Obtained by a Consecutive Twofold Suzuki and Twofold ... · 2.6 equiv.), Pd(PPh3)4 (58 mg, 0.05 mmol, 5 mol%) and cesium fluoride (604 mg, 4 mmol, 4 equiv.) were combined in a dry
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Synthesis and Molecular Properties of Methoxy-Substituted Diindolo[3,2-b:2’,3’-h]carbazoles for Organic Electronics Obtained by a Consecutive Twofold Suzuki and Twofold Cadogan ReactionHassan Srour,a Thu-Hong Doan,a Elisabeth Da Silva,a Richard J. Whitbyb* and Bernhard Witulskia*
aLaboratoire de Chimie Moléculaire et Thio-organique, CNRS UMR 6507; Normandy University, ENICAEN & UNICAEN, 6 Bvd Maréchal Juin, 14050 Caen, France. *E-mail : [email protected] of Chemistry, University of Southampton, HANTS, SO17-BJ, UK
Content1. General Remarks2. Experimental Part.3. Cyclic Voltammetry.4. DSC data5. TGA data6. UV-vis and Photoluminescence Spectra.7. Solid State Photoluminescence Spectra.8. Calculated HOMO-LUMO Orbitals at the DFT level.9. 1H NMR and 13C NMR spectra.
1. General Remarks
Commercially available reagents were used without further purification; solvents and gases were dried
by standard procedures. Organic solvents were evaporated using a rotary evaporator. Flash
chromatography was performed using silica gel 60, particle size 40-63 µm. Thin-layer chromatography
was performed using commercially Merck pre-coated aluminium backed TLC Silica gel 60 F254, with
spot detection under UV light.
Melting points (mp) were determined on the Electrothermal IA9000 Series Digital Melting Point
Apparatus and are uncorrected. NMR spectra were recorded in deuterated solvent on a 400 MHz or 500
MHz Bruker Avance III apparatus. The chemical shifts are calibrated to residual proton resonance of
TMS (δH 0 ppm) and DMSO-d6 (δH 2.50 ppm) and carbon resonance of the solvents CDCl3 (δC 77.16
ppm) and DMSO-d6 (δC 39.52 ppm). 1H NMR data are presented as follow: chemical shift, multiplicity
(s = singlet, br = broad, d = doublet, t = triplet, q = quartet, qt = quintuplet, sex = sextuplet, m =
multiplet), coupling constant (J, Hz), integration. 13C NMR data are presented as follows: chemical shift,
(C-H coupling patterns refer to the corresponding DEPT spectra; s = Cquat, d = CH, t = CH2, q = CH3).
Mass spectra (MS) and high-resolution mass data (HRMS) under electron spray ionization (ESI) mode
were obtained on a Q-TOF Micro WATERS spectrometer; mass spectra under electronic impact (EI)
were obtained with direct probe at 70 eV on a JEOL GCmate spectrometer.
1091, 1048, 926, 814 cm-1. HRMS calcd for C10H8NS ([M+H]+) 174.0377; found 174.0379.
4H-4-methyl-thieno[3,2-b]indole (40):2
The Cadogan reaction product 37 (80 mg, 0.46 mmol) was dissolved in dry DMF (10 mL) and then
sodium hydride (60% dispersion in oil, 55 mg, 1.38 mmol) was added by portions. After stirring 30 min
at room temperature, iodomethane (0.17 mL, 2.73 mmol) was added dropwise and the mixture stirred
at room temperature for 1h. The reaction mixture was diluted with water and extracted with
dichloromethane. The organic layers were combined, washed with brine and dried with MgSO4.
Compound 40 (85 mg, 0.45 mmol, 98% yield) was obtained after flash chromatography (silica gel n-n-
3 P. Appukkuttan, E. Van der Eycken, W. Dehaen, Synlett, 2005, 127-133.4 R.A. Abramovitch, T. Chellathurai, I.T. McMaster, T. Takaya, Ch.I. Azogu, D.P. Vanderpool, J. Org. Chem., 1977, 42, 2914.
pentane/ethyl acetate = 9:1 (v/v)) as a white solid, mp 79-81 °C (CHCl3/n-pentane); Rf 0.54 (SiO2, n-
71), 238 (13), 224 (100), 223 (51); HRMS calcd for C20H22NS ([M+H]+) 308.1480; found 308.1473.
6 K.E. Chippendale, B. Iddon, H. Suschitzky, J. Chem. Soc. Perkin Trans. I, 1972, 2023-2030.7 K. Takamatsu, K. Hirano, T. Satoh, M. Miura, Org. Lett., 2014, 16, 2892-2895.8 Y.B. KIM, H.M. KIM, Y. BEAK, T.H. KIM, ORGANIC COMPOUND AND ORGANIC ELECTROLUMINESCENT ELEMENT INCLUDING SAME, WIPO Patent Application WO/2014/104665.
N-n-hexyl-benzofuro[3,2-b]indole (42):
42
N
OO
36
NO2 NH
O
39
NaH,
n-HexBr
I
NO2
+
O(HO)2B
Suzuki
reaction
Cadoganreaction
(85%) (90%) (93%)
2-o-nitrophenylbenzofuran (36)9 was prepared by a microwave accelerated Suzuki cross-coupling
reactions of benzofurane-2-boronic acid and 2-bromonitrobenzene. 2-iodonitrobenzene (100 mg, 0.4
HRMS calc for C20H22NO [M+H+] 292.1701, found 292.1703.
3. Cyclic Voltammetry
N
NNC6H13
C6H13
C6H13
26
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6
-20
-10
0
10
20
30
40
I m (
A)
Vf (V)0,0 0,2 0,4 0,6 0,8 1,0
-10
0
10
20
I m (
A)
Vf (V)
1st oxidation
Figure 3.1. Cyclic voltammetry of 26 (10-3 M in CH2Cl2/0.1 M Bu4NPF6) at room temperature [left]. First oxidation potential [right]. Scan rate 100 mV/s; CV recorded vs SCE [left].
N
NNC6H13
C6H13
C6H13
OMeMeO
27
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6
-30
-20
-10
0
10
20
30
40
I m (
A)
Vf (V)0,0 0,2 0,4 0,6 0,8 1,0
-10
0
10
20
I m (µ
A)
Vf (V)
1st oxidation
Figure 3.2. Cyclic voltammetry of 27 (10-3 M in CH2Cl2/0.1 M Bu4NPF6) at room temperature [left]. First oxidation potential [right]. Scan rate 100 mV/s; CV recorded vs SCE [left].
N
NNC6H13
C6H13
C6H13
MeOOMe
MeO OMe
28
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4 1,6
-200
-100
0
100
200
300
400
500
I m (
A)
Vf (V)0,0 0,1 0,2 0,3 0,4 0,5 0,6 0,7 0,8 0,9 1,0
-20
-10
0
10
20
30
I m (
A)
Vf (V)
1st oxidation
Figure 3.3. Cyclic voltammetry of 28 (10-3 M in CH2Cl2/0.1 M Bu4NPF6) at room temperature [left]. First oxidation potential [right]. Scan rate 100 mV/s; CV recorded vs SCE [left].
N
N NO O
O O
C6H13 C6H13
C6H13
29
0,0 0,2 0,4 0,6 0,8 1,0
-20
0
20
40
I m (
A)
Vf (V)0,0 0,2 0,4 0,6 0,8 1,0
-20
0
20
40
I m (
A)
Vf (V)
1st oxidation
Figure 3.4. Cyclic voltammetry of 29 (10-3 M in CH2Cl2/0.1 M Bu4NPF6) at room temperature [left]. First oxidation potential [right]. Scan rate 100 mV/s; CV recorded vs SCE [left].
N
NNC6H13
C6H13
C6H13
OMeMeO
MeOOMe
30
0,0 0,2 0,4 0,6 0,8 1,0 1,2 1,4
-20
-10
0
10
20
30
I m (
A)
Vf (V)0,0 0,2 0,4 0,6 0,8 1,0
-30
-20
-10
0
10
20
30
40
I m (
A)
Vf (V)
1st oxidation
Figure 3.5. Cyclic voltammetry of 30 (10-3 M in CH2Cl2/0.1 M Bu4NPF6) at room temperature [left]. First oxidation potential [right]. Scan rate 100 mV/s; CV recorded vs SCE [left].
4. DSC data
N
NNC6H13
C6H13
C6H13
26
1er cycle
2nd cycle
N
NNC6H13
C6H13
C6H13
OMeMeO
27
1er cycle
2nd cycle
N
NNC6H13
C6H13
C6H13
MeOOMe
MeO OMe
28
1er cycle
2nd cycle
N
NNC6H13
C6H13
C6H13
OMeMeO
MeOOMe
30
1er cycle
2nd cycle
5. TGA of (27)
N
NNC6H13
C6H13
C6H13
OMeMeO
27
200 400 600 8000
20
40
60
80
100
Wei
ght (
%)
Temperature (oC)
6. UV-vis and Photoluminescence Spectra
N
NNC6H13
C6H13
C6H13
26
250 300 350 400 450 5000
20000
40000
60000
(L
mol
-1 c
m-1)
Wavelength (nm)400 420 440 460 480 500
0
2000
4000
6000
(L
mol
-1 c
m-1)
Wavelength (nm)
Figure 6.1: UV-vis absorption spectra of 26 in dichloromethane [left], and enlargement of the long-wavelength absorption [right].
440 460 480 500 520 5400,0
0,2
0,4
0,6
0,8
1,0Photoluminescence spectra
Inte
nsity
[a.u
.]
Wavelength (nm)400 420 440 460 480 500 520
0,0
0,2
0,4
0,6
0,8
1,0
Inte
nsity
[a.u
.]
Excitation spectra
Wavelength (nm)
Figure 6.2: Photoluminescence spectra of 26 (10-5 M in CH2Cl2, ex = 410 nm) [left], and excitation spectra (em = 480 nm) [right].
400 450 500 5500,0
0,2
0,4
0,6
0,8
1,0
Abs
orpt
ion
(nor
mal
ized
) [a.
u.]
Wavelength (nm)
absorption fluorescence
ex = 410 (nm)
0,0
0,2
0,4
0,6
0,8
1,0
Pho
tolu
min
esce
nce
Inte
nsity
[a.u
.]
Figure 6.3: Absorption and photoluminescence (ex = 410 nm) spectra of 26 in CH2Cl2.
N
NNC6H13
C6H13
C6H13
OMeMeO
27
250 300 350 400 450 5000
40000
80000
120000
Wavelength (nm)
(L
.mol
-1 c
m-1)
420 440 460 480 5000
2000
4000
6000
8000
10000
(L
.mol
-1.c
m-1)
Wavelength (nm)
Figure 6.4: UV-vis absorption spectra of 27 in dichloromethane [left], and enlargement of the long-wavelength absorption [right].
440 460 480 500 520 5400,0
0,4
0,8
Inte
nsity
[a.u
.]
Wavelength (nm)
Photoluminescence spectra
420 430 440 450 460 470 4800,0
0,4
0,8
Inte
nsity
[a.u
.]
Wavelength (nm)
Excitation spectra
Figure 6.5: Photoluminescence spectra of 27 (10-5 M in CH2Cl2, ex = 410 nm) [left], and excitation spectra (em = 490 nm) [right].
420 440 460 480 500 520 5400,0
0,2
0,4
0,6
0,8
1,0 Absorption
0,0
0,2
0,4
0,6
0,8
1,0
1,2
1,4
Photoluminescence
Abs
orpt
ion
(nor
mal
ized
) [a.
u.]
Wavelength (nm)
Pho
tolu
min
esce
nce
inte
nsity
[a.u
.]
Figure 6.6: Absorption and Photoluminescence (ex = 410 nm) spectra of 27 in CH2Cl2.
N
NNC6H13
C6H13
C6H13
MeOOMe
MeO OMe
28
250 300 350 400 450 5000
20000
40000
60000
80000
(L
.mol
-1 c
m-1)
Wavelength (nm)400 420 440 460 480 500
0
2000
4000
6000
8000
10000
12000
(L
.mol
-1 c
m-1)
Wavelength (nm)
Figure 6.7: UV-vis absorption spectra of 28 in dichloromethane [left], and enlargement of the long-wavelength absorption [right].
440 460 480 500 520 5400,0
0,4
0,8
Inte
nsity
[a.u
.]
Wavelength (nm)
Photoluminescence spectra
420 440 460 4800,0
0,4
0,8
Inte
nsity
[a.u
.]
Wavelength (nm)
Excitation spectra
Figure 6.8: Photoluminescence spectra of 28 (10-5 M in CH2Cl2, ex = 410 nm) [left], and excitation spectra (em = 490 nm) [right].
420 440 460 480 500 520 5400,0
0,2
0,4
0,6
0,8
1,0
Absorption Photoluminescence
Abs
orpt
ion
(nor
mal
ized
) [a.
u.]
Wavelength (nm)
Inte
nsity
[a.u
.]
0,0
0,2
0,4
0,6
0,8
1,0
Figure 6.9: Absorption and Photoluminescence (ex = 410 nm) spectra of 28 in CH2Cl2.
N
N NMeO OMe
MeO OMe
C6H13 C6H13
C6H13
29
250 300 350 400 450 5000
20000
40000
60000
80000
100000
Wavelength (nm)
(L
.mol
-1 c
m-1)
420 440 460 480 5000
2000
4000
6000
8000
10000
12000
14000
(L
.mol
-1 c
m-1)
Wavelength (nm)
Figure 6.10: UV-vis absorption spectra of 29 in dichloromethane [left], and enlargement of the long-wavelength absorption [right].
440 460 480 500 520 540 5600,0
0,2
0,4
0,6
0,8
1,0
Inte
nsity
[a.u
.]
Wavelength (nm)
Photoluminescence spectra
420 440 460 480 500 520 5400,0
0,2
0,4
0,6
0,8
1,0
Inte
nsity
[a.u
.]
Wavelength (nm)
Excitation spectra
Figure 6.11: Photoluminescence spectra of 29 (10-5 M in CH2Cl2, ex = 410 nm) [left], and excitation spectra (em = 472 nm) [right].
420 440 460 480 500 520 540 5600,0
0,2
0,4
0,6
0,8
1,0
absoption photoluminescence
0,0
0,4
0,8
Abs
orpt
ion
(nor
mal
ized
) [a.
u.]
Inte
nsity
[a.u
.]
Wavelength (nm)
Figure 6.12: Absorption and Photoluminescence (ex = 410 nm) spectra of 29 in CH2Cl2.
N
NNC6H13
C6H13
C6H13
OMeMeO
MeOOMe
30
250 300 350 400 450 5000
20000
40000
60000
80000
100000
120000
(L
.mol
-1 c
m-1)
Wavelength (nm)420 440 460 480 500
0
4000
8000
12000
16000
(L
.mol
-1 c
m-1)
Wavelength (nm)
Figure 6.13: UV-vis absorption spectra of 30 in dichloromethane [left], and enlargement of the long-wavelength absorption [right].
420 440 460 480 500 520 540 5600,0
0,4
0,8
Inte
nsity
[a.u
.]
Wavelength (nm)400 420 440 460 480 500
0,0
0,2
0,4
0,6
0,8
1,0
Nor
mal
ized
inte
nsity
[a.u
.]
Wavelength (nm)
Figure 6.14: Photoluminescence spectra of 30 (10-5 M in CH2Cl2, ex = 410 nm) [left], and excitation spectra (em = 490 nm) [right].
420 440 460 480 500 520 540 5600,0
0,4
0,8
absorption
Abs
orpt
ion
(nor
mal
ized
) [a.
u.]
Wavelength (nm)
Inte
nsity
[a.u
.]
0,0
0,4
0,8
1,2
1,6 photoluminescence
Figure 6.15: Absorption and Photoluminescence (ex = 410 nm) spectra of 30 in CH2Cl2.
7. Solid State Photoluminescence Spectra
500 600 700 800
0
10
20
30
Inte
nsity
(a.u
.)
Wavelength (nm)
26 (ex = 380 nm)
N
NNC6H13
C6H13
C6H13
500 600 700 800
0
10
20
30
Inte
nsity
(a.u
.)
Wavelength (nm)
27 (ex = 380 nm)
N
NNC6H13
C6H13
C6H13
OMeMeO
500 600 700 8000
50
100
150
200
250
300
350
Inte
nsity
(a. u
.)
Wavelength (nm)
28 (ex = 380 nm)
N
NNC6H13
C6H13
C6H13
MeOOMe
MeO OMe
500 600 700 800
0
10
20
30
Inte
nsity
(a.u
.)
Wavelength (nm)
29 (ex = 380nm)
N
NNC6H13
C6H13
C6H13MeO OMe
OMeMeO
500 600 700 800
0
10
20
30
40
Inte
nsity
(a.u
.)
Wavelength (nm)
30 (ex = 430 nm) - non emissive
N
N N
OMe MeO
MeO OMe
C6H13 C6H13
C6H13
Compound 26 27 28 29 30F of solid, (ex = [nm])
~1%(430)
2%(430)
14%(430)
2%(430)
0%(430)
F in solution, c = 10-6 M in CH2Cl2, (ex [nm]),
22% (430) 26% (430) 22% (430) 20% (440) 27% (420)
8. Calculated HOMO-LUMO OrbitalsThe molecules 26*-33* were minimized using Gaussian 09 revision D-01 and D-0211 with
the B3LYP functional12 and 6-31(d) basis set13 using a PCM model14 for dichloromethane
as solvent. Vibrational analysis confirmed the stationary points as minima. The HOMO-1,
HOMO, LUMO and LUMO+1 energy levels are given in the Table. Surface plots of the
LUMO, HOMO and HOMO-1 (as the energy gap between the HOMO-1 and HOMO is
often rather small) are given below. Each is drawn to enclose 98% of the electron density.
Table. Energies of orbitals for compounds 26*-33*.a
11 (a) A. D. Becke J. Chem. Phys., 1993, 98, 5648. (b) C. Lee, W. Yang and R. G. Parr, Phys. Rev. B 1988, 37, 785. (c) P. J. Stephens, F. J. Devlin, C. F. Chabalowski and M. J. Frisch, J. Phys. Chem., 1994, 98, 11623.12 R. Ditchfield, W.J. Hehre, J.A. Pople, J. Chem. Phys. 1971, 54 724.13 (a) V. Barone and M. Cossi, J Phys Chem A, 1998, 102, 1995. (b) M. Cossi, N. Rega, G. Scalmani, V. Barone, J. Comput. Chem. 2003, 24, 669.14 Gaussian 09, Revision D.01, M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G. A. Petersson, H. Nakatsuji, M. Caricato, X. Li, H. P. Hratchian, A. F. Izmaylov, J. Bloino, G. Zheng, J. L. Sonnenberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J. A. Montgomery, Jr., J. E. Peralta, F. Ogliaro, M. Bearpark, J. J. Heyd, E. Brothers, K. N. Kudin, V. N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, N. Rega, J. M. Millam, M. Klene, J. E. Knox, J. B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R. E. Stratmann, O. Yazyev, A. J. Austin, R. Cammi, C. Pomelli, J. W. Ochterski, R. L. Martin, K. Morokuma, V. G. Zakrzewski, G. A. Voth, P. Salvador, J. J. Dannenberg, S. Dapprich, A. D. Daniels, O. Farkas, J. B. Foresman, J. V. Ortiz, J. Cioslowski, and D. J. Fox, Gaussian, Inc., Wallingford CT, 2013.
N
NNCH3
CH3
CH3
26*
Figure 8.1.1: Calculated LUMO of 26*.
Figure 8.1.2: Calculated HOMO of 26*.
Figure 8.1.3: Calculated HOMO-1 of 26*.
N
NNCH3
CH3
CH3
OMeMeO
27*
Figure 8.2.1: Calculated LUMO of 27*.
Figure 8.2.2: Calculated HOMO of 27*.
Figure 8.2.3: Calculated HOMO-1 of 27*.
N
NNCH3
CH3
CH3
MeOOMe
MeO OMe
28*
Figure 8.3.1: Calculated LUMO of 28*.
Figure 8.3.2: Calculated HOMO of 28*.
Figure 8.2.3: Calculated HOMO-1 of 28*.
N
N NMeO OMe
MeO OMe
CH3 CH3
CH3
29*
Figure 8.4.1: Calculated LUMO of 29*.
Figure 8.4.2: Calculated HOMO of 29*.
Figure 8.4.3: Calculated HOMO-1 of 29*.
N
NNCH3
CH3
CH3
OMeMeO
MeOOMe
30*
Figure 8.5.1: Calculated LUMO of 30*.
Figure 8.5.2: Calculated HOMO of 30*.
Figure 8.5.3: Calculated HOMO-1 of 30*.
N
NNCH3
CH3
CH3
31*
SS
Figure 8.6.1: Calculated LUMO of 31*.
Figure 8.6.2: Calculated HOMO of 31*.
Figure 8.6.3: Calculated HOMO-1 of 31*.
N
NNCH3
CH3
CH3
32*
SS
Figure 8.7.1: Calculated LUMO of 32*.
Figure 8.7.2: Calculated HOMO of 32*.
Figure 8.7.3: Calculated HOMO-1 of 32*.
N
NNCH3
CH3
CH3
33*
OO
Figure 8.8.1: Calculated LUMO of 33*.
Figure 8.8.2: Calculated HOMO of 33*.
Figure 8.8.3: Calculated HOMO-1 of 33*.
9. 1H NMR and 13C NMR spectra.
NC6H13
BrBr
S3
Figure 9.1: 1H NMR spectrum of S3 in CDCl3, 400 MHz.
Figure 9.2: 13C NMR spectrum of S3 in CDCl3, 100 MHz.
NC6H13
Br
NO2O2N
Br
1
Figure 9.3: 1H NMR spectrum of 1 in CDCl3, 400 MHz.
Figure 9.4: 13C NMR spectrum of 1 in CDCl3, 100 MHz.
NC6H13
O2N NO2
10
Figure 9.5: 1H NMR spectrum of 10 in CDCl3, 400 MHz
Figure 9.6: 13C NMR spectrum of 10 in CDCl3, 100 MHz.
NC6H13
O2N NO2
MeO OMe
11
Figure 9.7: 1H NMR spectrum of 11 in CDCl3, 400 MHz.
Figure 9.8: 13C NMR spectrum of 11 in CDCl3, 100 MHz.
NC6H13
O2N NO2OMe
MeOOMe
MeO
12
Figure 9.9: 1H NMR spectrum of 12 in CDCl3, 400 MHz.
Figure 9.10: 13C NMR spectrum of 12 in CDCl3, 100 MHz.
NC6H13
O2N NO2OMeMeO
OMeMeO
13
Figure 9.11: 1H NMR spectrum of 13 in CDCl3, 400 MHz
Figure 9.12: 1H NMR spectrum of 13 in CDCl3, 100 MHz.
NC6H13
O2N NO2
MeO OMeMeOOMe
14
Figure 9.13: 1H NMR spectrum of 14 in CDCl3, 400 MHz.
Figure 9.14: 13C NMR spectrum of 14 in CDCl3, 100 MHz.
NC6H13
O2N NO2
SS
15
Figure 9.15: 1H NMR spectrum of 15 in CDCl3, 400 MHz.
Figure 9.16: 13C NMR spectrum of 15 in CDCl3, 100 MHz.
NC6H13
O2N NO2
SS
16
Figure 9.17: 1H NMR spectrum of 16 in CDCl3, 400 MHz.
Figure 9.18: 13C NMR spectrum of 16 in CDCl3, 100 MHz.
NC6H13
O2N NO2
OO
17
Figure 9.19: 1H NMR spectrum of 17 in CDCl3, 400 MHz.
Figure 9.20: 13C NMR spectrum of 17 in CDCl3, 100 MHz.
N
HN
HN
C6H13
18
Figure 9.21: 1H NMR spectrum of 18 in DMSO, 400 MHz.
Figure 9.22: 13C NMR spectrum of 18 in DMSO, 125 MHz.
N
HN
HN
C6H13
OMeMeO
19
Figure 9.23: 1H NMR spectrum of 19 in DMSO, 500 MHz.
Figure 9.24: 13C NMR spectrum of 19 in DMSO, 125 MHz.
N
HN
HN
C6H13MeOOMe
MeO OMe
20
Figure 9.25: 1H NMR spectrum of 20 in DMSO, 500 MHz.
Figure 9.26: 13C NMR spectrum of 20 in DMSO, 125 MHz.
N
HN
HN
C6H13
MeO OMe
MeO OMe
21
Figure 9.27: 1H NMR spectrum of 21 in DMSO, 400 MHz.
Figure 2.28: 13C NMR spectrum of 21 in DMSO, 100 MHz.
N
HN
HN
C6H13
OMeMeO
MeOOMe
22
Figure 9.29: 1H NMR spectrum of 22 in DMSO, 400 MHz.
Figure 9.30: 13C NMR spectrum of 22 in DMSO, 125 MHz.
N
NNC6H13
C6H13
C6H13
26
Figure 9.31: 1H NMR spectrum of 26 in C6D6, 500 MHz.
Figure 9.32: 13C NMR spectrum of 26 in C6D6, 125 MHz.
N
NNC6H13
C6H13
C6H13
OMeMeO
27
Figure 9.33: 1H NMR spectrum of 27 in C6D6, 500 MHz.
Figure 9.34: 13C NMR spectrum of 27 in C6D6, 125 MHz.
N
NNC6H13
C6H13
C6H13
MeOOMe
MeO OMe
28
Figure 9.35: 1H NMR spectrum of 28 in C6D6, 400 MHz.
Figure 9.36: 13C NMR spectrum of 28 in C6D6, 125 MHz.
N
NNC6H13
C6H13
C6H13MeO OMe
MeO OMe
29
Figure 9.37: 1H NMR spectrum of 29 in C6D6, 500 MHz.
Figure 9.38: 13C NMR spectrum of 29 in C6D6, 125 MHz.
N
NNC6H13
C6H13
C6H13
OMeMeO
MeOOMe
30
Figure 9.39: 1H NMR spectrum of 30 in C6D6, 500 MHz.
Figure 9.40: 13C NMR spectrum of 30 in C6D6, 125 MHz.
S
NO2
34
Figure 9.41: 1H NMR spectrum of 34 in CDCl3, 400 MHz.
Figure 9.42: 13C NMR spectrum of 34 in CDCl3, 100 MHz.
S
HN
37
Figure 9.43: 1H NMR spectrum of 37 in CDCl3, 400 MHz.
Figure 9.44: 13C NMR spectrum of 37 in CDCl3, 100 MHz.
N
S
40
Figure 9.45: 1H NMR spectrum of 40 in CDCl3, 400 MHz.
Figure 9.46: 13C NMR spectrum of 40 in CDCl3, 125 MHz.
S
NO2
35
Figure 9.47: 1H NMR spectrum of 35 in CDCl3, 400 MHz.
Figure 9.48: 13C NMR spectrum of 35 in CDCl3, 100 MHz.
NH
S
38
Figure 9.49: 1H NMR spectrum of 38 in CDCl3, 400 MHz.
Figure 9.50: 13C NMR spectrum of 38 in CDCl3, 100 MHz.
N
S
C6H13
41
Figure 9.51: 1H NMR spectrum of 41 in CDCl3, 400 MHz.
Figure 9.52: 13C NMR spectrum of 41 in CDCl3, 100 MHz.
O
NO2
36
Figure 9.53: 1H NMR spectrum of 36 in CDCl3, 400 MHz.
Figure 9.54: 13C NMR spectrum of 36 in CDCl3, 100 MHz.
NH
O
39
Figure 9.55: 1H NMR spectrum of 39 in CDCl3, 400 MHz.
Figure 9.56: 13C NMR spectrum of 39 in CDCl3, 100 MHz.
N
O
C6H13
42
Figure 9.57: 1H NMR spectrum of 42 in CDCl3, 400 MHz.
Figure 9.58: 13C NMR spectrum of 42 in CDCl3, 100 MHz.