2) 3(2) -4(2) C(52) 14(2) 24(2) 24(2) -2(2) -4(2) 0(2) C(53) 24(2) 24(2) 28(2) 0(2) -6(2) 3(2) C(54) 27(2) 29(2) 26(2) -8(2) -4(2) 1(2) C(55) 19(2) 21(2) 31(2) -4(2) -2(2) -2(2) C(56) 20(2) 8(2) 31(2) -1(2) -4(2) -4(2) C(57) 29(2) 20(2) 37(2) -3(2) 2(2) -1(2) C(58) 37(3) 115(4) 47(3) -13(3) 11(2) -39(3) C(59) 94(4) 168(6) 100(4) -16(4) 75(4) -64(4) C(61) 25(2) 16(2) 19(2) -1(2) -1(2) 5(2) C(62) 18(2) 22(2) 18(2) -1(2) 1(2) -6(2) C(63) 27(2) 12(2) 16(2) 0(2) -3(2) 0(2) C(64) 27(2) 14(2) 16(2) 1(2) -5(2) 4(2) C(65) 20(2) 20(2) 23(2) -2(2) -2(2) 2(2) C(66) 18(2) 12(2) 23(2) 1(2) -7(2) 0(2) C(67) 25(2) 24(2) 20(2) 3(2) -1(2) 4(2) C(68) 31(2) 18(2) 42(2) -3(2) 15(2) 5(2) C(69) 43(2) 25(2) 35(2) -1(2) 1(2) 1(2) C(71) 17(2) 21(2) 12(2) -2(2) 0(2) -5(2) C(72) 16(2) 16(2) 21(2) 0(2) 2(2) -1(2) C(73) 23(2) 12(2) 31(2) -3(2) -1(2) 4(2) C(74) 28(2) 29(2) 18(2) -4(2) 0(2) 3(2)
486 Appendix
C(75) 17(2) 19(2) 27(2) 1(2) -4(2) 1(2) C(76) 16(2) 15(2) 23(2) -1(2) 0(2) -2(2) C(77) 21(2) 20(2) 24(2) 2(2) -2(2) 4(2) C(78) 27(2) 16(2) 26(2) -4(2) 0(2) -1(2) C(79) 27(2) 27(2) 25(2) -2(2) 0(2) -5(2) C(81) 20(2) 15(2) 22(2) -1(2) 0(2) 9(2) C(82) 18(2) 21(2) 21(2) -4(2) -3(2) 5(2) C(83) 20(2) 24(2) 20(2) -5(2) 4(2) 6(2) C(84) 20(2) 23(2) 19(2) -7(2) -2(2) 7(2) C(85) 17(2) 20(2) 33(2) -5(2) -4(2) 0(2) C(86) 19(2) 24(2) 26(2) -1(2) -2(2) 3(2) C(87) 22(2) 20(2) 32(2) -2(2) -6(2) -1(2) C(88) 29(2) 29(2) 21(2) -1(2) -6(2) 1(2) C(89) 26(2) 34(2) 33(2) -2(2) -2(2) -5(2) C(510) 191(7) 222(8) 126(6) 33(6) -63(5) -60(6) C(610) 78(3) 54(3) 36(3) -3(2) 14(2) -3(2) C(611) 25(2) 28(2) 23(2) -5(2) -6(2) 8(2) C(612) 33(2) 16(2) 19(2) -5(2) -8(2) 6(2) C(613) 50(3) 21(2) 35(2) -7(2) -6(2) 11(2) C(614) 34(2) 19(2) 19(2) -5(2) -12(2) 1(2) C(615) 45(3) 17(2) 30(2) 0(2) -2(2) 6(2) C(616) 56(3) 17(2) 35(2) 1(2) -5(2) 2(2) C(617) 39(2) 32(3) 34(2) 8(2) 1(2) -7(2) C(618) 31(2) 22(2) 28(2) 1(2) -1(2) 4(2) C(619) 30(2) 24(2) 12(2) -4(2) -6(2) 1(2) C(710) 33(2) 39(2) 27(2) 1(2) -7(2) -2(2) C(810) 46(3) 86(4) 40(3) -28(2) 13(2) -14(2) C(811) 21(2) 33(2) 25(2) -5(2) -3(2) 2(2) C(812) 25(2) 33(2) 17(2) -1(2) 3(2) 11(2) C(813) 30(2) 38(2) 24(2) -1(2) -2(2) 9(2) C(814) 18(2) 26(2) 24(2) 1(2) 7(2) 9(2) C(815) 30(2) 33(2) 17(2) 9(2) 7(2) 11(2) C(816) 19(2) 31(2) 30(2) 8(2) 4(2) 4(2) C(817) 26(2) 31(2) 27(2) 2(2) 1(2) -1(2) C(818) 22(2) 22(2) 26(2) 6(2) -1(2) 5(2) C(819) 15(2) 23(2) 20(2) -1(2) 2(2) 2(2) ______________________________________________________________________ Table 5. Hydrogen coordinates (x 104) and isotropic displacement parameters (Å2 x 103) for C58H60O4. ______________________________________________________________________ x y z U(eq) ______________________________________________________________________ H(13) 7873 -1160 4593 29 H(14) 7478 -117 5224 32 H(15) 6173 993 5106 33 H(17A) 4743 1358 3966 32 H(17B) 4170 1239 4491 32 H(18A) 3698 -175 3809 45 H(18B) 4260 -1104 3642 45 H(19A) 2850 -694 3047 51 H(19B) 3669 207 2978 51
Crystal Structure Data 487
H(23) 4491 2456 5093 30 H(27A) 8559 3595 3959 27 H(27B) 8931 3986 4502 27 H(28A) 7418 2378 3184 33 H(28B) 6951 3234 3486 33 H(29A) 4953 2586 3404 41 H(29B) 5424 1733 3098 41 H(33) 8724 2616 5114 27 H(34) 9639 1313 5267 29 H(35) 10482 468 4632 25 H(37A) 10585 1028 3377 26 H(37B) 11611 772 3742 26 H(38A) 11504 2607 3548 33 H(38B) 10868 3506 3714 33 H(39A) 10144 3590 2913 55 H(39B) 10759 2684 2746 55 H(43) 11709 -787 3838 25 H(47A) 6632 -1228 3373 28 H(47B) 6848 -1970 3753 28 H(48A) 7065 696 3046 32 H(48B) 7532 -269 2891 32 H(49A) 9313 393 2608 39 H(49B) 8951 1370 2805 39 H(11A) 5183 -605 2638 65 H(11B) 3965 -957 2356 65 H(11C) 4502 -1535 2765 65 H(21A) 5611 3528 2788 79 H(21B) 4715 2732 2551 79 H(21C) 6130 2692 2486 79 H(211) 4571 3779 5666 33 H(21D) 4547 4938 6247 58 H(21E) 4886 5889 6031 58 H(21F) 5826 5453 6372 58 H(215) 6832 6471 5832 37 H(216) 8218 7232 5365 38 H(217) 8782 6553 4619 37 H(218) 8151 5090 4394 30 H(31A) 12087 4328 3099 91 H(31B) 12016 3959 2538 91 H(31C) 12698 3425 2929 91 H(41A) 7676 288 2039 66 H(41B) 8561 1147 1951 66 H(41C) 7331 1269 2232 66 H(411) 11955 -2375 3904 27 H(41D) 12277 -3837 4062 55 H(41E) 11565 -4559 3689 55 H(41F) 11098 -4389 4234 55 H(415) 9584 -4990 3591 42 H(416) 7736 -5367 3232 47 H(417) 6557 -4246 2975 46 H(418) 7185 -2751 3134 35 H(53) 1144 5937 -77 30 H(54) 2410 4781 -206 34 H(55) 2850 3897 429 29 H(57A) 1895 3334 1282 34 H(57B) 1774 4190 1657 34 H(58A) -575 4232 1330 83 H(58B) -1249 5146 1351 83 H(59A) -75 4702 2211 150 H(59B) -1212 5288 2171 150 H(65) 6750 4382 1122 25
488 Appendix
H(67A) 6735 5971 1238 27 H(67B) 5777 6335 1617 27 H(68A) 2769 5224 2138 37 H(68B) 2348 6180 2004 37 H(69A) 4276 6847 2230 41 H(69B) 4668 5891 2378 41 H(73) 5498 5512 362 26 H(74) 4598 6226 -259 30 H(75) 3765 7591 -86 25 H(77A) 4038 9083 542 26 H(77B) 3706 8809 1081 26 H(78A) 5709 8932 1752 28 H(78B) 5983 8750 1185 28 H(79A) 7748 8634 1600 32 H(79B) 7301 7641 1393 32 H(85) -460 7435 -57 29 H(87A) -772 6385 538 30 H(87B) -161 6620 1065 30 H(88A) 2171 8576 1553 32 H(88B) 2618 7772 1848 32 H(89A) 596 7190 1909 38 H(89B) 166 8022 1630 38 H(51A) -2486 4047 2032 274 H(51B) -1613 3791 2458 274 H(51C) -1416 3417 1907 274 H(61A) 2821 6843 2857 85 H(61B) 4123 6751 3087 85 H(61C) 3204 5884 3003 85 H(611) 6913 2760 1053 30 H(61D) 7138 1251 906 53 H(61E) 5912 653 793 53 H(61F) 6548 663 1319 53 H(615) 4587 314 1504 37 H(616) 2803 84 1911 43 H(617) 1671 1308 2128 42 H(618) 2278 2724 1893 33 H(71A) 7079 8319 2382 50 H(71B) 7975 7585 2195 50 H(71C) 6559 7339 2179 50 H(81A) 1386 8195 2559 89 H(81B) -11 8319 2484 89 H(81C) 966 9028 2281 89 H(811) -408 8614 -628 32 H(81D) -489 9640 -1206 46 H(81E) 768 10163 -1312 46 H(81F) -184 10639 -970 46 H(815) 1753 11298 -764 31 H(816) 3198 12171 -299 32 H(817) 3895 11644 429 34 H(818) 3282 10225 650 27 ______________________________________________________________________
489
3 Abbreviations
Ac Acetyl
anh. anhydrous
aq aqueous
Ar Aryl
Bn Benzyl
Boc tert-Butyloxycarbonyl
bp boiling point
br broad
Bu Butyl
Bz Benzoyl
C Celsius
calcd. calculated
CMD Concerted metalation-deprotonation
conc. concentrated
COSY Correlation spectroscopy
Cy Cyclohexyl
d day
DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene
DCM dichloromethane
DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone
DMA N,N-Dimethylacetamide
DMF N,N-dimethylformamide
DMSO Dimethyl sulfoxide
EI Electron-impact ionization
eq equivalents
et al. et alii
Et Ethyl
EtOAc Ethyl acetate
eV electron-volt
FAB Fast atom bombardment
g gram
h hour
HFIP 1,1,1,3,3,3hexafluoro-2-propanol
490 Appendix
HMBC Heteronuclear multiple bond coherence
HMQC Heteronuclear multiple quantum coherence
HMTA Hexamethylenetetramine
HPLC High performance liquid chromatography
HRMS High resolution mass spectrometry
Hz Hertz
i iso
IR Infrared
IUPAC International Union of Pure and Applied Chemistry
J coupling constant
l litre
lit. literature
m meta
M molecular weight
M+ molecular ion
MDA Methyl diazoacetate
Me methyl
min minutes
mNBA m-Nitrobenzyl alcohol
MOM Methoxymethyl
mp melting point
MS mass spectrometry
MTBE Methyl tert-butyl ether
n.d. not determinable
NBS N-bromosuccinimide
NMP 1-Methyl-2-pyrrolidinone
NMR Nuclear magnetic resonance
NOE Nuclear Overhauser effect
NOESY Nuclear Overhauser enhancement spectroscopy
Nu Nucleophile
o ortho
p para
PAH Polycyclic aromatic hadrocarbon
PE Petroleum ether (40/60)
Ph Phenyl
Phen Phenanthrene
PIDA (Diacetoxyiodo)benzene
Abbreviations 491
PIFA [Bis(trifluoroacetoxy)iodo]benzene
PivOH Pivalic acid
ppm parts per million
Pr Propyl
Py Pyridyl
Rf Retention factor
ROESY Rotating frame Overhauser enhancement spectroscopy
rt room temperature
SEAr electrophilic aromatic substitution
SNAr nucleophilic aromatic substitution
tert tertiary
TFA Trifluoroacetic acid
TFE 2,2,2-Trifluoroethanol
THF Tetrahydrofuran
TLC Thin-layer chromatography
TMS Trimethylsilyl
UV ultraviolet
Vis visible
493
4 References
1 For reviews and monographs on calixarenes, see: a) C. D. Gutsche, Calixarenes,
The Royal Society of Chemistry, Cambridge, 1989; b) J. Vicens, V. Böhmer (Ed.),
Calixarenes, a Versatile Class of Macrocyclic Compounds, Kluwer, Dordrecht,
1991; c) V. Böhmer and M. A. McKervey, Chemie in unserer Zeit 1991, 25, 195-
207; d) S. Shinkai, Tetrahedron 1993, 49, 8933-8968; e) V. Böhmer, Angew. Chem.
1995, 107, 785-818; Angew. Chem. Int. Ed. Engl. 1995, 34, 713–746; e) A. Ikeda
and S. Shinkai, Chem. Rev. 1997, 97, 1713-1734; f) C. D. Gutsche, Calixarenes
Revisited, The Royal Society of Chemistry, Cambridge, 1998; g) Z. Asfari, V.
Böhmer, J. Harrowfield, J. Vicens (Eds.), Calixarenes 2001, Kluwer, Dordrecht,
The Netherlands, 2001; h) Y. K. Agrawal, J. P. Pancholi and J. M. Vyas, J. Sci. Ind.
Res. 2009, 68, 745-768. 2 a) J.-M. Lehn, Angew. Chem. 1988, 100, 91-116; Angew. Chem. Int. Ed. Engl.
1988, 27, 89-112; b) J.-M. Lehn, Angew. Chem. Int. Ed. Engl. 1990, 29, 1304-1319;
c) J.-M. Lehn, Pure & Appl. Chem. 1994, 66, 1961-1966; d) H.-J. Schneider,
Angew. Chem. Int. Ed. Engl. 2009, 48, 3924-3977. 3 For examples, see: a) F. Arnaud-Neu, E. M. Collins, M. Deasy, G. Ferguson, S. J.
Harris, B. Kaitner, A. J. Lough, M. A. McKervey, E. Marques, B. L. Ruhl, M. J.
Schwing-Weill and E. M. Seward, J. Am. Chem. Soc. 1989, 111, 8681-8691; b) J.
M. Harrowfield, M. I. Ogden, W. R. Richmond, B. W. Skelton and A. H. White, J.
Chem. Soc., Perkin Trans. 2 1993, 2183-2190; c) A. Casnati, A. Pochini, R.
Ungaro, F. Ugozzoli, F. Arnaud, S. Fanni, M.-J. Schwing, R. J. M. Egberink, F. de
Jong and D. N. Reinhoudt, J. Am. Chem. Soc. 1995, 117, 2767-2777; c) P. Lhoták
and S. Shinkai, J. Phys. Org. Chem. 1997, 10, 273-285; d) J. S. Kim, O. J. Shon, J.
W. Ko, M. H. Cho, I. Y. Yu and J. Vicens, J. Org. Chem. 2000, 65, 2386-2392; e)
A. Arduini, D. Demuru, A. Pochini and A. Secchi, Chem. Commun. 2005, 645-647;
f) O. Danylyuk and K. Suwinska, Chem. Commun. 2009, 5799-5813. 4 For examples see: a) N. Pelizzi, A. Casnati and R. Ungaro, Chem. Commun. 1998,
2607-2608; b) J. Scheerder, M. Fochi, J. F. J. Engbersen and D. N. Reinhoudt, J.
Org. Chem. 1994, 59, 7815-7820; c) A. Casnati, L. Pirondini, N. Pelizzi and R.
Ungaro, Supramol. Chem. 2000, 12, 53-65.
494 Appendix
5 For examples see: a) G. D. Andreetti, J. Chem. Soc., Chem. Commun. 1979, 1005-
1007; b) G. D. Andreetti, A. Pochini and R. Ungaro, J. Chem. Soc., Perkin Trans. 2
1983, 1773-1779; c) L. J. Bauer and C. D. Gutsche, J. Am. Chem. Soc. 1985, 107,
6063-6069; d) A. Arduini, W. M. McGregor, D. Paganuzzi, A. Pochini, A. Secchi,
F. Ugozzoli and R. Ungaro, J. Chem. Soc., Perkin Trans. 2 1996, 839-846; e) A.
Arduini, W. M. McGregor, A. Pochini, A. Secchi, F. Ugozzoli and R. Ungaro, J.
Org. Chem. 1996, 61, 6881-6887. 6 For recent reviews, see: a) W. Sliwa, Croatica Chemica Acta 2002, 75, 131-153; b)
I. Leray and B. Valeur, Eur. J. Inorg. Chem. 2009, 3525-3535; c) W. Sliwa and M.
Deska, ARKIVOC 2008, 1, 87-127; d) E. Shokova and V. Kovalev, Russ. J. Org.
Chem. 2009, 45, 1275-1314; e) S. Siddiqui and P. J. Cragg, Mini-Reviews in
Organic Chemistry 2009, 6, 283-299; f) W. Sliwa and T. Girek, J. Incl. Phenom.
Macrocycl. Chem. 2010, 66, 15-41. 7 For reviews on inherently chiral calixarenes, see: S.-Y. Li, Y.-W. Xu, J.-M. Liu and
C.-Y. Su, Int. J. Mol. Sci. 2011, 12, 429-455. 8 G. McMahon, S. O’Malley and K. Nolan, ARKIVOC 2003, 7, 23-31. 9 V. Souchon, I. Leray and B. Valeur, Chem. Commun. 2006, 4224-4226. 10 a) V. Souchon, S. Maisonneuve, O. David, I. Leray, J. Xie and B. Valeur,
Photochem. Photobiol. Sci. 2008, 7, 1323-1331; b) S. Y. Park, J. H. Yoon, C. S.
Hong, R. Souane, J. S. Kim, S. E. Matthews and J. Vicens, J. Org. Chem. 2008, 73,
8212-8218. 11 X. Zeng, H. Sun, L. Chen, X. Leng, F. Xu, Q. Li, X. He, W. Zhang and Z.-Z.
Zhang, Org. Biomol. Chem. 2003, 1, 1073-1079. 12 S. K. Kim, J. H. Bok, R. A. Bartsch, J. Y. Lee and J. S. Kim, Org. Lett. 2005, 7,
4839-4842. 13 A. Casnati, A. Sartori, L. Pirondini, F. Bonetti, N. Pelizzi, F. Sansone, F. Ugozzoli
and R. Ungaro, Supramol. Chem. 2006, 18, 199 - 218. 14 For a recent review, see: F. Sansone, L. Baldini, A. Casnati and R. Ungaro, New J.
Chem. 2010, 34, 2715-2728. 15 A. Casnati, M. Fabbi, N. Pelizzi, A. Pochini, F. Sansone and R. Ungaro, Bioorg.
Med. Chem. Lett. 1996, 6, 2699-2704.
References 495
16 V. Sidorov, F. W. Kotch, G. Abdrakhmanova, R. Mizani, J. C. Fettinger and J. T.
Davis, J. Am. Chem. Soc. 2002, 124, 2267-2278. 17 R. Cacciapaglia, A. Casnati, L. Mandolini, D. N. Reinhoudt, R. Salvio, A. Sartori
and R. Ungaro, J. Am. Chem. Soc. 2006, 128, 12322-12330. 18 G.-y. Qing, Y.-b. He, F. Wang, H.-j. Qin, C.-g. Hu and X. Yang, Eur. J. Org.
Chem. 2007, 2007, 1768-1778. 19 S. Shirakawa, A. Moriyama and S. Shimizu, Eur. J. Org. Chem. 2008, 2008, 5957-
5964. 20 For a review on calixarenes in metal-based catalysis, see: D. M. Homden and C.
Redshaw, Chem. Rev. 2008, 108, 5086-5130. 21 C. Dieleman, S. Steyer, C. Jeunesse and D. Matt, J. Chem. Soc., Dalton Trans.
2001, 2508-2517. 22 K. Araki, A. Yanagi and S. Shinkai, Tetrahedron 1993, 49, 6763-6772. 23 J. Seitz and G. Maas, Chem. Commun. 2002, 338-339. 24 M. Frank, G. Maas and J. Schatz, Eur. J. Org. Chem. 2004, 2004, 607-613. 25 For reviews, see: a) B. König and M. Hechavarria Fonseca, Eur. J. Inorg. Chem.
2000, 2303-2310; b) W. Sliwa, Chemistry of Heterocyclic Compounds 2004, 40,
683-700; c) S. Kumar, D. Paul and H. Singh, ARKIVOC 2006, 9, 17-25; d) M.-X.
Wang, Chem. Commun. 2008, 4541-4551. 26 M. H. Patel and P. S. Shrivastav, Chem. Commun. 2009, 586-588. 27 For a review on oxacalixarenes, see: W. Maes and W. Dehaen, Chem. Soc. Rev.
2008, 37, 2393-2402. 28 a) N. Sommer and H. A. Staab, Tetrahedron Lett. 1966, 7, 2837-2841; b) P. A.
Lehmann, Tetrahedron 1974, 30, 727-733; c) F. Bottino, S. Foti and S. Pappalardo,
Tetrahedron 1976, 32, 2567-2570. 29 G. W. Smith, Nature 1963, 198, 879. 30 a) H. Kumagai, M. Hasegawa, S. Miyanari, Y. Sugawa, Y. Sato, T. Hori, S. Ueda,
H. Kamiyama and S. Miyano, Tetrahedron Lett. 1997, 38, 3971-3972; b) N. Kon,
N. Iki and S. Miyano, Tetrahedron Lett. 2002, 43, 2231-2234.
496 Appendix
31 For reviews on thiacalixarenes, see: a) P. Lhoták, Eur. J. Org. Chem. 2004, 1675-
1692; b) N. Morohashi, F. Narumi, N. Iki, T. Hattori and S. Miyano, Chem. Rev.
2006, 106, 5291-5316. 32 J. L. Katz, M. B. Feldman and R. R. Conry, Org. Lett. 2004, 7, 91-94. 33 H. Tsue, K. Ishibashi, H. Takahashi and R. Tamura, Org. Lett. 2005, 7, 2165-2168. 34 W. Fukushima, T. Kanbara and T. Yamamoto, Synlett 2005, 19, 2931-2934. 35 Further azacalixarenes: a) A. Ito, Y. Ono and K. Tanaka, J. Org. Chem. 1999, 64,
8236-8241; b) A. Ito, Y. Ono and K. Tanaka, Angew. Chem. Int. Ed. Engl. 2000,
39, 1072-1075. 36 A. Baeyer, Ber. Dtsch. Chem. Ges. 19 1886, 2184. 37 For reviews, see: a) C. Floriani, Chem. Commun. 1996, 1257-1263; b) P. A. Gale, J.
L. Sessler and V. Kral, Chem. Commun. 1998, 1-8; c) P. A. Gale, P. Anzenbacher
Jr and J. L. Sessler, Coord. Chem. Rev. 2001, 222, 57-102; d) W. Sliwa,
Heterocycles 2002, 57, 169-185. 38 P. A. Gale, J. L. Sessler, V. Král and V. Lynch, J. Am. Chem. Soc. 1996, 118, 5140-
5141. 39 V. Král, P. A. Gale, P. Anzenbacher, Jr., K. Jursíková, V. Lynch and J. L. Sessler,
Chem. Commun. 1998, 9-10. 40 R. Pajewski, R. Ostaszewski and J. Jurczak, Org. Prep. Proced. Int. 2000, 32, 394 -
397. 41 a) M.-X. Wang, X.-H. Zhang and Q.-Y. Zheng, Angew. Chem. Int. Ed. Engl. 2004,
43, 838-842; b) M.-X. Wang and H.-B. Yang, J. Am. Chem. Soc. 2004, 126, 15412-
15422. 42 a) C. D. Gutsche, M. Iqbal and D. Stewart, J. Org. Chem. 1986, 51, 742-745; b) B.
Dhawan, S.-I. Chen and C. D. Gutsche, Makromol. Chem. 1987, 188, 921-950. 43 Synthesis of calix[n]arenes: a) C. D. Gutsche and M. Iqbal, Org. Synth. 1990, 68,
234-237; b) C. D. Gutsche, B. Dhawan, M. Leonis and D. Stewart, Org. Synth.
1990, 68, 238-242; c) J. H. Munch and C. D. Gutsche, Org. Synth. 1990, 68, 243-
246. 44 a) A. Ninagawa, H. Matsuda, Makromol. Chem., Rapid Commun. 1982, 3, 65-67;
b) D. R. Stewart, C. D. Gutsche, Organic Preparations and Procedures Int. 1993,
25, 137-139; c) M. A. Markowitz, V. Janout, D. G. Castner and S. L. Regen, J. Am.
References 497
Chem. Soc. 1989, 111, 8192-8200; d) D. R. Stewart and C. D. Gutsche, J. Am.
Chem. Soc. 1999, 121, 4136-4146. 45 a) H. Kämmerer and G. Happel, Makromol. Chem. 1978, 179, 1199-1207; b) H.
Kämmerer and G. Happel, Makromol. Chem. 1980, 181, 2049-2062; c) H.
Kämmerer, G. Happel and B. Mathiasch, Makromol. Chem. 1981, 182, 1685-1694. 46 K. H. No and C. D. Gutsche, J. Org. Chem. 1982, 47, 2713-2719. 47 M. Tashiro, Synthesis 1979, 921-936. 48 a) C. D. Gutsche and J. A. Levine, J. Am. Chem. Soc. 1982, 104, 2652-2653; b) C.
D. Gutsche, J. A. Levine and P. K. Sujeeth, J. Org. Chem. 1985, 50, 5802-5806; c)
C. D. Gutsche and L.-G. Lin, Tetrahedron 1986, 42, 1633-1640. 49 For examples, see: a) J.-D. van Loon, A. Arduini, W. Verboom, R. Ungaro, G. J.
van Hummel, S. Harkema and D. N. Reinhoudt, Tetrahedron Lett. 1989, 30, 2681-
2684, b) A. Dondoni, A. Marra, M.-C. Scherrmann, A. Casnati, F. Sansone and R.
Ungaro, Chem. Eur. J. 1997, 3, 1774-1782; c) E. Pinkhassik, V. Sidorov and I.
Stibor, J. Org. Chem. 1998, 63, 9644-9651. 50 For examples, see: a) K. Iwamoto, A. Yanagi, K. Araki and S. Shinkai, Chem. Lett.
1991, 473-476; b) A. Ikeda, T. Nagasaki, K. Araki and S. Shinkai, Tetrahedron
1992, 48, 1059-1070; c) G. Dyker, M. Mastalerz and K. Merz, Eur. J. Org. Chem.
2003, 4355-4362. 51 G. D. Andreetti, V. Böhmer, J. G. Jordon, M. Tabatabai, F. Ugozzoli, W. Vogt and
A. Wolff, J. Org. Chem. 1993, 58, 4023-4032. 52 a) W. Verboom, P. J. Bodewes, G. van Essen, P. Timmerman, G. J. van Hummel,
S. Harkema and D. N. Reinhoudt, Tetrahedron 1995, 51, 499-512; b) M. Mascal,
R. T. Naven and R. Warmuth, Tetrahedron Lett. 1995, 36, 9361-9364; c) P. A.
Reddy and C. D. Gutsche, J. Org. Chem. 1993, 58, 3245-3251; d) S. A. Herbert and
G. E. Arnott, Org. Lett. 2009, 11, 4986-4989. 53 K. Iwamoto, K. Araki and S. Shinkai, Tetrahedron 1991, 47, 4325-4342. 54 C. D. Gutsche, B. Dhawan, J. A. Levine, K. H. No and L. J. Bauer, Tetrahedron
Lett. 1983, 39, 409-426.
498 Appendix
55 a) C. D. Gutsche, B. Dhawan, K. H. No and R. Muthukrishnan, J. Am. Chem. Soc.
1981, 103, 3782-3792; b) C. D. Gutsche, B. Dhawan, K. H. No and R.
Muthukrishnan, J. Am. Chem. Soc. 1984, 106, 1981. 56 a) C. D. Gutsche and L. J. Bauer, Tetrahedron Letters 1981, 22, 4763-4766; b) C.
D. Gutsche and L. J. Bauer, J. Am. Chem. Soc. 1985, 107, 6052-6059. 57 a) K. Araki, K. Iwamoto, S. Shinkai and T. Matsuda, Chem. Lett. 1989, 1747-1750;
b) K. Iwamoto, K. Araki and S. Shinkai, J. Org. Chem. 1991, 56, 4955-4962. 58 a) K. Iwamoto, K. Fujimoto, T. Matsuda and S. Shinkai, Tetrahedron Lett. 1990,
31, 7169-7172; b) L. C. Groenen, J.-D. van Loon, W. Verboom, S. Harkema, A.
Casnati, R. Ungaro, A. Pochini, F. Ugozzoli and D. N. Reinhoudt, J. Am. Chem.
Soc. 1991, 113, 2385-2392; c) W. Verboom, S. Datta, Z. Asfari, S. Harkema and D.
N. Reinhoudt, J. Org. Chem. 1992, 57, 5394-5398. 59 C. Jaime, J. de Mendoza, P. Prados, P. M. Nieto and C. Sanchez, J. Org. Chem.
1991, 56, 3372-3376. 60 a) M. Conner, V. Janout and S. L. Regen, J. Am. Chem. Soc. 1991, 113, 9670-9671;
b) A. Ikeda, H. Tsuzuki and S. Shinkai, J. Chem. Soc., Perkin Trans. 2 1994, 1994,
2073-2080; c) A. Arduini, M. Fabbi, M. Mantovani, L. Mirone, A. Pochini, A.
Secchi and R. Ungaro, J. Org. Chem. 1995, 60, 1454-1457. 61 a) H. Goldmann, W. Vogt, E. Paulus and V. Böhmer, J. Am. Chem. Soc. 1988, 110,
6811-6817; b) M. Jorgensen and F. C. Krebs, J. Chem. Soc., Perkin Trans. 2 2000,
1929-1934. 62 a) P. D. J. Grootenhuis, P. A. Kollman, L. C. Groenen, D. N. Reinhoudt, G. J. van
Hummel, F. Ugozzoli and G. D. Andreetti, J. Am. Chem. Soc. 1990, 112, 4165-
4176; b) T. Harada, J. M. Rudzinski, E. Osawa and S. Shinkai, Tetrahedron 1993,
49, 5941-5954. 63 For examples, see: a) S. Shinkai, S. Mori, H. Koreishi, T. Tsubaki and O. Manabe,
J. Am. Chem. Soc. 1986, 108, 2409-2416; b) S. Shinkai, T. Arimura, H. Satoh and
O. Manabe, J. Chem. Soc., Chem. Commun. 1987, 1495-1496; c) T. Arimura, H.
Kawabata, T. Matsuda, T. Muramatsu, H. Satoh, K. Fujio, O. Manabe and S.
Shinkai, J. Org. Chem. 1991, 56, 301-306; d) A. Ikeda, T. Nagasaki and S. Shinkai,
J. Phys. Org. Chem. 1992, 5, 699-710; e) A. Sirit and M. Yilmaz, Turk. J. Chem.
2009, 33, 159-200 (Review).
References 499
64 For reviews on inherently chiral calixarenes, see: a) V. Böhmer, D. Kraft and M.
Tabatabai, Journal of Inclusion Phenomena and Molecular Recognition in
Chemistry 1994, 19, 17-39; b) S.-Y. Li, Y.-W. Xu, J.-M. Liu and C.-Y. Su, Int. J.
Mol. Sci. 2011, 12, 429-455. 65 A. Dalla Cort, L. Mandolini, C. Pasquini and L. Schiaffino, New J. Chem. 2004, 28,
1198-1199. 66 A. Szumna, Chem. Soc. Rev. 2010, 39, 4274-4285. 67 Example of asymmetric functionalization of the upper rim: V. Böhmer, F.
Marschollek and L. Zetta, J. Org. Chem. 1987, 52, 3200-3205. 68 Example of asymmetric functionalization of the lower rim: C.-m. Shu and W.-s.
Chung, J. Org. Chem. 1999, 64, 2673-2679. 69 Example of asymmetric functionalization of the lower rim at upper and lower rim:
M. O. Vysotsky, M. A. Tairov, V. V. Piroshenko and V. I. Kalchenko, Tetrahedron
Lett. 1998, 39, 6057-6060. 70 K. Iwamoto, H. Shimizu, K. Araki and S. Shinkai, J. Am. Chem. Soc. 1993, 115,
3997-4006. 71 a) A. Ikeda, M. Yoshimura, P. Lhotak and S. Shinkai, J. Chem. Soc., Perkin Trans.
1 1996, 1945-1950; b) R. Miao, Q.-Y. Zheng, C.-F. Chen and Z.-T. Huang, J. Org.
Chem. 2005, 70, 7662-7671. 72 a) M. Mastalerz, PhD Thesis, Ruhr-Universität Bochum, 2005; b) M. Mastalerz, W.
Hüggenberg and G. Dyker, Eur. J. Org. Chem. 2006, 3977-3987. 73 W. Hüggenberg Master Thesis, Ruhr-Universität Bochum, 2006. 74 M. Mastalerz and G. Dyker, Synlett 2006, 9, 1419-1421. 75 For a review, see: P. E. Georghiu, Z. Li, M. Ashram, S. Chowdhury, S. Mizyed, A.
H. Tran, H. Al-Saraierh and D. O. Miller, Synlett 2005, 6, 879-891. 76 S. Chowdhury and P. E. Georghiu, J. Org. Chem. 2002, 67, 6808-6811. 77 O. G. Barton, B. Neumann, H.-G. Stammler and J. Mattay, Org. Biomol. Chem.
2008, 6, 104-111. 78 W. Hüggenberg, A. Seper, I. M. Oppel and G. Dyker, Eur. J. Org. Chem. 2010,
6786-6797.
500 Appendix
79 a) H. Hopf, H. Greiving, P. G. Jones and P. Bubenitschek, Angew. Chem. Int. Ed.
Engl. 1995, 34, 685-687; b) H. Hopf, H. Greiving, C. Beck, I. Dix, P. G. Jones, J.-
P. Desvergne and H. Bouas-Laurent, Eur. J. Org. Chem. 2005, 567-581. 80 a) S. Kanamathareddy and C. D. Gutsche, J. Org. Chem. 1996, 61, 2511-2516; b)
M. Vézina, J. Gagnon, K. Villeneuve, M. Drouin and P. D. Harvey,
Organometallics 2001, 20, 273-281; c) J. Gagnon, M. Vézina, M. Drouin and P. D.
Harvey, Can. J. Chem. 2001, 79, 1439-1446. 81 L. C. Groenen, B. H. M. Ruel, A. Casnati, P. Timmerman, W. Verboom, S.
Harkema, A. Pochini, R. Ungaro and D. N. Reinhoudt, Tetrahedron Lett. 1991, 32,
2675-2678. 82 S. Shimizu, A. Moriyama, K. Kito and Y. Sasaki, J. Org. Chem. 2003, 68, 2187-
2194. 83 C.-m. Shu, T.-s. Yuan, M.-c. Ku, Z.-c. Ho, W.-c. Liu, F.-s. Tang and L.-G. Lin,
Tetrahedron 1996, 52, 9805-9818. 84 G. Hennrich, M. T. Murillo, P. Prados, H. Al-Saraierh, A. El-Dali, D. W.
Thompson, J. Collins, P. E. Georghiou, A. Teshome, I. Asselberghs and K. Clays,
Chem. Eur. J. 2007, 13, 7753-7761. 85 M. Larsen and M. Jørgensen, J. Org. Chem. 1996, 61, 6651-6655. 86 A. Sartori, A. Casnati, L. Mandolini, F. Sansone, D. N. Reinhoudt and R. Ungaro,
Tetrahedron 2003, 59, 5539-5544. 87 M. Larsen, F. C. Krebs, M. Jørgensen and N. Harrit, J. Org. Chem. 1998, 63, 4420-
4424. 88 A. M. Sanseverino and M. C. S. de Mattos, J. Braz. Chem. Soc. 2001, 12, 685-687. 89 I. R. Robertson and J. T. Sharp, Tetrahedron 1984, 40, 3095-3112. 90 E. E. Schweizer and A. T. Wehman, J. Chem. Soc. C 1971, 343-346. 91 a) N. Miyaura and A. Suzuki, Chem. Rev. 1995, 95, 2457-2483; b) A. Suzuki,
Journal of Organometallic Chemistry 1999, 576, 147-168; c) H. Gröger, J. Prakt.
Chem. 2000, 342, 334-339; d) A. Suzuki, Chem. Commun. 2005, 4759-4763. 92 a) J. K. Stille, Angew. Chem. Int. Ed. Engl. 1986, 25, 508-524; b) M. A. J. Duncton
and G. Pattenden, J. Chem. Soc., Perkin Trans. 1 1999, 1235-1246. 93 a) E. Negishi, A. O. King and N. Okukado, J. Org. Chem. 1977, 42, 1821-1823; b)
E. Negishi, T. Takahashi and A. O. King, Org. Synth. 1988, Coll. Vol. 8, 430-434.
References 501
94 K. Tamao, K. Sumitani and M. Kumada, J. Am. Chem. Soc. 1972, 94, 4374-4376. 95 For reviews on syntheses of biaryls, see: a) J. Hassan, M. Sévignon, C. Gozzi, E.
Schulz and M. Lemaire, Chem. Rev. 2002, 102, 1359-1470; b) O. Reiser, Chemie in
unserer Zeit 2001, 35, 94-100; c) L. Yin and J. Liebscher, Chem. Rev. 2007, 107,
133-173. 96 B. Liégault, D. Lee, M. P. Huestis, D. R. Stuart and K. Fagnou, J. Org. Chem.
2008, 73, 5022-5028. 97 D. R. Stuart and K. Fagnou, Science 2007, 316, 172-175. 98 For reviews on direct arylations see: a) F. Kakiuchi and N. Chatani, Adv. Synth.
Catal. 2003, 345, 1077-1101; b) L.-C. Campeau and K. Fagnou, Chem. Commun.
2006, 1253-1264; c) L.-C. Campeau, D. R. Stuart and K. Fagnou, Aldrichimica
Acta 2007, 40, 35-41; d) D. Alberico, M. E. Scott and M. Lautens, Chem. Rev.
2007, 107, 174-238. e) G. P. McGlacken and L. M. Bateman, Chem. Soc. Rev.
2009, 38, 2447-2464; f) L. Ackermann, R. Vicente and A. R. Kapdi, Angew. Chem.
2009, 121, 9976-10011; for reviews on direct arylation of heteroaromatic
compounds see: a) T. Satoh and M. Miura, Chem. Lett. 2007, 36, 200-205; b) I. V.
Seregin and V. Gevorgyan, Chem. Soc. Rev. 2007, 36, 1173-1193; c) T. Harschneck
and S. F. Kirsch, Nachrichten aus der Chemie 2010, 58, 544-547 99 L.-C. Campeau, M. Parisien, A. Jean and K. Fagnou, J. Am. Chem. Soc. 2006, 128,
581-590. 100 a) D. Garcia-Cuadrado, A. A. C. Braga, F. Maseras and A. M. Echavarren, J. Am.
Chem. Soc. 2006, 128, 1066-1067; b) D. García-Cuadrado, P. de Mendoza, A. A.
C. Braga, F. Maseras and A. M. Echavarren, J. Am. Chem. Soc. 2007, 129, 6880-
6886; c) M. Lafrance, C. N. Rowley, T. K. Woo and K. Fagnou, J. Am. Chem. Soc.
2006, 128, 8754-8756. 101 S. I. Gorelsky, D. Lapointe and K. Fagnou, J. Am. Chem. Soc. 2008, 130, 10848-
10849. 102 B. S. Lane, M. A. Brown and D. Sames, J. Am. Chem. Soc. 2005, 127, 8050-8057. 103 O. Daugulis, A. Lazareva, Org. Lett. 2006, 8, 5211-5213.
502 Appendix
104 a) M. Lafrance and K. Fagnou, J. Am. Chem. Soc. 2006, 128, 16496-16497; b) B.
Liégault, D. Lapointe, L. Caron, A. Vlassova and K. Fagnou, J. Org. Chem. 2009,
74, 1826-1834. 105 J.-P. Leclerc, M. André and K. Fagnou, J. Org. Chem. 2006, 71, 1711-1714. 106 Z. Marcinow, A. Sygula, A. Ellern and P. W. Rabideau, Org. Lett. 2001, 3, 3527-
3529. 107 a) H. A. Reisch, M. S. Bratcher and L. T. Scott, Org. Lett. 2000, 2, 1427-1430; b)
X. H. Cheng, S. Höger and D. Fenske, Org. Lett. 2003, 5, 2587-2589; c) Y.
Avlasevich, S. Müller, P. Erk and K. Müllen, Chem. Eur. J. 2007, 13, 6555-6561;
d) S. Pascual, P. de Mendoza and A. M. Echavarren, Org. Biomol. Chem. 2007, 5,
2727-2734. 108 For reviews see: a) L. J. Gooßen, N. Rodrìguez and K. Gooßen, Angew. Chem. Int.
Ed. Engl. 2008, 47, 3100-3120; b) S. M. Bonesi, M. Fagnoni and A. Albini, Angew.
Chem. Int. Ed. Engl. 2008, 47, 10022-10025. 109 a) L. J. Gooßen, G. Deng and L. M. Levy, Science 2006, 313, 662-664; b) A.
Voutchkova, A. Coplin, N. E. Leadbeater and R. H. Crabtree, Chem. Commun.
2008, 6312-6314; c) C. Wang, I. Piel and F. Glorius, J. Am. Chem. Soc. 2009, 131,
4194-4195. 110 O. G. Barton, PhD Thesis, Universität Bielefeld, 2008. 111 J. N. Moorthy and S. Samanta, J. Org. Chem. 2007, 72, 9786-9789. 112 a) R.-Y. Kuo, C.-C. Wu, F.-R. Chang, J.-L. Yeh, I.-J. Chen, Y.-C. Wu, Bioorg.
Med. Chem. Lett. 2003, 13, 821-823; b) M. Lafrance, N. Blaquière and K. Fagnou,
Chem. Commun. 2004, 2874-2875. 113 M. Carril, R. SanMartin, I. Tellitu and E. Domínguez, Org. Lett. 2006, 8, 1467-
1470. 114 a) G. Dyker, J. Org. Chem. 1993, 58, 234-238; b) J. J. González, N. García, B.
Gómez-Lor and A. M. Echavarren, J. Org. Chem. 1997, 62, 1286-1291. 115 D. E. Ames and A. Opalko, Tetrahedron 1984, 40, 1919-1925. 116 T. Satoh, M. Miura and M. Nomura, Journal of Organometallic Chemistry 2002,
653, 161-166. 117 D. Kuck, A. Schuster, R. A. Krause, J. Tellenbröker, C. P. Exner, M. Penk, H.
Bögge and A. Müller, Tetrahedron 2001, 57, 3587-3613.
References 503
118 V. B. Kumbhar, A. R. Joseph, A. D. Natu, R. S. Kusurkar and M. V. Paradkar, J.
Chem. Res. 2007, 590-593. 119 a) C. D. Gutsche and P. F. Pagoria, J. Org. Chem. 1985, 50, 5795-5802; b) Z.-T.
Huang and G.-Q. Wang, Chem. Ber. 1994, 127, 519-523; c) S. Kumar, H. M.
Chawla and R. Varadarajan, Tetrahedron Lett. 2002, 43, 2495-2498. 120 K. H. No and M. Hong, J. Chem. Soc., Chem. Commun. 1990, 572-573. 121 P. Kuhn, D. Sémeril, C. Jeunesse, D. Matt, P. J. Lutz, R. Louis and M. Neuburger,
Dalton Trans. 2006, 3647-3659. 122 A. Yoshida, K. Goto and T. Kawashima, Bull. Chem. Soc. Jpn. 2006, 79, 793-795. 123 a) G. Dyker, M. Mastalerz and I. M. Müller, Eur. J. Org. Chem. 2005, 3801-3812;
b) G. Hennrich, M. T. Murillo, P. Prados, K. Song, I. Asselberghs, K. Clays, A.
Persoons, J. Benet-Buchholz and J. De Mendoza, Chem. Commun. 2005, 2747-
2749. 124 C. Huynh and G. Linstrumelle, Tetrahedron 1988, 44, 6337-6344. 125 a) S. J. Havens and P. M. Hergenrother, J. Org. Chem. 2002, 50, 1763-1765; b) Y.
Kuramochi, A. S. D. Sandanayaka, A. Satake, Y. Araki, K. Ogawa, O. Ito and Y.
Kobuke, Chem. Eur. J. 2009, 15, 2317-2327. 126 I. V. Alabugin, K. Gilmore, S. Patil, M. Manoharan, S. V. Kovalenko, R. J. Clark
and I. Ghiviriga, J. Am. Chem. Soc. 2008, 130, 11535-11545. 127 L.-C. Campeau, P. Thansandote and K. Fagnou, Org. Lett. 2005, 7, 1857-1860. 128 C. E. Miller, J. Chem. Ed. 1965, 42, 254-259. 129 B. Klenke and W. Friedrichsen, J. Chem. Soc., Perkin Trans. 1 1998, 3377-3379. 130 a) S. Kajigaeshi, T. Kakinami, H. Yamasaki, S. Fujisaki, M. Kondo and T.
Okamoto, Chem. Lett. 1987, 2109-2112; b) S. Kajigaeshi, T. Kakinami, M.
Moriwaki, S. Fujisaki, K. Maeno and T. Okamoto, Synthesis 1988, 545-546. 131 A. Dondoni, C. Ghiglione, A. Marra and M. Scoponi, J. Org. Chem. 1998, 63,
9535-9539. 132 R. B. Bedford, S. L. Hazelwood (née Welch), M. E. Limmert, D. A. Albisson, S.
M. Draper, P. N. Scully, S. J. Coles and M. B. Hursthouse, Chem. Eur. J. 2003, 9,
3216-3227. 133 F. Sannicolo, Gazz. Chim. Ital. 1985, 115, 91-95.
504 Appendix
134 T. Yamato, T. Furukawa, S. Saito, K. Tanaka and H. Tsuzuki, New. Chem. Lett.
2002, 26, 1035-1042. 135 S. Nahm and S. M. Weinreb, Tetrahedron Letters 1981, 22, 3815-3818. 136 M. S. Malamas, W. F. Fobare, W. R. Solvibile, F. E. Lovering, J. S. Condon, A. J.
Robichaud, US Patent 7732457. 137 C. Bonini, L. Chiummiento, M. Funicello, M. T. Lopardo, P. Lupattelli, A. Laurita
and A. Cornia, J. Org. Chem. 2008, 73, 4233-4236. 138 H. Plieninger, G. Ege and M. I. Ullah, Chem. Ber. 1963, 96, 1610-1617. 139 Reviews on hypervalent iodine reagents in general: a) P. J. Stang and V. V.
Zhdankin, Chem. Rev. 1996, 96, 1123-1178; b) A. Varvoglis, Tetrahedron 1997,
53, 1179-1255; c) V. V. Zhdankin and P. J. Stang, Chem. Rev. 2002, 102, 2523-
2584; d) T. Wirth, Angew. Chem. Int. Ed. 2005, 44, 3656-3665. 140 Reviews on PIFA: a) G. Pohnert, J. Prakt. Chem. 2000, 342, 731-734; b) X.-Y.
Han, Synlett 2006, 17, 2851-2852. 141 a) M. D. Hossain and T. Kitamura, Bull. Chem. Soc. Jpn. 2006, 79, 142-144; b) T.
K. Page and T. Wirth, Synthesis 2006, 18, 3153-3155. 142 a) J. S. Swenton, K. Carpenter, Y. Chen, M. L. Kerns and G. W. Morrow, J. Org.
Chem. 1993, 58, 3308-3316; b) J. S. Swenton, A. Callinan, Y. Chen, J. J. Rohde,
M. L. Kerns and G. W. Morrow, J. Org. Chem. 1996, 61, 1267-1274. 143 a) A. E. Fleck, J. A. Hobart and G. W. Morrow, Synth. Commun. 1992, 22, 179-
187; b) A. McKillop, L. McLaren and R. J. K. Taylor, J. Chem. Soc., Perkin Trans.
1 1994, 2047-2048; c) O. Karam, J.-C. Jacquesy and M.-P. Jouamnetaud,
Tetrahedron Lett. 1994, 35, 2541-2544. 144 a) K. V. Rama Krishna, K. Sujatha and R. S. Kapil, Tetrahedron Lett. 1990, 31,
1351-1352; b) A. Callinan, Y. Chen, G. W. Morrow and J. S. Swenton,
Tetrahedron Lett. 1990, 31, 4551-4552; c) Y. Kita, T. Takada, M. Gyoten, H.
Tohma, M. H. Zenk and J. Eichhorn, J. Org. Chem. 1996, 61, 5857-5864. 145 T. Takada, M. Arisawa, M. Gyoten, R. Hamada, H. Tohma and Y. Kita, J. Org.
Chem. 1998, 63, 7698-7706. 146 a) Y. Kita, M. Arisawa, M. Gyoten, M. Nakajima, R. Hamada, H. Tohma and T.
Takada, J. Org. Chem. 1998, 63, 6625-6633; b) Y. Kita, M. Egi, T. Takada and H.
Tohma, Synthesis 1999, 5, 885-897.
References 505
147 T. C. Bruice, N. Kharasch and R. J. Winzler, J. Org. Chem. 1953, 18, 83-91. 148 B. Miller and M. P. McLaughlin, J. Org. Chem. 1982, 47, 5204-5207. 149 A. Fischer and G. N. Henderson, Can. J. Chem. 1983, 61, 1045-1052. 150 M. Mastalerz, G. Dyker, U. Flörke, G. Henkel, I. M. Oppel and K. Merz, Eur. J.
Org. Chem. 2006, 4951-4962. 151 Y. Kita, H. Tohma, M. Inagaki, K. Hatanaka and T. Yakura, J. Am. Chem. Soc.
1992, 114, 2175-2180. 152 J. Guillon, J.-M. Leger, C. Dapremont, L. A. Denis, P. Sonnet, S. Massip and C.
Jarry, Supramol. Chem. 2004, 16, 319-329. 153 H. Gilman and B. J. Gaj, J. Org. Chem. 1957, 22, 447-449. 154 R. M. McKinlay and J. L. Atwood, Angew. Chem. Int. Ed. Engl. 2007, 46, 2394-
2397. 155 M. Parisien, D. Valette and K. Fagnou, J. Org. Chem. 2005, 70, 7578-7584. 156 T. Takada, M. Arisawa, M. Gyoten, R. Hamada, H. Tohma and Y. Kita, J. Org.
Chem. 1998, 63, 7698-7706. 157 H. Hamamoto, G. Anilkumar, H. Tohma and Y. Kita, Chem. Eur. J. 2002, 8, 5377-
5383. 158 For reviews on tetrazines see: a) M. J. Hearn and F. Levy, Org. Prep. Proced. Int.
1987, 19, 215-248; b) N. Saracoglu, Tetrahedron 2007, 63, 4199-4236; c) G.
Clavier and P. Audebert, Chem. Rev. 2010, 110, 3299-3314. 159 Y.-H. Gong, P. Audebert, G. Clavier, F. Miomandre, J. Tang, S. Badre, R. Meallet-
Renault and E. Naidus, New J. Chem. 2008, 32, 1235-1242. 160 For a review on the coordination chemistry of tetrazines see: W. Kaim, Coord.
Chem. Rev. 2002, 230, 127-139. 161 a) W.-J. Wang and J.-S. Wang, Mol. Cryst. Liq. Cryst. 2005, 440, 147-152; b) C.-J.
Hsu, S.-W. Tang, J.-S. Wang and W.-J. Wang, Mol. Cryst. Liq. Cryst. 2006, 456,
201-208. 162 a) A. Pinner, Chem. Ber. 1893, 26, 2126-2135; b) A. Pinner, Chem. Ber. 1897, 30,
1871-1890.
506 Appendix
163 a) N. O. Abdel-Rahman, M. A. Kira and M. N. Tolba, Tetrahedron Lett. 1968, 9,
3871-3872; b) P. Audebert, S. d. Sadki, F. Miomandre, G. Clavier, M. C. Vernières,
M. Saouda and P. Hapiot, New. J. Chem. 2004, 28, 387-392. 164 V. M. Tsefrikas, S. Arns, P. M. Merner, C. C. Warford, B. L. Merner, L. T. Scott
and G. J. Bodwell, Org.Lett. 2006, 8, 5195-5198. 165 R. Stolle, J. Prakt. Chem. 1906, 278-300. 166 N. Biedermann and J. Sauer, Tetrahedron Lett. 1994, 35, 7935-7938. 167 O. R. Gautun and P. H. J. Carlsen, Molecules 2001, 6, 969-978. 168 Reviews: a) D. L. Boger, Tetrahedron 1983, 39, 2869-2939; b) D. L. Boger, Chem.
Rev. 1986, 86, 781-793. 169 a) T. Sasaki, K. Kanematsu and T. Hiramatsu, J. Chem. Soc., Perkin Trans. 1 1974,
1213-1215; b) M. J. Haddadin, S. J. Firsan and B. S. Nader, J. Org. Chem. 1979,
44, 629-630; c) S. Satish, A. Mitra and M. V. George, Tetrahedron 1979, 35, 277-
285; d) M. J. Haddadin, B. J. Agha and M. S. Salka, Tetrahedron Lett. 1984, 25,
2577-2580; e) D. R. Soenen, J. M. Zimpleman and D. L. Boger, J. Org. Chem.
2003, 68, 3593-3598; f) E. C. Constable, C. E. Housecroft, M. Neuburger, S.
Reymann and S. Schaffner, Eur. J. Org. Chem. 2008, 1597-1607. 170 R. A. Carboni and R. V. Lindsey, J. Am. Chem. Soc. 1959, 81, 4342-4346. 171 a) W. E. Smith, J. Org. Chem. 1972, 37, 3972-3973; b) L. F. Lindoy, G. V. Meehan
and N. Svenstrup, Synthesis 1998, 1029-1032. 172 S. W. Johnson, S. Connelly, I. A. Wilson and G. W. Kelly, J. Med. Chem. 2008, 51,
6348-6358. 173 E. Van Heyningen, J. Org. Chem. 1961, 26, 3850-3856. 174 a) S. K. Sharma, M. Tandon and J. W. Lown, Eur. J. Org. Chem. 2000, 2095-2103;
b) L. Colombo, C. Gennari, M. Santandrea, E. Narisano and C. Scolastico, J. Chem.
Soc., Perkin Trans. 1 1980, 136-140; c) H. M. Chang, K. Y. Chui, F. W. L. Tan, Y.
Yang, Z. P. Zhong, C. M. Lee, H. L. Sham and H. N. C. Wong, J. Med. Chem.
1991, 34, 1675-1692. 175 A. O. Fitton, A. Rigby and R. J. Hurlock, J. Chem. Soc. (C) 1969, 230-233. 176 M. H. Klingele and S. Brooker, Eur. J. Org. Chem. 2004, 3422-3434. 177 S. Xun, G. LeClair, J. Zhang, X. Chen, J. P. Gao and Z. Y. Wang, Org. Lett. 2006,
1697-1700.
References 507
178 Reviews on oxadiazoles: a) Ž. Jakopin and M. Sollner Dolenc, Curr. Org. Chem.
2008, 12, 850-898; b) H. Rajak, M. D. Kharya and P. Mishra, International Journal
of Pharmaceutical Sciences and Nanotechnology 2009, 2, 21-58; c) R. R. Somani
and P. Y. Shirodkarb, Pharma Chemica 2009, 1, 130-140; d) D. S. Musmade, N. S.
Dighe, S. R. Pattan, M. S. Sanap, P. A. Chavan, M. S. Kedar, S. K. Tambe and P. J.
Shirote, Pharmacologyonline 2010, 108-116. 179 W. T. Flowers, D. R. Taylor, A. E. Yipping and C. N. Wright, J. Chem. Soc. (C)
1971, 1986-1991. 180 G.-W. Rao and W.-X. Hu, Bioorg. Med. Chem. Lett. 2006, 16, 3702-3705. 181 L. I. Robins, R. D. Carpenter, J. C. Fettinger, M. J. Haddadin, D. S. Tinti and M. J.
Kurth, J. Org. Chem. 2006, 71, 2480-2485. 182 L. I. Belen'kii, S. I. Luiksaar, N. D. Chuvylkin and M. M. Krayushkin, Russ. Chem.
Bull. 2000, 49, 886-893. 183 a) K.-P. Hartmann and M. Heuschmann, Tetrahedron 2000, 56, 4213-4218; b) J.
Rebek, S. Gu, S. Biros, US Patent 7579350, 2006. 184 F. Sansone, S. Barboso, A. Casnati, M. Fabbi, A. Pochini, F. Ugozzoli and R.
Ungaro, Eur. J. Org. Chem. 1998, 897-905. 185 a) J.-D. van Loon, A. Arduini, L. Coppi, W. Verboom, A. Pochini, R. Ungaro, S.
Harkema and D. N. Reinhoudt, J. Org. Chem. 1990, 55, 5639-5646; c) R. H.
Vreekamp, W. Verboom and D. N. Reinhoudt, J. Org. Chem. 1996, 61, 4282-4288;
d) M. Segura, B. Bricoli, A. Casnati, E. M. Muoz, F. Sansone, R. Ungaro and C.
Vicent, J. Org. Chem. 2003, 68, 6296-6303. 186 X. H. Sun, W. Li, P. F. Xia, H.-B. Luo, Y. Wei, M. S. Wong, Y.-K. Cheng and S.
Shuang, J. Org. Chem. 2007, 72, 2419-2426. 187 M. Jørgensen, M. Larsen, P. Sommer-Larsen, W. Batsberg Petersen and H. Eggert,
J. Chem. Soc., Perkin Trans. 1 1997, 2851-2855. 188 a) F. L. Scott and P. A. Cashell, J. Chem. Soc. C: Organic 1970, 2674-2677; b) M.
G. Rosenberg and U. H. Brinker, J. Org. Chem. 2003, 68, 4819-4832. 189 S. Trosien, Master Thesis, Ruhr-Universität Bochum, 2011. 190 a) H. E. Gottlieb, V. Kotlyar and A. Nudelmann, J. Org. Chem. 1997, 62, 7512-
7515; b) G. R. Fulmer, A. J. M. Miller, N. H. Sherden, H. E. Gottlieb, A.
508 Appendix
Nudelman, B. M. Stoltz, J. E. Bercaw and K. I. Goldberg, Organometallics 2010,
29, 2176-2179. 191 G. M. Sheldrick, Acta Cryst. 2008, A64, 112 192 W. L. Armarego and C. Chai. Purifcation of Laboratory Chemicals.
Butterworth Heinemann, 5th edition, 2004. 193 E. E. Sch weizer, A. T. Wehman, J. Chem. Soc. C. 1971, 343-346. 194 K. Auwers, T. Makovits, Chem. Ber. 1908, 45, 2332.