Numerous works have been devoted to the design of new fluorescent sensors for various
applications such as clinical toxicology environmental bioorganic chemistry and waste
management [1] To develop optical molecular probes or sensors for toxic metals ruthenium
complexes with ditopic 110-phenanthrolines seem to be an appropriate solution Moreover
aminoquinolines possess good fluorescent properties but have not yet been investigated as a
signaling subunit in chemosensors In this work Pd-catalyzed amination of 6-bromoquinoline (1)
and 3-bromo-110-phenanthroline (2) with linear polyamines 3a-d was investigated to prepare
The fluorescent derivatives of 6-aminoquinoline 4 were synthesized in good yields (up to 62)
using PdBINAP system as catalyst (Scheme) The amination of 3-bromo-110-phenanthroline is
more complicated and Josiphos ligand should be used to obtain 3-amino-110-phenanthrolines 5 in
Scheme Pd-catalyzed amination of 6-bromoquinoline (1) and 3-bromo-110-phenanthroline (2)
This reaction is a key step in the synthesis of fluorescent receptors 6-8 (Figure) The sensing
properties of receptors 7 and 8 in the presence of various amounts of environmentally-relevant
Acknowledgements The work was performed in the frames of French-Russian Associated
Laboratory ldquoLAMREMrdquo and financially supported by the RFBR (grant N 12-03-93107) and CNRS
113
P2
MECHANISM OF CARBON MONOXIDE OXIDATION OVER SUPPORTED
CuO CATALYSTS
YuA Agafonov1 NA Gaidai
1 NV Nekrasov
1 LC Loc
2 N Tri
2 HT Cuong
2 HS Thoang
2
AL Lapidus1
1 - Institute of Organic Chemistry RAS Moscow Russia
2 - Institute of Chemical Technology Vietnam Acad Sci Techn Ho Chi Minh City Vietnam
Supported CuO catalysts with additives of other oxides are effective ones for CO oxidation
Introduction of small amounts of noble metals in these catalysts allows to increase their activity
which can exceed the activity of supported platinum catalysts ndash the most active known ones in CO
oxidation Designing new catalysts for this process requires depth knowledge on the reaction
mechanism This work is devoted to the study of mechanism of CO oxidation over the following
supported on -Al2O3 catalysts 10 (wt) CuO (CuAl) 10 CuO+20 CeO2 (CuCeAl) 10
CuO+10 Cr2O3 (CuCrAl) without and with addition of Pt The content of Pt varied in the range
of 005 ndash 03 wt The following physico-chemical methods were used for catalyst investigation
BET N2-Adsorption XRD TPR SEM EDS and IR-CO adsorption There are the surface data of
studied catalysts in Table
It is seen that the Cr Ce and Pt
enhanced the reducibility of copper
catalysts what expressed in the decrease
of the reduction temperature and the
increase of the reduction extent (the
reducibility of catalysts CuAl and
CuCeAl was increased in 25 ndash 3 times)
It was shown that the optimal Pt content
is 01 With this amount of Pt catalyst
PtCuCeAl was capable to convert
completely CO to CO2 at 110oC
(without Pt - at 125oC) The process
mechanism was studied by unstationary
response method Relaxation curves
describing a transition of the system to a
new steady state were obtained by a
jump change of the corresponding concentrations The residence time defined as the ratio of the
reaction system volume to the flow rate was 2-5 times lower than the turnover time It is meant that
the observed transition phenomena were associated with the intrinsic processes It was shown that
Pt weakened the interaction of active phase which resulted in an increase of the reaction rate The
initial substances participated in the reaction in adsorbed state the most part of the surface was
occupied by oxygen over all the catalysts Ce was facilitated the mobility of oxygen Pt was
increased the bond strengh of CO O2 and CO2 with the surface of catalysts Not only adsorbed
oxygen but lattice oxygen took part in the reaction but the last oxygen in less extent The change of
introduced glass filler in the reactor showed that reaction of CO oxidation proceeds mainly through
heterogeneous mechanism the share of homogeneous mechanism does not exceed 15 It was
shown that CO and O2 adsorption were quick steps one intermediate compound was formed in
slow step of the process The overall step-scheme of CO oxidation was proposed over studied
catalysts The work is supported by RFBR (13-03-93001_Viet_a) and NAFOSTED grant 10403-201260
Catalysts SBET
m2g
dCu
nm
γCu
Tmax
C
KRed
Oxide Catalysts
CuAl 1770 119 131 375 130
CuCrAl 1660 155 100 355 284
CuCeAl 670 - - 321 176
Pt-containing oxide catalysts
01PtCuAl 959 116 134 274 367
02PtCuAl 951
005PtCuCrAl 892 188 83 308 299
01PtCuCeAl 801 352 44 255 458
Table Surface characteristics of the studied catalysts
specific surface area (SBET) crystal size of Cu (dCu)
dispersion of Cu (γCu ) maximum reduction
temperature (Tmax) and extent of reduction for ions
Cu2+
(KRed )
114
P3
EFFICIENT CATALYTIC HYDRODEOXYGENATION OF
UNPROTECTED CYCLIC IMIDES TO CYCLIC AMINES BY
HETEROGENEOUS CATALYSIS
AM Maj I Suisse F Agbossou-Niedercorn
University Lille Nord de France UCCS UMR 8181 CNRS ENSCL C7 CS90108 59652 Villeneuve
d Ascq Cedex France
Cyclic amines comprising fused saturated N-heterocycles are valuable synthetic intermediates They
are found in numerous drug candidates such as bicifadine cytisine gliclazide or telaprevir to name
just a few (Figure 1) The catalytic hydrogenation of imides appears to be the most elegant and
promising reaction to produce properly and efficiently such amines Since the reaction might
potentially lead to several compounds it needs to be controlled by an appropriate catalyst which
has to perform selectively two successive reductive cleavages of the C=O functionalities without
breaking the cycle
Figure 1 Bioactive cyclic amines
As part of our ongoing interest for the application of catalytic hydrogenation in the preparation of
cyclic amines[1]
we became interested in the synthesis of fused N-heterocycles Herein we report
on the first efficient total reduction of nitrogen-unsubstituted cyclic imides in the presence of
heterogeneous catalysts generated in situ from rhodium and molybdenum carbonyls (Scheme)
Various substrates could be reduced with high selectivities and yields (both up to 100) Platinum
catalysts proved also efficient to hydrogenate some cyclic imides In addition all catalysts could be
recycled at least three times without significant loss of activity Finally hydrodeoxygenation of a
model cyclic imide was successfully performed on a gram scale[2]
References
[1] a) Maj A M Suisse I Meacuteliet C Agbossou-Niedercorn F Tetrahedron Asymmetry 2010
21 2010 b) Maj A M Suisse I Meacuteliet C Hardouin C Agbossou-Niedercorn F
Tetrahedron Lett 2012 53 4747 c) Maj A M Suisse I Hardouin C Agbossou-
Niedercorn F Tetrahedron 2013 69 9322
[2] Maj A M Suisse I Pinault N Robert N Agbossou-Niedercorn F ChemCatChem
accepted
HN
pTol
N
O
NH
NH
NH
S
OOO
N
O
HN
NHO
N
O
N
N
H
H
NHO O
NHO
Bicifadine Cytisine Gliclazide Telaprevir
N
O
O
H( )n
n = 0 or 1
N
O
H( )n N H( )nN
OH
H( )n+ +catalyst
PH2 T
solvent
up to 100 yield
115
P4
REACTIONS OF N-ALKYLHALOGENALDIMINES WITH OO-
DIALKYDITHIOPHOSPHORIC ACIDS
NG Aksenov RA Khairullin MB Gazizov RN Burangulova
Kazan National Research Technological University Department of Organic Chemistry Kazan
Russian Federation
We found that direction of interaction of N-alkyl-2-halogenaldimines (1-2) with ОО-
dialkyldithiophosphoric acids (3) mainly depends on the nature of halogen Reaction between ОО-
dialkyldithiophosphoric acids (3) and N-alkyl-2-chloroaldimines (1) was first studied by dynamic 1Н
13С and
31Р NMR in the temperature intervals from -60 degC to 25 degС It was found that reaction
proceeds in two steps At first step which proceeds at -60 degС the protonation of imine nitrogen
occurs and intermediate iminium salts are formed ndash ОО-dialkyldithiophosphates N-
alkylchloroaldiminium (4) At the second step which is observable at -5-0 degС the chlorine atom is
substituted by ОО-dialkyldithiophosphate group The final products of the reaction are chlorides of
N-alkyl-2-ОО-dialkyldithiophosphatopropaniminium (5) We propose that salt (4) is transfromed
into product (5) through the intermediacy of salt (6) with delocalized azaallyl dication as a result of
heterolytic dissociation of the bond tertiary carbon-chlorine
Synthetic result of the reaction of dithioacid (3) with N-alkyl-2-bromoaldimine (2) is completely
different ndash as major products were obtained phosphorylsulfide (7) and iminium salt of unsubstituted
aldimine (8) Thus we for the first time discovered the reaction of reduction of organic bromine
derivative (2) by ОО-dialkyldithiophosphoric acid At temperatures -80 ndash -70 degС 31
Р NMR
spectroscopy allowed to detect the formation of intermediate salt (9 δ 108 ppm)
The work is supported by RFBR and the Government of Tatarstan project 13-03-7098_p
povolzhe _а2013 and Ministry of education and Science (task 201456 within the framework
of basic part of stat task)
116
P5
METAL-FREE TRANSANNULATION REACTION OF INDOLES WITH
NITROSTYRENES SIMPLE PRACTICAL SYNTHESIS OF QUINOLINE
DERIVATIVES
AV Aksenov1 NA Aksenov
1 IV Aksenova
1 AN Smirnov
1 M Rubin
2
1 - Department of Chemistry North Caucasus Federal University Stavropol Russian Federation
2 - Department of Chemistry University of KansasLawrence USA
A convenient metal-free method for preparation of a large variety of 3-aryl- and 3-alkylsubstituted
2-quinolones 4 as well as 23-disubstituted quinolines was proposed This approach involves
previously unknown transannulation of 2-substituted indoles 1 in the reaction of β-nitrostyrenes 2 in
polyphosphoric acid The method is based on the ring-expansion of the pyrrole cycle in indoles
upon attack of amphyphilic reagents at the enamine double bond
N
R2
R1
R3
N+
O
ON
R2
R1
R3
N O H
O P( O )( O H )2
P P A
H+
H+
N
R2
R1
R3
O
NH
O H
OH2
N+
O P( O )( O H )2
N O H
R2
R3
R1
ON
N
R2
R1
R3
O P( O )( O H )2
ON H
N
R2
R1
R3
O P( O )( O H )2
R3
N H
O P( O )( O H )2
N
R2
O
R1
R3
N
N H
R1
OR2
OP
O
O H
OH
N
R1
R3
O
N
P
O
O H
O H
R2
O
N
R1
O
NH
+O
P
O
O
R2
R3
H+
N O
R3
R1
R2
NH
O P( O )( O H )2
+
2
1
-
+3
+
4
R
1= H Me R
2= Ph Me R
3= Ph 4-MeOC6H4 4-iPr-C6H4 34-Me2C6H3 4-EtOC6H42-FC6H4 34-
Cl2C6H3 3-BrC6H4 n-Pr
Introduction of an alkyl substituent into β-position of β-nitrostyrene 6 renders formation of
quinoline 7 as major product The mechanism of this transformation is identical to the one shown
above but includes elimination of water and aromatization at the last step
NH
R2 N
+R3
O
O N
R3
NH2
R2
O
+ +
1 6 7 5 R
2= Ph Me R
3= Ph Ph
Convenient and general metal-free approaches to 3-aryl and 3-alkyl-substituted 2-quinolones as
well as to 23-disubstituted quinolines were developed which included the previously unknown
process of transannulation of 2-substituted indoles in the reaction with β-nitrostyrenes in
polyphosphoric acid The reaction was also efficiently combined into a cascade with a Fisher indole
synthesis Unlike most other known methods the described protocol utilizes readily available
starting materials Unique properties of PPA serving as a mild proton donor source of efficient
leaving group (or temporary protecting group) water scavenger and high boiling solvent makes it
an ideal media for the described transformation
This work was carried out with financial support from the RFBR (grant 13-03-003004)
117
P6
MECHANOCHEMICAL SYNTHESIS OF CHROMIUM CARBOXYLATES
AND THEIR CATALYTIC PROPERTIES IN ETHYLENE TRIMERIZATION
KA Alferov1 LA Petrova
2 VD Makhaev
2 GP Belov
1
1 - Institute of Problems of Chemical Physics RAS Department of Polymers and Composite
Materials Chernogolovka Russian Federation
2 - Institute of Problems of Chemical Physics RAS Department of Functional Inorganic Materials
Chernogolovka Russian Federation
Selective synthesis of individual alpha olefins (1-butene 1-hexene 1-octene) is an urgent problem
because these compounds are widely used for the production of ethylene copolymers plasticizers
lubricants etc [1 2] One of the most efficient systems for ethylene trimerization is a system based
on chromium tris(2-ethylhexanoate) (Cr(EH)3) 25-dimethylpyrrole and organoaluminum
compounds Methods for the synthesis of Cr(EH)3 based on reactions in solutions are quite
laborious and lingering The products obtained by the methods are sticky and unhandy The
operations for the isolation and purification of the product complicate its production [3 4 5]
Nowadays green chemistry seems as a very promising research area so the processes of solvent-
free solid reactant interactions attract much attention We have developed a method for the
synthesis of Cr(EH)3 based on the solvent-free mechanochemical interaction of solid CrCl3 and
NaEH with subsequent heating of the reaction mixture [6] Physicochemical properties of the
reaction products and mechanically activated CrCl3-NaEH mixtures at different CrCl3NaEH ratios
were investigated by IR-spectroscopy XRDA and DCS The solid phase interaction of CrCl3 and
NaEH occurs in two main stages 1) the reagents mixture mechanical activation resulting in their
dispersion and mixing at the molecular or cluster level and 2) thermally initiated exothermic
interaction of the activated reactants to give the final products The use of the method makes it
possible to shorten the process duration appreciably
The obtained reaction mixtures and isolated Cr(EH)3 as well as commercially available Cr(EH)3 (8-
10 wt in mineral spirits) were tested as components of the Cr(EH)325-
dimethylpyrroleAlEt3CCl4 catalytic system for ethylene trimerization The productivity and
selectivity of the catalyst based on Cr(EH)3 synthesized by the mechanochemical method were
similar to the results obtained for the commercial Cr(EH)3 Moreover reaction mixtures produced
directly after the synthesis of Cr(EH)3 also form an active catalyst for ethylene trimerization
Syntheses differed in the time of mechanochemical activation (1-4 h) and reagent ratio
(NaEHCrCl3 = 23 ndash 39) were also performed The catalytic systems based on thus obtained
reaction mixtures demonstrated close values of productivity (11-13 kg(gCrmiddoth)) and selectivity (1-С6
= 82-85 wt C8+ = 13-15 wt PE = 01-03 wt) in ethylene to 1-hexene trimerization
The study was in part financially supported by the Russian Foundation for Basic Research (project
no 12-03-00974-a) and by the Presidium of the Russian Academy of Sciences Basic research
Program 3
[1] Dixon JT Green MJ Hess FM Morgan DH J Organomet Chem 689(23) 3641-3668
(2004)
[2] McGuinness D S Chem Rev 111(3) 2321-2341 (2011)
[3] Briggs JR US 466838 (Union Carbide Corporation) March 14 1986
[4] Knudsen RD et al US 20070043181 A1 (Chevron Phillips Chemical Company) August 19 2005
[5] Sydora OL et al US 20130150642 A1 (Chevron Phillips Chemical Company) December 12
2011
[6] Rus Patent Application 201315651220(088111) (IPCP RAS) December 20 2013
118
P7
EFFECT OF CHEMICAL STRUCTURE OF VIOLOGEN-DERIVATIVES AS
AN ARTIFICIAL CO-ENZYME ON THE CARBON DIOXIDE REDUCTION
ACTIVITY OF FORMATE DEHYDROGENASE
Y Amao1 S Ikeyama
2
1 - Osaka City UniversityAdvanced Research Institute for Natural Science and Technology
OsakaJapan
2 - Osaka City UniversityGraduate School of Science OsakaJapan
Many studies on electro-catalyzed CO2 reduction have been performed using specific electrode
materials On the other hand studies on CO2 fixation also have investigated photocatalysis on
semiconductors such as titanium dioxide silicon carbide and strontium titanate However these
systems use ultraviolet irradiation and the total reaction is low yield whereas highly efficient CO2
fixation system using visible light is more desirable We previously reported a system for visible
light-induced methanol synthesis from CO2 with the system formate aldehyde and alcohol
dehydrogenases and methylviologen (MV2+
) photoreduction by the visible light photosensitization
of water soluble zinc porphyrin in the presence of an electron donor in aqueous media On this
system the reduced form of methylviologen (MV+
) is used as an artificial co-enzyme for these
dehydrogenases To improve the yield for methanol production from CO2 conversion of CO2 to
formic acid with formate dehydrogenase (FDH) and reduced formed viologen is most important
step
In this work some artificial co-enzymes with 44rsquo- bipyridine skeletons as shown in Figure 1 are
synthesized and effect of chemical structures of
artificial co-enzymes on the activity of the reduction
of CO2 to formic acid with FDH are investigated
The conversion of CO2 to formic acid with FDH and
one-electron reduced form of artificial co-enzyme
was carried out as following method The sample
solution containing 30 micromol of artificial co-enzyme
57 mmol of sodium dithionate and FDH (10 units)
in 36 ml of CO2 saturated sodium pyrophosphate
buffer (pH 74) at 305 ˚C for 1 min The formic acid
concentration produced is measured by ionic chromatography
By using MV2+
as the reference the formic acid production increased by using cationic artificial co-
enzymes (H2NH2CH2C-V-CH2CH2NH2 and CH3-V-CH2CH2NH2) On the other hand the HCOOH
production decreased by using anionic co-enzymes (HOOCH2C-V-CH2COOH and CH3-V-
CH2COOH) The production of formic acid in this reaction depends on chemical structures of
artificial co-enzymes Among the artificial co-enzymes H2NH2CH2C-V-CH2CH2NH2 has high
affinity for FDH compared with the other compounds
Figure 1 Chemical structures of viologen-derivatives as artificial co-enzymes for formate dehydrogenase
119
P8
Cu(I)-CATALYZED ARYLATION OF BIOLOGICALLY ACTIVE
DI- AND POLYAMINES
AD Averin MV Anokhin SP Panchenko IP Beletskaya
MV Lomonosov Moscow State University Department of Chemistry Moscow Russia
Di- and polyamines like putrescine cadaverine spermidine and spermine were chosen for the
studies of their Cu(I)-catalyzed NNrsquo-diarylation for the synthesis of new compounds with diverse
biological activity Arylation was carried out using iodobenzene 4-fluoroiodobenzene 4-
(trifluoromethyl)iodobenzene and 4-iodobiphenyl The reactions of butane-14-diamine were
successfully catalyzed with either CuIL1 (L1 = L-proline) or CuIL2 (L2 = 2-
isobutyrylcyclohexanone) systems while pentane-15-diamine demonstrated better results with
CuIL2 system Cs2CO3 was taken as a base in all cases
Selective N
1N
3-diarylation of triamine and N
1N
4-diarylation of tetraamine turned to be a more
complicated task and target compounds were obtained in moderate yields using CuIL2 catalytic
system
Acknowledgement The work was financially supported by the RFBR grant N 12-03-00796
120
P9
NITRATING AND NITROSATING REAGENTS IN NOVEL
HETEROCYCLIZATION REACTIONS READY ACCESS TO HIGHLY
SUBSTITUTED PYRIMIDINE AND ISOXAZOLE DERIVATIVES
EB Averina KN Sedenkova DA Vasilenko TS Kuznetsova NS Zefirov
Lomonosov Moscow State University Department of Chemistry
Recently we have elaborated novel synthetic approaches to five- and six-membered N- and NO-
heterocycles basing on the heterocyclization of electrophilic alkenes or three-membered carbocycles
under the treatment with nitrating or nitrosating reagents
The reaction of tetranitromethane with electrophilic alkenes in presence of triethylamine was found
to afford 5-nitroisoxazoles 1 ndash highly reactive and versatile compounds which may be used as
precursors of diverse functionalized compounds [1] Employing the reduction of nitroisoxazoles 2
we suggested the regioselective method of synthesis of 5-aminoisoxazoles 2 that was used to
accomplish a structure design of biologically active compounds The series of compounds 2 was
obtained in good yields (50-90) and their antiviral activity was investigated
A series of previously unknown 4-fluoropyrimidine 1-oxides 4 was obtained via three-component
heterocyclization involving gem-bromofluorocyclopropanes 3 nitrosating or nitrating agent and
organic nitrile [2] Preparative method of synthesis of 4-fluoropyrimidines 5 from corresponding N-
oxides under the treatment with PCl3 was elaborated
F
Br RCN
R1
R2
R1
R2 N
N
F
O
RR1 R2
CBrF
R1
R2 N
N
F
R
[NO+]
RR1R2 Alk Ar
[NO+] NOBF4
NO2BF4 NO2OTf
3 4
5
NO
EWG
NO2
R2
EtOH
C(NO2)4 -Et3N
PCl3
NO
EWG
NH2
R2
SnCl2
2
R1 = EWG (C(O)R
CO2R P(O)(OEt)2
NO2 CO2R)
R2 = H Alk
1
4-Fluorosubstituted pyrimidine N-oxides 4 and pyrimidines 5 demonstrate high reactivity in
aromatic nucleophilic substitution with various O- N- P-nucleophiles In particular a series of 4-
aminopyrimidines and pyrimidine N-oxides potent as compounds with antiviral activity was
obtained via this reaction
In conclusion simple and efficient synthetic methods allowing polyfunctionalized isoxazoles
pyrimidines and pyrimidine N-oxides including those with valuable properties from readily
available starting materials were developed
We thank the Russian Foundation for Basic Research (Projects 14-03-31989-mol_а 14-03-00469-
a) and Presidium RAS (program 8P) for financial support of this work [1] (a) YA Volkova EB Averina YK Grishin P Bruheim TS Kuznetsova NS Zefirov J Org Chem
2010 75 3047-3052 (b) EB Averina YA Volkova YV Samoilichenko YK Grishin VB
Rybakov AG Kutateladze ME Elyashberg TS Kuznetsova NS Zefirov Tetrahedron Lett 2012
53 1472ndash1475 [2] (a) KN Sedenkova EB Averina YuK Grishin AG Kutateladze VB Rybakov
TS Kuznetsova NS Zefirov J Org Chem 2012 77 9893ndash9899 (b) KN Sedenkova EB Averina
YuK Grishin TS Kuznetsova NS Zefirov Tetrahedron Lett 2014 55 483ndash485
121
P10
TRANSFER HYDROGENATION OF ACETOPHENONE OVER BIS-IMINE
RHODIUM(I) COMPLEX DFT STUDY
NM Badyrova1 Z Lin
2 LO Nindakova
1
1 - Irkutsk State Technical University Physical and Technical Institute Irkutsk Russia
2 - The Hong Kong University of Science and Technology Department of Chemistry Hong Kong
(P R China)
There are two reaction mechanisms for asymmetric transfer hydrogenation reactions of ketones over
a diamine rhodium(I) complex leading to optically active secondary alcohols a stepwise process
through an intermediate hydride complex derived from an alkoxy complex via -hydride
elimination and a concerted process where the hydrogen is directly transferred from the alkoxy
complex to the coordinated substrate [1]
Here we investigated mechanism of hydrogen transfer reaction (Scheme 1) from 2-propanol to
acetophenone over a bis-imine-rhodium(I)-chloride complex with optical active bisndashimine ligand
RR-1 on the basis of DFT theoretical calculations
Scheme 1
Based on the mechanism proposed by Guiral et al [1] we designed a catalytic cycle (Scheme 2)
This cycle starts with the hydride complex 1 The first step is reversible dissociation of a Rh-N
bond in the 18-electron hydride complex leading to a 16-electron intermediate (the hydride complex
2) From 2 there are two possible pathways to achieve hydride transfer to acetophenone an external
pathway vial 3a and an internal pathway via 3b (Scheme 2) Both the two hydride transfer pathways
give the alkoxy complex 4 which leads to 5 after with a metathesis with 2-propanol to release the
product molecule Next step involves -H elimination to give 6 followed by release of the side-
product (acetone) to regenerate the starting hydride complex 1
Scheme 2
N N
N NRh
H
N N
N
NRh
O
CH
H3CPh
N N
N
NRh
O
CH
H3CCH3
N N
N
NRh
H
O
C
H3C CH3
N N
N
NRh
H
N N
N
NRh
H
OC
CH3
Ph
N N
N
NRh
H O
CH3C
Ph
(CH3)2CHOH
(CH3)PhCHOH(CH3)2CO
1
2
3a
3b
4
56
Geometry optimizations of all species have been performed by means of the DFT M06 hybrid
method [2] The 6-31G(d) basis set was chosen to describe C N O H atoms and the LanL2DZ
basis set was used for Rh All of the calculations were performed with the Gaussian 09 program [3] 1 Guiral V Delbecq F Sautet P Organometallics 2000 19 1589-1598
2 Zhao Y Truhlar D G Theor Chem Account 2008 120 215-241
3 Frisch M J et al Gaussian 09 Revision A1 Gaussian Inc Wallingford CT 2009
122
P11
RHODIUM(II) CATALYZED REACTIONS FOR SYNTHESIS OF NOVEL
AND DIVERSE FURO[23-D]PYRIMIDINEDIONES AND
THIOXOFURO[23-D]PYRIMIDINEONES
ER Baral KB Somai Magar YR Lee
School of Chemical Engineering Yeungnam University Gyeongsan 712-749 Republic of Korea
Furopyrimidines the derivatives of pyrimidine and analog of purine have been demonstrated to
have antimalarial antifolate antitumor antiviral antibacterial and antifungal and antihypertensive
properties1-2
Accordingly several methods have been devised to synthesize furopyrimidines3-4
The
general methods for the synthesis of furo[23-d]pyrimidinediones by ceric ammonium nitrate
mediation involving ionic (non-carbenoid) mechanism is limited with the substrate scope in terms
of olefins and alkynes with low yields5 while three component reactions of NNrsquo-dimethylbarbituric
acid with benzaldehydes and isocyanides provided 23-disubstituted furans6 However there is a
need for more convenient and efficient synthetic methods for the preparation of furo[23-
d]pyrimidinedione derivatives and in particular the synthesis of thioxofuro[23-d]pyrimidinedione
derivatives has not been reported to date
In this conference we present the rhodium (II)-catalyzed reactions of cyclic diazo compounds
derived from barbituric acid or thiobarbituric acid with arylacetylenes and styrenes These reactions
provide a rapid synthetic route to the preparation of a variety of novel and diverse furo[23-
d]pyrimidine-24-diones 2-thioxodihydrofuro[23-d]pyrimidin-4-ones dihydrofuro[23-
d]pyrimidine-24-diones and 2-thioxotetrahydrofuro[23-d]pyrimidin-4-ones
N
N
O
O
N2R
R
X
X=O SR=Me Et
Y
Rh2(OPiv)4
N
N
O
R
R
X O Y
Y
Rh2(OPiv)4
N
N
O
R
R
X O Y
PhFrt - 60 oCtoluene
reflux
References
1 G Jaumlhne H Kroha A Muumlller M Helsberg I Winkler G Gross T Scholl Angew Chem Int
Ed Engl 1994 33 562-563
2 Q Dang Y Liu M D Erion J Am Chem Soc 1999 121 5833-5834
3 A Sniady M D Sevilla S Meneni T Lis S Szafert D Khanduri J M Finke R Dembinski
Chem Eur J 2009 15 7569-7577
4 A Sniady A Durham M S Morreale A Marcinek S Szafert T Lis K R Brzezinska T
Iwasaki T Ohshima K Mashima R Dembinski J OrgChem 2008 73 5881-5889
5 K Kobayashi H Tanaka K Tanaka K Yoneda Synth Commun 2000 30 4277-4291
6 M B Teimouri R Bazhrang Bioorg Med Chem Lett 2006 16 3697-3701
123
P12
DUAL REACTIVITY OF NTROARENES IN [4+2]-CYCLOADDITION
REACTIONS
MA Bastrakov AM Starosotnikov SA Shevelev
ND Zelinsky Institute of Organic Chemistry RAS Laboratory of Nitrogen-containing Aromatic
Compounds Moscow Russia
[4+2]-Cycloaddition is one of the fundamental protocols for the construction of a new ring which
accompanies the formation of two bonds This reaction is known for nitroalkenes1a
as well as for
few highly electrophilic (low aromatic) benzoazoles1b-c
These compounds readily undergo Diels-
Alder reactions at C-C double bond activated by the nitro group Also they form anionic σ-adducts
with very weak nucleophiles1b
As a part of our research on highly electrophilic heterocyclic systems we have found that 46-
dinitroanthranil reacts with dienes and nucleophilic dienophiles in mild conditions2
Moreover we have proposed methods for the synthesis of new policyclic heteroaromatic
compounds on the nitroarenes basis consisting in annelation of a furoxan ring to different
dinitrobenzoazoles and azines3 Some of these compounds readily undergo [4+2]-cycloaddtition
with dienes and dienophiles
This work was supported by the Russian Foundation for Basic Research Projects No 13-03-00452
14-03-31508 mol_a and Grant of the President of the Russian Federation for State Support to young
Russian scientists Grant MK-359920133
1 (a) SE Denmark A Thorarensen Chem Rev 1996 96 137 (b) S Lakhdar R Goumont T
Boubaker M Mokhtari F Terrier Org Biomol Chem 2006 4 1910 (c) S Kurbatov R
Goumont S Lakhdar J Marrot F Terrier Tetrahedron 2005 61 8167
2 AM Starosotnikov MA Leontieva MA Bastrakov AV Puchnin VV Kachala IV
Glukhov SA Shevelev Mendeleev Commun 2010 20 165
3 MA Bastrakov AM Starosotnikov IV Glukhov SA Shevelev Russ Chem Bull Int Ed
2009 58 426
124
R2NH
COOH
N
O
O
R
R = C2H5 (3) n-C3H7 (4) n-C4H9 (5)
(3 4 5)
COOH
O
O
OR +
R = H (1) CH3 (2)
R = CH3
135oC
R = H
COOH
N
O
O
R
COOH
NR2
COOH
O+
(6-8) (9 10)
R = C2H5 (6 9) n-C3H7 (7 10) n-C4H9 (8) The exact structure of regioisomer is not established
(1 2)135oC
COOH
N
O
OR
R+ +
R = CH3 C2H5 R = H CH3
R
HN
OH
COOH
N
O
OR
OH
P13
UNEXPECTED FORMATION OF N-ALKYLIMIDES IN REACTION OF
MALEOPIMARIC AND CITRACONOPIMARIC ACIDS WITH
SECONDARY AMINES
MP Bei1 AP Yuvchenko
1 AV Baranovsky
2
1 - The Institute of Chemistry of New Materials 36 FSkoriny st Minsk 220141 Belarus
2 - The Institute of Bioorganic Chemistry 52 Kuprevich st Minsk 220141 Belarus
The Diels-Alder reaction of levopimaric acid with active dienophiles produces adducts (maleo- fumaro-
quinopimaric acids) which are useful precursors in the synthesis of chiral ligands terpenoquinones
biologically active compounds Recently we have reported the synthesis of isomer of citraconopimaric acid
(2) an analog of well-known maleopimaric acid (1) bearing methyl group at C-151
The method includes
preparation of the adduct of pine rosin with citraconic anhydride (formed in situ from itaconic acid) followed
by recrystallization of the product from carbon tetrachloride and benzene
We have initiated the investigation of the reaction of citraconopimaric acid (2) with some secondary aliphatic
amines in order to study the steric influence of the CH3 group at C-15 of the acid (2) on regioselectivity of
anhydride ring opening by nucleophilic agents
It was established that the heating of citraconopimaric acid (2) solution in diethylamine dipropylamine in
autoclave dibutylamine at 135ordmC for 30h leads to the formation of N-ethyl- N-propyl- N-butylimides of
citraconopimaric acid (3minus5) Unlike citraconopimaric acid (2) reactions of maleopimaric acid (1) with
diethyl- dipropylamine at 135ordmC gave N-ethyl- N-propylimides of maleopimaric acid (6 7 yields 60minus80)
and amidodiacids (9 10 yields 10minus15) and the reaction with dibutylamine gave only maleopimaric acid
N-butylimide (8)2
The formation of N-alkylimides (3minus8) in the above transformations could be result of a thermal degradation
of intermediate amidoacids giving stable cyclic imides Would this assumption be true the formation of
mixture of two imides should be observed in the reaction of acids (1 2) with unsymmetrical secondary
amines Thus when acids (1 2) were treated with methyl- or ethyl-(2-hydroxyethyl)amine the formation of
a mixture of two imides indeed was observed2
[1] MP Bei AP Yuvchenko Patent of the Republic of Belarus 13646 2009
[2] MP Bei AP Yuvchenko AV Baranovsky Proceed Nat Acad Sci Belarus 2013 N 4 104
125
P14
SYNTHESIS OF TRYPTAMINES FROM CYCLOPROPYLKETONES
ARYLHYDRAZONES AND THEIR BIOLOGICAL STUDIES
AYu Belyy1 RF Salikov
2 YuV Tomilov
2
1 - Higher Chemical College of Russian Academy of Sciences
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
Tryptamine derivatives are psychoactive compounds and are widely used as 5-HT agonists We
have found that cyclopropyl methyl ketone hydrazones rearrange into a mixture of
tetrahydropyridazines and tryptamines the best yield of tryptamine being observed in the case of
generated in situ bromophenylhydrazone The rearrangement of cyclopropyl ketones with a bulky
group in most cases gives tetrahydropyridazines exclusively
The tryptamine derivatives obtained demonstrated their antitumor activity against human
neuroblastoma cell line SH-SY5Y The best result was shown by 2-methyl-5-bromotryptamine
(IC50 = 506 microМ) with the therapeutic index of 4 determined from the toxicity against human
embryonic kidney cells (HEK 293)
In order to investigate the biological activity of this interesting class of compounds we derived the
tryptamines in three different ways substitution of bromine indole nitrogen alkylation and primary
amine nitrogen The biological studies are under performance
126
P15
DEHYDROGENATION OF LOW ALIPHATIC ALCOHOLS ON COPPER
SUPPORTED STRUCTURED CATALYST
DA Bokarev1 EA Ponomareva
2 EV Egorova
2
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Lomonosov Moscow State University of Fine Chemical Technologies Moscow Russia
The important direction of the chemical industry development is engineering of new alternative
manufactures based on renewable sources of raw materials These materials could be methanol and
ethanol especially applied for synthesis of methylformiat and acetaldehyde respectively
2CH3OH rarr HCOOCH3+2H2
C2H5OH rarr CH3CHO +H2
To realize the process of dehydrogenation with high technical parameters new catalytic systems
must be worked out Recently new classes of heterogeneous catalysts based on structured carbon
fibers were developed They possess a number of advantages - homogeneous distribution of a
stream low pressure drop Moreover fibers structured catalysts offer flexibility and endless forms
that allow using them in reactors of a various constructions
It was shown that 5 wt of copper supported by impregnation appeared to be optimal in the
process of alcohol dehydrogenation Compared to powder and granular carbon materials used
earlier catalysts based on structural carbon fibers showed higher activity and selectivity due to
better distribution of active component on the surface of the carrier (fig1)
Fig 1 Distribution of copper particles on the surface of carbon structured fiber (left) and granular
carbon material Sibunit (right)
Thus application of structured carbon fibers as a support of copper catalytic system leads to
increase of activity in comparison with known literature data That allows to make a conclusion
about appropriateness of using it in the process of dehydrogenation of low aliphatic alcohols
Activity ndash 126 gMeOHgCuh and 237 gEtOHgCuh
Activity ndash 24 gMeOHgCuh and 68 gEtOHgCuh
127
P16
ARYLAMINATION OF 137-TRIAZAPYRENES
IV Borovlev OP Demidov NA Saigakova GA Amangasieva
North Caucasus Federal University Department of Chemistry Stavropol Russia
In our previous reports we have shown that 137-triazapyrene displays peculiar properties due to
the unique fusion of the carbocyclic and heterocyclic rings Specifically these properties include the
unusual ease of oxidative nucleophilic substitution of hydrogen such as amination [1] and
alkylamination [2] which proceed in aqueous media The aim of this work is the synthesis of
arylamino derivatives of this heterocycle In spite of a common mechanism the conditions
mentioned above are not suitable for arylamination reaction due to the low nucleophilicity of aryl
amines and their high sensitivity towards oxidation This is why SNH-arylamination reactions are
still rare
We have found that the interaction of 137-triazapyrenes 1 with an excess of sodium arylamides
obtained in situ in absolute DMSO proceeds at room temperature to form the 6-aryl(hetaryl)amino-
137-triazapyrenes 2 in 32-97 yields It was shown that the decisive factor for rearomatization of
σH-adducts is crucial access to the air oxygen
NN
N
R
X
NN
N N H A r
R
X
1 A rN H - N a +
D M S O R T O2
1 2
2 H2O
R = H Me X = H Ar NR2
Under the same conditions (DMSO room temperature) the reaction of the rather accessible 68-
dialkoxy-137-triazapyrenes 3 with sodium aryl amide has resulted to a product of nucleophilic
ipso substitution of one of the two RO groups - 6-alkoxy-8-aryl(hetaryl)amino-137-triazapyrenes
4
NN
NR O O R
NN
N N H A rA r N H
NN
NR O N H A r
1 A rN H - N a +
D M S O R T
3 5
2 H2O
1 A rN H - N a +
re flu x in g to lu en e
2 H2O
4 R = Me Et
Products of double ipso substitution ndash 68-bis(aryl(hetaryl)amino)-137-triazapyrenes 5 were
synthesized by refluxing of the compounds 3 with excess of the sodium arylamides in toluene for a
long time Consecutively replacing one methoxy group in 68-dimethoxy-137-triazapyrene in
DMSO and the second - in toluene we obtained asymmetrically substituted diamine - 6-
phenylamino-8-(pyridin-4-ylamino)-137-triazapyrene
This project received financial support from the Ministry of Education and Science of the Russian
Federation in the framework of the State Assignment to the Higher Education Institutions
41412014K
[1] O P Demidov I V Borovlev N A Saigakova O A Nemykina N V Demidova and S V
Pisarenko Khim Geterotsikl Soedin 142 (2011) [Chem Heterocycl Compd 47 114 (2011)]
[2] I V Borovlev O P Demidov N A Saigakova S V Pisarenko O A Nemykina J
Heterocycl Chem 48 No 5 1206 (2011)
128
P17
SUSTAINABLE APPROACHES FOR ORGANIC SYNTHETIC PROCESSES
LC Branco K Zalewska G Carrera MN Da Ponte
REQUIMTE Departamento de Quнmica Faculdade de Ciкncias e Tecnologia Universidade Nova
de Lisboa 2829-516 Caparica Portugal
For many synthetic approaches the incorporation of CO2 as alternative reagent or green solvent can
improve significantly the efficiency (yields purity reaction conditions) for several organic
processes In recent years the use and capture of Carbon Dioxide (CO2) became a hot research topic
including their application for organic and pharmaceutical chemistry1 The possibility to use carbon
dioxide as useful reagent for different synthetic approaches or supercritical CO2 for efficient
extraction and separation processes has been reported1
The combination of ionic liquids and supercritical fluids has been reported for many organic
transformations in particular catalytic reactions2 The possibility to use scCO2 in order to extract the
pure products without IL or catalyst contamination is one of the advantages for these processes
Several publications proof the advantages for ILs and scCO2 combinations in order to recycle the
catalytic media during many reaction cycles without loss of efficiency
In this communication we described the applicability of carbon dioxide approaches in two different
organic synthetic processes3
a) The use of CO2 as reagent for the preparation of reversible chiral and non-chiral carbamate
salts by the reaction with different amines (eg primary alkyl and aryl amines or polyamines)
aminoacids and pharmaceutical compounds in the presence of an organic superbase (eg DBU or
tetramethylguanidine) According with the optimized reaction conditions itacutes possible to tune the
chemical and thermal stability as well as potential application of the final salts
b) The potential use of scCO2 for extraction and separation processes in the case of three
asymmetric catalytic reactions in the presence of ionic liquids andor chiral ionic liquids as
solvent or chiral media respectively In particular Sharpless asymmetric dihydroxylation of olefins
(in the presence of osmium catalyst) asymmetric Aldol and Michael reactions (in the presence of
chiral organocatalysts based on chiral ILs) will be presented
The peculiar properties of carbon dioxide including as supercritical fluid open excellent
perspectives for the application in novel organic synthetic transformations as well as their use in
industrial processes
Acknowledgements We thank the Fundaccedilatildeo para a Ciecircncia e Tecnologia for financial support
(PEst-CEQBLA00062011 and PTDCCTM1036642008 projects and SFRHBD671742009 for
KZ PhD grant)
References 1 a) Goodrich B F de la Fuente J C Gurkan B E Zadigian D J Price E A Huang Y
Ind Eng Chem Res 2011 50 111 b) Camper D Bara J E Gin D L Noble R D Ind
Eng Chem Res 2008 47 8496
2 Afonso C A M Branco L C Candeias N R Gois P M P Lourenccedilo N M T Mateus
N M M Rosa J N Chem Commun 2007 2669
3 a) Carrera G V M da Ponte M N Branco L C Tetrahedron 2012 68 7408 b) Branco L
C Serbanovic A da Ponte M N Afonso C A M ACS Catalysis 2011 1 1408 c) Carrera
G V SM Costa A Ponte M N Branco LC Synlett 2013 24 2525
129
P18
1H AND
13C ASSIGNMENTS OF THREE SERIES BIOACTIVE
IMIDAZO[21-B]THIAZOLE DERIVATIVES
AS Bunev EV Sukhonosova GI Ostapenko PP Purygin
Togliatti State University Togliatti Russia
The complete 1H and
13C NMR assignments of three series bioactive imidazo[21-b]thiazoles were
achieved by combination of one and two-dimensional NMR experiments and the NMR signals of
these compounds were analyzed and compared
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No 426)
130
P19
SYNTHESIS OF 145-TRISUBSTITUTED IMIDAZOLES CONTAINING
TRIFLUOROMETHYL GROUP
AS Bunev MA Vasiliev GI Ostapenko VE Statsyuk
Togliatti State University Togliatti Russia
A new synthetic protocol for the synthesis of 145-trisubstituted imidazoles (2a-i) containing
trifluoromethyl group has been developed using van Leusen reaction which incorporates two-
component condensation reaction trifluoroacetimidoyl chlorides (1a-i) with tosylmethylisocyanide
This protocol provides a novel and improved method for obtaining trifluoromethyl containing 145-
trisubstituted imidazoles in good yields
The authors are grateful to the Ministry of Education and Science of the Russian Federation (State
job No 426)
131
P20
THE QUANTUM-CHEMICAL STUDY OF THE KEY STEP OF THE
CYCLIZATION OF 411-DIMETHOXY-510-DIOXO-2- ANTHRA[23-B]-
FURAN-3-CARBOXYLATES
EE Bykov AS Tikhomirov AE Shchekotikhin MN Preobrazhenskaya
Gause Institute of New Antibiotics RASM Moscow Russia
Highly active inhibitors of topoisomerase I capable of blocking the growth of tumor cells with
activated mechanisms of multiple drug resistance were discovered in the series of derivatives 411-
dihydroxy-510-dioxoanthra[23-b]furan-3-carboxylic acids [1] Previously a scheme of preparation
of 2-substituted derivatives of 411-dimethoxy-510-dioxoanthra[23-b]furan-3-carboxylic acids was
developed However yields of anthrafurandiones by this method seriously depended on a substituent
in position 2 [2] To understand this a quantum-chemical estimations of the key step of the
intermolecular cyclization of the intermediate enol forms of ethyl 2-(3-bromo-14-dimethoxy-910-
dioxo-910-dihydroanthracene-2-yl)-3-hydroxypropanoates 1a-c to the corresponding anthra[23-
b]furan-510-diones 2a-c were carried out
The quantum-chemical calculations by DFT method B3LYP6-31+G(d) by means program package
Gaussian-09 [3] confirmed that the activation barriers (ΔE
) of cyclization of enol form 1a-c
depend on the nature of the substituent R The groups R that have different electronic properties
influence actively on the electron density of the internal nucleophile what is enolic oxygen atom
(see Table QO and ΕHOMO) The calculated values of ΔE
correlate with the yield of the anthra[23-
b]furan-510-diones 2a-c [2] Thus quantum-chemical evaluation of the key step of cyclization
confirmed that the electron-withdrawing substituents reduce the reactivity of enol intermediates 1a-
c in the cyclization to the corresponding anthra[23-b]furan-510-diones 2a-c
Table Parameters for the reaction of cyclization of anthra[23-b]furan-510-diones 2a-c
Derivative 2a 2b 2c
R -CH3 -Ph -CF3
ΔE (kcalmol) 2184 227 2586
ΕHOMO (ev) -201 -223 -245
QO -0687 -0577 -0567
The yield [2] 72 40 3
References
1 Shchekotikhin A E et al Patent RU 2412166 (2011)
2 Tikhomirov A S Shchekotikhin A EChem Heterocycl Compd 2014 50 271
3 httpwwwgaussiancom
132
P21
MACROPOLYCYCLIC COMPOUNDS COMPRISING DIAZACROWN
ETHER MOIETIES AND FLUOROPHORE GROUPS
NM Chernichenko AD Averin IP Beletskaya
MV Lomonosov Moscow State University Department of Chemistry Moscow Russia
Macrobicyclic compounds comprising structural fragments of diazacrown ethers and oxadiamines
were synthesized using Pd-catalyzed amination reactions using Pd(dba)2BINAP system [1] They
were further modified with various fluorophore substituents using catalytic and non-catalytic
approaches to create promising fluorescent chemosensors and molecular probes for metal cations
Modification was carried out at N atoms of the cryptand and at C atoms of the benzyl spacer
Macrotricycles and isomeric trismacrocycles were obtained via Pd-catalyzed macrocyclization
reactions of NNrsquo-bis(35-dibromobenzyl) diazacrown ether derivatives with oxadiamines using
either BINAP or RuPhos ligands and were further modified with dansyl fluorophores
Acknowledgement The work was financially supported by the RFBR grant N 12-03-93107
[1] AA Yakushev NM Chernichenko MV Anokhin AD Averin AK Buryak F Denat IP
Beletskaya Molecules 2014 19 940-965
133
P22
SYNTHESIS OF 1Н-IMIDAZOLECARBOXAMIDES
IV Zavarzin VN Yarovenko SL Semenov EI Chernoburova MM Krayushkin
N D Zelinsky Institute of Organic Chemistry Laboratory for Chemistry of Steroid Compounds
Moscow Russia
We earlier proposed the method for synthesis of 45-dihydro-1Н-imidazolecarboxamides (1) by the
reaction of chloroacetamides with aliphatic diamines in the presence of sulfur12
(Scheme 1)
R N H
O
C lH
2N(C H
2) n
2N H
2
R N H
O
NH
( C H2)
N
1n n = 1 2
Scheme 1
In this work we propose the method for the transformation of products 1 into 1Н-
imidazolecarboxamides 2 We found that the interaction of 1а-с with NiAl alloy in aqueous
methanol at 20оС results in the dehydrogenation of dihydroimidazole fragments to form imidazoles
2а-с
NN
NH
O H
R
NN
NH
O H
R
Ni A l K O H
M e O H H2O
1 a -c 2 a -c
R = 2 -F 3 -O M e 2 4 -M e
Scheme 2
References
1 VN Yarovenko SA Kosarev IV Zavarzin MM Krayushkin Russ Chem Bull (Int Ed)
1999 No 4 p 753
2 MM Krayushkin VN Yarovenko IV Zavarzin Russ Chem Bull (Int Ed) 2004 No 3 p
491
134
P23
FEPMD PROTOCOL TO MODEL SELECTIVITY OF KINASE
INHIBITORS
GG Chilov OV Stroganov FN Novikov AA Zeifman VS Stroylov IYu Titov IV
Svitanko
ND Zelinsky Institute of Organic Chemistry RAS
With over 500 different kinase enzymes encoded in a human genome and appreciation the role of
kinases as promising therapeutic targets the selectivity profile of a kinase inhibitor is an important
indicator of its potential off-target effects including adverse effects which sometimes might be
quite severe and even preclude application of a drug in clinical practice One of the recent examples
of how the lack of selectivity of a kinase inhibitor drug may restrict its clinical application because
of abundant life-threatening adverse effects is presented by Ponatinib - a potent inhitor of Abl
kinase (primary therapeutic target) as well as over 40 off-target kinases With the intent to
overcome adverse effcts of Ponatinib we designed a PF-114 molecule which appeard to be
comparable to Ponatinib with respect to Abl suppression but inhibited only 10 off-target kinases In
order to rationalize enhanced selectivity we established a FEPMD protocol in which for each
kinase Ponatinib molecule was transformed to PF-114 and the dG of such transition was recorded
The modeled system consisted of a full atom kinase domain with inhibitor docked into ATP-bindin
site and immersed in a box of explicit solvent FEP transition was split into 3 steps decharging
initial molecule (Ponatinib) converting Van der Waals parameters to another molecule (PF-114)
and then charging the resulting molecule Each transition was split in its turn into 10 windows each
taking 2 ns of MD simulation Totally 15 kinases were modeled for the selectivity of inhibition It
appeared that calculated selecivities correlaeted with experimental data with R of 063 Structural
findings from FEPMD simulations uncovered 2 factors contributing to the enhanced selectivity of
PF-114 its unfavorable (compared to Ponatinib) interaction with main chain carbonyl oxygen
present in the active site of BRAF Src ERBB4 FGFR1 VEGFR2 TRKC TRKB and
unfavorable interaction with water molecule in the active sites of BRAF EPHA7 FGFR1 FLT1
MAPK11 MAPK14 kinases Current results suggests that full atomic FEPMD modeling may be a
valuable instrument in the design of kinase inhibitors with improved selectivity
135
P24
FEATURES OF NATURAL POLYSACCHARIDE BASED THIN FILMS
FORMATION
YV Chudinova2 DV Kurek
2
1 - MVLomonosov Moscow State University Moscow Russia
2 - Centre laquoBioengineeringraquo RAS Moscow Russia
Natural polysaccharide based thin films are promising biomaterials for using in different fields of
science Thin films were prepared by layer-by-layer (LbL) technique via alternately dipping the
substrate into polycation and polyanion solutions to form polyelectrolyte multilayers During each
adsorption cycle one a monolayer is built up and the surface charge is reversed This assembly
process allows obtaining films with desired characteristic Layer-by-layer method offers several
advantages over other thin film deposition techniques for example it is simple rapid and
inexpensive
Polyelectrolyte LbL films can be assembled from chitosan pectin and other natural polymers
Pectin is one of the basic components of plant cell wall It has a complex structure and contained
linear and branched regions Chitosan is produced by deacetylation of chitin which is the structural
element in the exoskeleton of crustaceans and cell walls of fungi Chitosan and pectin are
considered as some of the most attractive natural polyelectrolytes because they are nontoxic
biodegradable and biocompatible polymers Their oppositely charged surface permits to use them
for generating biocompatible surfaces via multilayer assembly
The main characteristic of biofilms such as surface topography roughness thickness molecular
structure adhesion forces were determined by atomic force microscopy (AFM)
Influence of polyelectrolyte type and number of layers on the film buildup were investigated Pectin
covers mica surfaces very well and filling degree is nearly 100 Chitosan forms heterogeneous
structures on the mica surface with a lesser filling degree Chitosan with different molecular weight
was studied Results showed that in all cases were formed particles and aggregates
Influence of substrate type and its possible modifications was considered Surface topography
height roughness of the films which formed on the substrates with different properties were varied
Further effect of the concentration and the presence of other polysaccharide were observed Pectin-
chitosan and chitosan-pectin coatings which formed via layer-by-layer technique had different
morphological characteristics
The adhesion of the polyelectrolyte multilayer films has been investigated by contact mode of
AFM Adhesion is the attraction forces between the AFM tip and the film surfaces by force-curves
mode [1] Obtained data demonstrated relationship between adhesion forces and surfaces properties
Understanding of the molecular structure and pathways of formation such thin films allows to
predict the characteristics and produce coating materials for use in various fields of biology and
medicine
References
1 Guo Y-B Wang D-G Adhesion and friction of nanoparticlespolyelectrolyte multilayer films
by AFM and micro-tribometer Tribology International- N 44 - P 906ndash915 - 2011
136
P25
SYNTHESIS OF N-(PICRYLAMINO)NITROPYRAZOLES
IL Dalinger IA Vatsadze TK Shkineva AV Kormanov SA Shevelev
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Laboratory of
Nitrogen-containing Aromatic Compounds Moscow Russian Federation
One of the directions of modern design of nitroazole-based high-energy compounds consists in the
introduction of an N-amino group to the endocyclic nitrogen atom of the nitroazole ring This
results in the preparation of N-amino derivatives of nitrotetrazole [1] nitrotriazoles [1-3]
nitroimidazoles [4] and nitropyrazoles [3 5-8]
However the possibility functionalization N-aminonitroazoles additional energy-rich groups with
saving of nitro groups in azole cycle poorly understood and limited only N-nitration [4a] N-
trinitroethylation [3 4c] and the introduction of a fragment of [124]triazolo[43-b]-
[1245]tetrazine [9]
In continuation of our works on chemistry of polynitropyrazoles [10] and for the purpose of
broadening of synthetic potential of N-aminonitroazoles as versatile building-blocks for
constructing new energy-rich compounds we developed method functionalization N-amino group
using picryl fragment on the example of N-aminonitropyrazoles 1
This method is based on arylation N-aminonitropyrazoles 1 under the action of picrylchlorid (PicCl)
in the presence of base (К2СО3) when heated in MeCN within 2-6 h The result is synthesized
representatives of a previously unknown type of energy-rich compounds - N-
(picrylamino)nitroazoles 2 which are isomers well known C-(picrylamino)nitroazoles [11]
Compounds 2 with two nitro groups in the pyrazole ring are organic NH-acids medium strength
(рКа 40 - 45 in MeCN-Н2О) [1] TM Klapoumltke DG Piercey J Strierstorfer Dalton Trans 2012 41 9451
[2] P Yin Y Zhang DA Parrish JM Shreeve J Mater Chem A 2013 1 585
[3] Y Zhang DA Parrish JM Shreeve J Mater Chem A 2014 2 3200
[4] (a) R Duddu PR Dave R Domavarapy N Gelber D Parrish Tetrahedron Letters 2010 51 399 (b)
MM Breiner DE Chavez DA Parrish Synlett 2013 24 519 (c) P Yin Y Zhang Y Zhang DA
Parrish JM Shreeve J Mater Chem A 2013 1 7500
[5] G Herveacute C Roussel H Graindorge Angew Chem Int Ed Engl 2010 49 3177
[6] C He J Zhang DA Parrish JM Shreeve J Mater Chem A 2013 1 2863
[7] VM Vinogradov IL Dalinger SA Shevelev Mendeleev Commun 1993 111
[8] X Zhao C Qi L Zhang Y Wang S Li F Zhao S Pang Molecules 2014 19 896
[7] NV Palysaeva KP Kumpan MI Struchkova IL Dalinger AV Kormanov NS Aleksandrova
VM Chernyshev DF Pyreu KYu Suponitsky AB Sheremetev Оrg Lett 2014 16 406
[10] (a) IL Dalinger IA Vatsadze TK Shkineva GP Popova SA Shevelev Synthesis 2012 44 2058
(b) IL Dalinger IA Vatsadze TK Shkineva GP Popova SA Shevelev YV Nelyubina J
Heterocycl Chem 2013 59 911
[11] (a) PN Neuman J Heterocycl Chem 1970 7 1159 (b) MD Coburn J Heterocycl Chem 1970 7
345 and 1971 8 153
The research was supported by the Division of Chem and Material Sciences of the RAS (OKh-4)
137
P26
MeLaOXZrO2 CATALYSTS FOR CO OXIDATION
NA Davshan AL Kustov OP Tkachenko LM Kustov
IOC RAS Lab14 Moscow Russia
Mixed metal oxides with a composition АВО3 known as perovskites exhibit the high thermal
stability and enhanced catalytic activity in CO and hydrocarbon oxidation The perovskite-type
materials are less expensive as compared to supported noble metals The materials can be
significantly improved by supporting the perovskites onto porous carriers with a developed surface
area The goal of our work was to prepare characterize and test in CO oxidation a series of MeLaO3
perovskites (Me = Co Fe Ni) supported onto a mesoporous zirconia as a robust and durable carrier
The synthesis of mesoporous ZrO2 was carried out according to the previously developed and
modified procedure [1] A glycine complex of lanthanum and cobalt or iron or nickel was prepared
by the recipe described in [2 3] The samples of supported lanthanum-metal perovskites were
prepared by impregnation of the precalcined mesoporous carrier (ZrO2) with a solution of the
prepared La-CoFeNi glycine complex
The chemical analysis of the samples for the contents of the metals (Zr Co Ni Fe and La) was
carried out by atomic emission spectroscopy
Diffuse-reflectance FTIR spectra were recorded at room temperature in the frequency range of
6000-400 cm-1
with a resolution of 4 cm-1
using а NICOLET ldquoProtegerdquo 460 spectrometer supplied
with a diffuse-reflectance attachment The following probe molecules were used to test surface sites
of different nature СО as a probe for Lewis acid sites and low-coordinated metal ions CD3CN as a
probe for both Lewis and Broensted (if present) acid sites The probe molecules were adsorbed at
room temperature and equilibrium pressures of 5 Torr for СО 96 Torr for CD3CN (saturated
pressures)
The phase composition of the samples and the particle size of the supported metal were examined
by X-ray diffraction (XRD) analysis X-ray absorption (XANES + EXAFS) spectra (Co K edge at
7709 eV and Ni K edge at 8333 eV) were measured at the Hasylab X1 station (DESYGermany)
using a Si(111) double crystal monochromator The EXAFS data analysis was performed using the
software VIPER [4] Reference spectra were taken using standard reference compounds CoO
Co3O4 Co-foil NiO and Ni -foil The required scattering amplitudes and phase shifts were
calculated by the ab initio FEFF810 code [6] X-ray photoelectron spectra were recorded by XSAM
800 spectrometer with Mg Kα X-ray (12536 eV) source
Catalyst testing was carried out in a laboratory scale fixed bed quartz reactor (internal diameter 3
mm) operating at an atmospheric pressure The feed gas mixture consisted of 45 vol CO 225
vol O2 and He balance The total feed flow rate was held constant at 10 cm3min with a volume
hourly space velocity (VHSV) of 6000 hminus1
The following order of the activity in CO oxidation as the temperature of the 50 conversion (T50)
was found in the temperature range from 50 to 400degC LaCoO3ZrO2 (200oC) gt LaFeO3ZrO2
(275oC) gt LaNiO3ZrO2(300
oC)
[1] V A Sadykov L A Isupova I A Zolotarskii L N Bobrova A S Noskov V N Parmon E
A Brushtein T V Telyatnikova V I Chernyshev V V Lunin Appl CatalA 204 (2000) 59
[2] EV Makshina Thesis of Cand Sci Dissertation Moscow State Univ 2008
[3] LM Kustov Top Catal 4 (1997) 131
[4] KV Klementiev wwwcellesBeamlinesCLAESSsoftwareviperhtml
[5] AL Ankudinov B Ravel JJ Rehr SD Conradson Phys Rev B 58 (1998) 7565
138
P27
SELECTIVE FUNCTIONALIZATION OF ALKYNES WITH NATURALLY
OCCURRING ORGANOSULFUR COMPOUNDS
ES Degtyareva VP Ananikov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Nowadays crude oil remains one of the most important resources in the industry Crude oil is a
complex mixture mostly of hydrocarbons with small amounts of sulfur- and nitrogen-containing
impurities To produce more valuable fuels oil fractions are subject to catalytic processes like
reforming isomerization and cracking For ecological as well as technological reasons
organosulfur components should be removed before the petroleum refining However it would be
much more interesting to utilize these sulfur species as a naturally-occurring source of chemical
reagents for example for functionalization of hydrocarbons
The promising and efficient way to create a C-S bond is an addition reaction of thiols and disulfides
to unsaturated hydrocarbons [12] A convenient and selective metal-catalyzed methods for the
addition of thiols and disulfides to alkynes have been recently reported The present study is
dedicated to the development of such catalytic system in order to involve crude oil as a reagent in
organic synthesis
As the first step in our study we describe analytic approach for high sensitivity mass spectrometric
measurements with ability to detect trace amount of products Since most of the components in the
crude oil are nonpolar special polar tags were introduced for electrospray ionization (ESI)
detection To achieve this aim the alkynes with easily polarizable groups were synthesized Good
results were achieved using 1-(pentyn-4)-1H-imidazole and in the model reaction involving the
mixture of C6H5SH C6H11SH and C6H13SH all products were clearly detected (Figure 1) Detailed
study of the catalytic system and ESI-MS characterization will be presented and discussed
Figure 1 An example of ESI spectrum registered for the reaction mixture in the crude oil
(1) Ananikov V P Kabeshov M A Beletskaya I P Khrustalev V N Antipin M Y Organometallics
2005 24 1275ndash1283
(2) Ananikov V P Orlov N V Zalesskiy S S Beletskaya I P Khrustalev V N Morokuma K
Musaev D G J Am Chem Soc 2012 134 6637ndash6649
139
P28
PLATINUM GROUP METALS COMPLEXES OF HYBRID CHALCOGEN
LIGANDS SYNTHESES STRUCTURES AND CATALYSTS IN C-C
COUPLING REACTIONS
S Dey
Chemistry Division Bhabha Atomic Research Centre Mumbai- 400 085 India
The chemistry of chalcogenated platinum group metal complexes has been of considerable interest
for several years due to their fascinating structural features their relevance in catalysis [1] and
lately in materials science [23] These complexes are mostly non-volatile insoluble or poorly
soluble oligomeric species in organic solvents thus limiting their utility as precursors for the
synthesis of metal chacogenides for electronic devices or making them inconvenient for any
homogeneous catalysis reaction To inhibit polymerization of metal chalcogenolates and to develop
phosphine free Pd-catalysts internally functionalized ligands containing both soft chalcogen and
hard N donor atoms has been quite successful such as pyridine chalcogenolates [4] or aliphatic
amine chalcogenolate ligands [56]
We have designed and developed several internally functionalized ligands (N E)2 N EAr (E = S
Se Te N E = Me2NCH2CH2E Me2NCH2CH2CH2E Ar = Ph tol Mes) and bis(4-
pyridyl)dichalcogenide and synthesized their palladium(II) and platinum(II) complexes Versatile
coordination behaviour of these ligands are shown in their complexes (Chart 1) The unusual colour
of [MCl(E N)(PR3)] (blue-violet Pd red Pt) has been attributed due to metal mediated ligand (E)
ndash to ndash ligand (PR3) charge transfer transitions The cationic complexes [Pt(PEt3)2(py2E2)]2(CF3SO3)4
with Pt pyridyl bond have been isolated via self-assembly reaction The complexes
[PdCl2(N EAr)]n exist in monomer and dimer forms their ratio depends on the size of chelate ring
and chalcogen atom The catalytic activity of [PdX(N E)]n (X = Cl OAc) [PdCl2(N EAr)]n and
trans-[PdCl(4-Sepy)(PPh3)2] in Suzuki C C cross coupling reaction will also be discussed
Chart
M
E
E
M
N
N
M
E
E
M
X
NX
N
M
E
N
M
E
N
M
N
E
X
X
X
X
Ar
Ar E
N
M
N
E E
N
M
N
E E
N
M
M
E
N
M
EN
+4
Acknowledgement Dilip Paluru K V Vivekananda A Wadawale N Bhuvanesh B M Bhanage and V K Jain are
acknowledged for collaborations
References
1 Q Yao E P Kinney C Zheng Org Lett 2004 6 2997 2999
2 S Dey V K Jain Platinum Met Rev 2004 48 16 29
3 B Radha G U Kulkarni Adv Funct Mater 2010 20 879 884
4 K V Vivekananda S Dey A Wadawale N Bhuvanesh V K Jain Dalton Trans 2013 42
14158 14167
5 D K Paluru S Dey A Wadawale V K Jain J Organomet Chem 2013 728 52 56
6 B J Khairnar S Dey V K Jain B M Bhanage Tetrahedron Lett 2014 55 716 719
140
P29
THE REACTIONS OF 13-DIARYL-3-CYCLOHEXANONILPROPANE-1-
ONE WITH HYDROGEN SELENIDE IN SITU IN CONDITIONS OF ACID
CATALYSIS
DYu Direnko1 YaB Drevko
2 BI Drevko
2
1 - Penza branch of the military Academy of logistics
2 - FGU VPO Saratov State Agrarian University named after NI Vavilov
It is known that when arylaliphatic 15-dicetones interacts with hydrogen selenide in conditions of
acid catalysis the corresponding 4H-selenopyran structures can be formed 1 which are used as
veterinary and healthcare products However dicyclic diaryl-4H-selenopyrans have not been
described until today
We have studied the chemical reaction of 1-paramethoxy-3-phenyl-3-cyclohexanonilpropane-1-one
1 with hydrogen selenide in situ in conditions of acid catalysis The reaction has been conducted in
the presence trimethoxyphosphine 1 In the result of the compound 1 was obtained in 2-
paramethoxy-4-phenyl-5678-tetrahydro-4H-selenochromen 2 with quantitative output ndash 80
(Melting point = 108-1090С)
O O S e
C H3
O H P C l3 Z n S e
p
1 2
P h
P h
P h
P h - O C H3
p - O C H3
In the course of reaction settled crystal compounds and mother solution were analyzed by method
of the capillary gas-liquid partition chromatography with mass-selective detector HP 58905972
Tinj=200оС tset=3 min Tset=50
оС Tend=280
оС Т = 10
оСmin carrier gas ndash helium
= 1 mlmin
It was found that every molecular ion or fragment which contained selenium presented in the form
of six signal intensities conforming to the content of the selenium isotopes in the nature Se74
(087) Se76
(902) Se77
(758) Se78
(2352) Se80
(4982) Se82
(919)
The compound 2 is subjected to isomerisation at high temperature So there are signals of four
compounds with retention time 2703 min 2906 min 293 min 4008 min on the chromatogram
(mz = 381 the output of this molecular ion is accompanied by loss of one hydrogenrsquos isotope)
As well as one compound was identified and its molecular ion was conformed to
dehydroselenochromen (mz = 380 retention time is 3335 min) This ion also was identified
through GH-MS that confirmed the received mass spectrum
Therefore formation of product (dehydroselenochromen (mz = 380)) demonstrates the new
direction of disproportionation of dehydroselenochromen structures on alicyclic fragment
Literature
1 Drevko YaB Fedotova OV The synthesis of the first representatives of benzenediamine
dehydroselenochromens CHC200610P1586-1587
141
P30
SYNTHESIS OF UNNATURAL PROLINE DERIVATIVES USING THE AZA-
COPE-MANNICH-REACTION
DS Belov NK Ratmanova AV Kurkin IA Andreev
Lomonosov Moscow State University
Oxygenated bicyclic amino acids constitute an important class of secondary metabolites Many of
these nonproteinogenic amino acids are subunits of structurally diverse natural products Various
methods to access these biologically important compounds were advised by synthetic community
and subsequently used by pharmaceutical companies However pharmaceutical industry usually
relies on the most robust and reliable reactions
Aza-Cope-Mannich rearrangement is a powerful reaction which was successfully used in academia
settings was however largely overlooked by medicinal chemists1 We have shown recently that it
can be routinely scaled up to 1 mole23
In this work we demonstrated that a number of proline
analogs can be efficiently prepared with full control of stereochemistry
Scheme 1
The aminoalcohols required for the rearrangement were effectively prepared in several steps form
commercially available oxiranes (Scheme 1) The aza-Cope-Mannich reaction provided both cis and
trans fused unnatural proline analogs 2 3 or 4 in high yields The ratio of products was dependent
upon the reaction conditions and the nature of substituents R1 and R2 The reaction also proved to
be scalable (gt1 g)
This study was supported by the Russian Foundation for Basic Research (Projects No 14-03-
31685 14-03- 31709 14-03-01114)
1 Overman L E Humphreys P G Welmaker G S Org React 2011 75 747-820
2 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A Tetrahedron 2011 67
9214ndash9218
3 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125ndash10134
142
P31
SYNTHESIS OF OXYGENATES OF DIFFERENT CLASSES ON
HETEROGENIOUS KCOMOS-CATALYSTS
VS Dorokhov OL Eliseev AL Lapidus VM Kogan
N D Zelinsky institute of organic chemistry Moscow Russia
Heterogeneous catalytic systems based on alkali-modified molybdenum disulphide are promising
for alcohols synthesis from СО and Н2 [12] The model of dynamic nature of the active sites of
transition metal sulphide catalysts was taken as a conceptual basis for the work [3]
We conducted investigations of structure and functioning mechanism of MoS2-based catalysts
active phase in oxygenates synthesis reaction We found out that alkali metal (potassium) forms
unite phase with MoS2 and significantly changes it structure Addition of potassium increases
average number of layers and average linear size of MoS2 crystallites As it follows from our
catalytic experiments both Co and K increases selectivity of alcohols formation Besides addition
of potassium suppresses hydrogenation and hydrodesulphurisation reactions [4]
We suggested that formation of alcohols from СО and Н2 occurs on active sites located on the
edges of the MoS2 slabs It is likely that active sites responsible for alcohols synthesis consist of a
combination of two MoS2 clusters one of which is promoted with Co and K is intercalated
between the crystallite layers Formation of alcohol molecule depends on accessibility of alkali ion
to coordination of alcoxyl intermediate oxygen The scheme of possible mechanism of synthesis-
gas conversion on KCoMoS catalyst was published in [5]
The addition of ethanol or ethylene to synthesis gas substantially changes the reaction rate and
composition of the products [5] Presence of these components in the gas feed can significantly
increase CO conversion According to our results alcohols can adsorb on KCoMoS-catalysts active
sites and enter a series of side reactions which leads to formation of ethers esters aldehydes
ketones and organic acids Therefore the use of additives to syngas makes it possible to obtain a
wide range of oxygenates of different classes The further development of this approach can be
efficient for controlling selectivity in processes of simultaneous synthesis of various classes of
organic compounds
Acknowledgment This work was financially supported by the Russian Foundation for Basic
Research (Project No 14-03-31769 mol_a)
References
1) Surisetty VR et al App Cat A 404 (2011) 1-11
2) Feng M Recent Patents Catal 1 (2012) 13-26
3) Kogan VM Nikulshin PA Rozhdestvenskaya NN Fuel 100 (2012) 2ndash16
4) Dorokhov VS et al Kinetics and Catalysis 54 N 2 (2013) 243ndash252
5) Kogan VM et al Russ Chem Bull 2 (2014) in press
143
P32
THE MECHANISM OF ALCOHOL FORMATION OVER TMS CATALYSTS
VS Dorokhov1 EA Permyakov
1 OL Eliseev
2 VM Kogan
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalytic reaction of carbon
oxides Moscow Russia
The aim of this work is to investigate a structure of transitional metal sulfide (TMS) catalyst active
sites in mixed alcohol synthesis (MAS) from synthesis gas and to develop possible mechanism of
this reaction The model of dynamic nature of the active sites of TMS catalysts was taken as a
conceptual basis for the work [12] As it follows from our catalytic experiments both Co and K
affect alcohol selectivity towards hydrocarbon (HC) formation It is likely that the active sites
responsible for alcohol formation are located on the edges of the MoS2 slabs Besides K poisons
C-S hydrogenolysis sites and HDS activity decreases Basing on the experimental data we suggest
the structure of the MAS site as a combination of two MoS2 clusters one of which is promoted with
Co and K is intercalated between the crystallite layers and the scheme of possible mechanism of
synthesis-gas conversion on K-Co-Mo-S catalysts (Fig 1)
C O
nC O
CH3OH
C n+1 H 2n+3 OH
2 H
H
H
H
H
K
C
S
C o
M o
S
S
S
S
S
M o
M o
H
C H 4
3 H
H2O
M o
K
H
H
CO
S
C o
M o
S
S
S
S
S
M o
M o
K
C O
S
C o
M o
S
S
S
S
S
M o
M o
K
C H3
S
C o
M o
S
S
S
S
S
M o
M o
H
K
C H3
S
C o
M o
S
S
S
S
S
M oO
M o
H
HH
K
CO
S
C o
M o
S
S
S
S
S
M o
M o
K
C H2
S
C o
M o
S
S
S
S
S
M o
O
H
M o
K
S S
C o
M o
S
SS
S
M o
H H
K
C O
CnH
2n+1
S
C o
M o
S
S
S
S
S
M o
M o
2 H
effec t
of K
C
o
and s
upport
(4 n -4 )H(n -1 )H
2O
CnH
2n+1 M o
H
K
C H2
S
C o
M o
S
S
S
S
S
M o
CnH
2n+1 M o
K
CH2
S
C o
M o
S
S HO
S
S
S
M o
Cn+1
H2n+4
H2O
3 H
H
CH3
M o
K
C O
Cn-1
H2n-2
S
C o
M o
S
S
S
S
S
M o
eff
ec
t o
f K
C
o a
nd
su
pp
ort
Fig 1 Suggested
mechanism of
alcohols and HC
formation over
KCoMoS active
sites Black
rectangle defines
the initial step of
reaction As an initial step of the mechanism CO adsorption on the vacancy was taken After partial
hydrogenation of carbon by dissociatively adsorbed hydrogen the C=O bond lengthens allowing
the oxygen atom to coordinate on K+ ion intercalated between the MoS2 crystallite layers
Coordination of the oxygen on the K+ ion stabilizes the alkoxylenated intermediate and prevents the
C-O bond from breaking which is necessary for the succeeding process of alcohol formation
Oxygen coordination onto the Mo atom of the neighboring cluster leads to hydrogenolysis of the C-
O bond The alkyl fragment can either be hydrogenated to form HC or take part in the carbon-chain
growth ndash next CO molecule is inserted between C and Mo Oxygen of a newly inserted CO can
coordinate on K or Mo determining formation of either alcohols or HC It was found that the ratio
of alcohols to HC yields decreases with an increase of reaction temperature It means that alcohols
formation becomes kinetically less favorable at higher temperatures than the C-O bond
hydrogenolysis This observation is in agreement with the suggested mechanism
[1] VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2ndash16
[2] VM Kogan PA Nikulshin Catal Today 149 (2010) 224ndash231
144
P33
CATALYTIC CYCLOMAGNESIATION OF 12-DIENES IN THE
SYNTHESIS OF PHEROMONES AND ACETOGENINErsquoS PRECURSORS
VA Dyakonov AA Makarov OA Trapeznikova UM Dzhemilev
Institute of Petrochemistry and Catalysis Russian Academy of Sciences Laboratory Catalytic
Synthesys Ufa Russia
An efficient method for the synthesis of valuable N- О- and Si-containing 1Z5Z-diene compounds
was developed The method comprises Cp2TiCl2-catalyzed cross-cyclomagnesiation of 12-dienes
by Grignard reagents (RMgRrsquo) to give 25-dialkylidenemagnesacyclopentanes in up to 96 yields
This approach was successfully used in the synthesis of 5Z9Z-dienoic acids precursors of
acetogenins and insect pheromones
Q
R
RQ
M g
RQE tM g B r
[T i] M g()n
+1
[T i] = C p2T iC l
2 n = 1 Q = T M S R = B n (k ) H ex ( l) n = 2 Q = O B n R = H ex ( a ) Q = O T H P R = H ex (b ) Q =
O T H P R = B n (c ) Q = M o rp h R = B n ( h ) Q = M o rp h R = H ex ( i) n = 3 Q = T H P R = C1 2
H2 5
(d ) n = 4 Q = T H P
R = B u (e ) Q = T H P R = H ex ( f) n = 6 Q = T H P R = B u ( g )
2
H3O + (D
3O + )
3 4
( )n
( )n
Acylation of diene 4g with acetyl bromide gave hexadeca-7Z11Z-dien-1-yl acetate 5 the pink
bollworm Pectinophora gossypiella attractant in a final yield of 89
T H P O -( C H
2)
6T H P O -( C H
2)
6
M g
( C H2)
3M e
T H P O -( C H2)
6
( C H2)
3M e
( C H
2)
3M e
A c O -( C H2)
6
( C H2)
3M e
M e
O
B r
E tM g B r
[T i] M g H3O +
+
8 9
9 4
4g 5
3g
The same approach was used to obtain the key synthons in the preparation of some acetogenins
exhibiting high antitumor antimalarial and immunosuppressive activities Cross cyclomagnesiation
of 12-hexadecane and 2-(45-hexadiene-1-yloxy)tetrahydropyran followed by hydrolysis furnished
2-(hexacosa-4Z8Z-dien-1-yloxy)tetrahydropyran 4h (yield 84) which is the key intermediate in
the preparation of the acetogenin cis-Solamin 6
T H P OM g
O T H P
H2 3
C1 2
OH H
O HOH
O
O
O T H P
( )1 0
( )
2
E tM g B r [T i]
( )1 0
( )2
2 0 oC E t2O
H3O +
( )1 0
( )2 ( )
1 1
8 7
3h
4h 6
+
This work was performed under financial support from the Russian Science Fondation (Grant 14-
13-00263) and by Russian Foundation for Basic Research (Grant 14-03-97024)
145
P34
SYNTHESIS AND ANTIHELMINTIC ACTIVITY OF 5-O-DERIVATIVES OF
IVERMECTIN
IV Zavarzin1 MKh Dzhafarov
2 NV Krukovskaya
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - KI Skryabin Moscow State Academy of Veterinary Medicine and Biotechnology Moscow
Russia
Ivermectin 1 and its derivatives are widely used as antihelmintic medical formulations In this case
the parasites eventually develop resistance to these substances12
It is therefore highly relevant to
develop new antihelmintic agents We were the first who obtained the 5-O-ivermectin derivatives 2
by acylation of an ivermectin 1 anhydrides of carboxylic acids In addition to the carboxylic acids
the corresponding esters and amides are also obtained
R 1 O
O
O O O
C H3
CH3
OH
O
CH3
O
O
O
C H3
C H3
O
RC H
3
C H3
O HO M e
M e O
O H
OO
R 1 =
2 R = M e E t
1 R = M e E t R 1 = H
Carboxylic acid 2 as well as their esters and amides show high antihelmintic activity
Literature
1 Tyrell К Leo F Veterinary Parasitology - 2009 - 11 - Р 98-102
2 Varady M Cobra J Letkova V Kovac G Veterinary Parasitology - 2009 - 2-3 ndash Р 267-
271
146
P35
TRENDS IN EVOLUTION OF ANTIPARASITIC CHEMICAL AGENTS
MKh Dzhafarov
KI Skryabin Moscow State Academy of Veterinary Medicine and biotechnology
Chemotherapy and prevention are of high priority in control of helminthoses and other dangerous
parasitoses of humans animals and plants [1]
However the intensive administration of antiparasitic preparations leads to development of
resistance which is one of the ways of biochemical adaptation of helminths insects and arthopods
to the first- and second-order environmental changes (the host and ecological niche occupied by the
host where certain stages of the complex-cycle pest metamorphoses take place) which necessitates
regular renewal of the range of chemical agents among different measures [2]
Systematization of the data on the antiparasitic substances in the light of new discoveries and
developments is an important step for a successful struggle against parasitic diseases
In particular based on the systemic analysis of features of the chemical structure of anthelminthic
substances the hypothesis on the viability of the targeted search for such compounds among the
derivatives of conditionally progenitor cyclic hydrocarbons ndash benzene indene naphthalene 1Н-
cyclopenth [a]-naphthalene anthracene and phenanthrene ndash by alternating absolutely unsaturated
and saturated structures including heterocyclic analogues containing nitrogen oxygen and sulfur
and different substitutes and functional groups was voiced
References
1 Dzhafarov MKh Russian J Agrobiology Animal biology series 2013 4 p26-44
2 Dzhafarov MKh Vasilevich FI Advances in Pharmacology and Pharmacy 2014 2 30-45
147
P36
RHODIUM-CATALYZED REDUCTIVE CARBONYLATION OF
IODOBENZENE
OL Eliseev TN Bondarenko TN Myshenkova AL Lapidus
NDZelinsky Institute of organic chamistry Moscow Russia
Aromatic aldehydes is useful class of products because of diverse reactivity of formyl group
Usually they are synthesized by GattermannndashKoch ReimerndashTiemann VielsmeierndashHaag and Duff
reactions However these methods suffers from drawbacks like low yield poor selectivity and
generating waste and side products12
Alternatively catalytic formylation (reductive carbonylation)
of aryl halides with synthesis gas in the presence of palladium phosphine complexes was firhst
reported in 1974 by Schoenberg and Heck3 and lately by Beller
4ndash6 and Nagarkar
7 groups
Somewhat surprisingly up to now rhodium was unexplored as a catalyst for reductive
carbonylation of aryl halides This encouraged us to test rhodium salts and complexes in reductive
carbonylation of iodobenzene as a model substrate I
+ C O + H 2
R h -ca tC H O
b ase
+ b aseH I
Rhodium phosphine complexes such as HRh(CO)(PPh3)3 and RhCl(CO)(PPh3)2 were found to be
excellent catalysts They surpass PdCl2(PPh3)2 in respect to activity and selectivity to benzaldehyde
Aromatic solvents such as toluene and o-xylene seems to be the most suitable medium Other
solvents such as heptane 14-dioxane MEK DMF and acetonitrile gave poor yield of
benzaldehyde In methanol solution methyl benzoate was the main product
Reaction is highly sensitive to the nature of the base Replacing NEt3 with NBu3 resulted in almost
threefold reduction in benzaldehyde yield Somewhat higher but still low yield was achieved with
Huumlnigs base Inorganic bases such as potassium and cesium carbonates gave poor iodobenzene
conversion and benzaldehyde yield
Synthesis gas pressure renders effect on reaction Iodobenzene conversion reaches 100 at a total
pressure of about 1ndash15 MPa and slightly decreases at higher pressure Both selectivity and yield of
benzaldehyde increase with pressure increasing while selectivity to benzene decreased Biphenyl is
a main product at atmospheric pressure but it fully disappears at a pressure 1 MPa and higher
In conclusion rhodium (I) triphenylphosphine complexes are good catalysts for reductive
carbonylation of iodobenzene The best catalyst formulation found 05 RhCl(CO)(PPh3)2 150
NEt3 toluene At 110degC and 15 MPa (COH2 = 11) iodobenzene is totally converted within 2
hours giving benzaldehyde with the yield of 88
References
1 F Aldabbagh Compr Org Funct Group Transform II 2005 3 99
2 L P Crawford S K Richardson Gen Synth Methods 1994 16 37
3 A Schoenberg R F Heck J Am Chem Soc 1974 96 7761
4 S Klaus H Neumann A Zapf D Sturbing S Hubner J Almena T Riermeier P Groszlig M
Sarich W-R Krahnert K Rossen M Beller Angew Chem Int Ed 2006 45 154
5 A Brennfuhrer H Neumann St Klaus T Riermeier J Almenab M Beller Tetrahedron 2007
63 6252
6 H Neumann R Kadyrov Xiao-Feng Wu M Beller Chem Asian J 2012 7 2213
7 A S Singh B M Bhanage J M Nagarkar Tetrahedron Letters 2011 52 2383
148
P37
MODELING OF THE ELECTROCHEMICAL IMPEDANCE IN ANODIC
DISSOLUTION OF IRON USING A GENETIC ALGORITHM APPROACH
AR Enikeev1 IM Gubaidullin
2 MA Maleeva
3
1 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry Ufa Russia
2 - Institute of petrochemistry and catalysis Laboratory of mathematical chemistry
3 - AN Frumkin Institute of Physical Chemistry and Electrochemistry RAS Moscow Russia
In order to predict the general corrosion damage to metals and alloys development of deterministic
models and the acquisition of values for various model parameters are of paramount importance
Now it is generally accepted that elucidating an intricate reaction mechanism by means of steady-
state techniques alone is a very difficult task [1] In fact the steady-state approach provides too little
information in comparison with the complexity of the process under investigation In the present
work we used model with three adsorbed species it was possible to explain the iron dissolution in
sulphate and chloride media
It was recently found that impedance diagrams reveal at least three time constants concerning the
faradaic process in the iron-sulphate systems was proposed by Keddam [2]
Reaction mechanis
The reaction kinetic parameters was calculated by genetic algorithm The experimental impedance
diagrams showed one high-frequency capacitive arc and three time constant at lower frequencies
appearing as inductive or capacitive loops They are attributed in the models respectively to the
double layer capacitance in parallel with the transfer resistance and to the relaxation of three
reaction intermediates
1 E J Kelly J Electrochem Sot 112 124
2 M Keddam R Mattos and H Takenoutl J Electro-them Sot 128 257 266 (1981)
149
P38
KINETICS AND MECHANISM OF THE CATALYTIC OXIDATION OF 4-
TERT-BUTYLPHENOL BY AQUEOUS SOLUTIONS OF H2O2 IN THE
PRESENCE OF TITANOSILICATES
LV Enikeeva IM Gubaydullin NF Murzasheva
Institute of petrochemistry and catalysis RAS Laboratory of mathematical chemistry Ufa Russia
Selective oxidation of phenol is of great interest in terms of education practically valuable product -
hydroquinone and catechol This work is part of studies on the oxidation of phenols in aqueous
solutions of hydrogen peroxide in the presence of metallosilicates
For initial evaluation of the activity of titanosilicate catalysts in oxidation reactions of organic
compounds we used a decomposition reaction of H2O2 in the absence of substrate We studied the
catalytic activity in the decomposition reaction metallosilicates H2O2 apparent activation energy of
the reaction in the presence of different samples metallosilicates were calculated expression for the
reaction rate which shows good agreement with the experimental data was proposed model
validation on the value is performed
A series of catalytic activity of the samples in the reaction of hydrogen peroxide decomposition was
created
At the moment we study the oxidation reaction of tretbutilfenola by aqueous solutions of H2O2 The
scheme of the reaction the reaction kinetic parameters was calculated
150
P39
NEW CHEMICAL TRANSFORMATIONS OF Ni(acac)2 WITH POSSIBLE
INVOLVEMENT OF SUPERATOMIC Ni2O2 CORE AS REVEALED BY ESI-
MS AND MSMS
DB Eremin VP Ananikov
Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
More than twenty signals of nickel-containing ions were detected upon studying of electrospray
ionization mass spectrum of the Ni(acac)2 sample prepared in a plastic tube However changing
sample preparation procedure to a glass vial gave a clear spectrum with four signals corresponding
to mz 2570141 [Ni(acac)2 + Na]+ mz 4130040 [Ni2(acac)3]
+ mz 53503838 [Ni2(acac)4 +
Na]+ and mz 6690285 [Ni3(acac)5]
+ (Figure 1A) A prominent difference in the spectra was
caused by various plastic-derived contaminants that were coordinated to the metal center
Figure 1 (A) ESI-MS spectra of solution of Ni(acac)2 in acetonitrile prepared under standard
conditions (with contaminant signals marked by blue symbols) and prepared without a contact with
plastic (mz = 250 ndash 1000 range acac = C5H7O2) (B) Experimental survival yield curves of most
abundant ions
CID (Collision-induced dissociation) MSMS experiments were carried out to estimate relative
stability and to study reactivity during fragmentation process Fragmentation of the bimetallic ion
[Ni2(acac)3]+
was of most interest Eight fragment ions of different composition were detected
Seven of them were formed as a result of CndashC CndashH and CndashO bond cleavage nevertheless they
retained the Ni2O2 core a supposed superatomic structure which caused exceptional behavior
observed in the fragmentation After the fragmentation at the applied collision energy of 40 eV
ketene pentyn-3-on-2 buten-3-on-2 acetaldehyde carbon monoxide and hydroxide-anion were
formed Other bi- tri- and monometallic species detected did not undergo such transformations
under MSMS conditions Survival yields were calculated (Figure 1B) and a series of relative
stability was proposed Ni2 gtgt Ni1 asymp Ni3 The signal of [Ni2(acac)3]+ remained as most intensive
after heating of the solution
Mass spectra with the similar ionic composition were obtained for vanadyl and copper(II)
acetylacetonates as well as after the addition of two-fold excess of acetylacetone to the solution of
the acetates M(OAc)2 (M = Ni Cu Pd) Chemical reactivity of detected ions and the role of
bimetallic species are currently under investigation
151
P40
FORMATION OF A COMPLEX WITH FLUOROGENE LABEL IS A
RELIABLE WAY OF CREATION OF AN EXPRESS-METHOD OF
ACETYLCHOLINESTERASE ACTIVITY ASSAY
OV Fateenkova ET Gainulina DK Gulikova SB Ryzhikov VN Fateenkov
IM Sechenov First Moscow State Medical University Faculty of
Pharmacy Russia Moscow
Assay of erythrocyte acetylcholinesterase (AChE) activity of human is widely used for the
successful decision of many problems facing to a modern science development of effective antidots
for treatment of defeats by toxic organophosphorus inhibitors medicines for treatment of illness
Alzheimer and Parkinson etc
In a lot of cases there is a necessity of express-analyses of defeat by toxic organophosphorus
inhibitors As an example it is possible to refer to events in the Tokyo underground in 1985 year
and also in territory of several syrian cities in 2013 year when in the terrorist purposes sarin has
been applied and there was a necessity of urgent diagnostics of a degree of defeat of significant
number of victims of this act of terrorism
Known methods of AChE activity assay do not correspond to modern requirements to correlation
of parameters ldquosensibility - time of formation of an analytical signalraquo
In the given work the express-method of acetylcholinesterase activity assay is offered on the basis
of formation of an intensively fluorescing complex by the given enzyme with fluorogene label
thioflavine T (TF) TF is reversible inhibitor of AChE and selectively binds to the peripheral site of
this enzyme
Figure Dependence of fluorescence intensity of TF (15 М) from AChE activity
With increase of AChE activity at constant concentration of ТF (15 М) in the investigated interval
of reagents concentrations the dependence of fluorescence intensity of system TF - AChE has
linear character (fig) At addition AChE to solution TF formation of an analytical signal (increase
of fluorescence intensity) on a wave of 490 nm is observed within of several seconds and the
achieved of fluorescence intensity remains stable more than 15 min The absence of influence of
human butirylcholinesterase and bull whey albumin on fluorescence intensity of thioflavine T on
length of a wave of 490 nm is confirms selective character of interaction of human erythrocyte
acetylcholinesterase with TF 1 De Ferrari GV Mallender WD Inestrosa NC Rosenberry TL J Biol Chem 2001 276 23282
2 Antokhin AM Gainullina ET Taranchenko VF Ryzhikov SB Yavaeva DK Russ Chem Rev 2010 79 8
713
152
P41
QUANTUM CHEMICAL MODELING OF CONFORMATIONS OF TERT-
BUTYL HYDROPEROXIDE
GT Garaeva VI Anisimova IA Suvorova NN Batyrshin
Kazan National Research Technological University 420015 Kazan KMarks 68
Data on internal rotation of tert-butyl hydroperoxide (TBHP) advance the field of conformational
analysis and can be used for investigation of reactivity of industrially important hydroperoxides
which are primary products of hydrocarbon oxidation processes
For TBHP internal rotation only about C-O and O-O bonds is possible Earlier it was demosntrated
that TBHP has two conformations ndash gauche and trans [1] Figure 1 (curves 12) shows that all
possible equilibrium structures of TBHP have identical energy while analysis of bond lengths and
angles (Table 1) also supports identity of these structures and therefore monomeric form of TBHP
exsists only in one conformation (Fig 2) [2]
Table 1 ndash Parameters of TBHP according to B3LYP6-311++G(dfp) calculations
Bond length Aring Angle deg Torsion angledeg OH
sm-1
С-О О-О О-Н СОО ООН С2С
1О
1О
2 С
3С
1О
1О
2 С
4С
1О
1О
2 С
1ООН
1450 1456 0966 1095 1002 -601 -1780 638 -1226 3785
1 Suvorov I A Association and the thermal decomposition of tertiary hydroperoxides Thesis
Candidate chem sciIA Suvorov - Kazan 2003 - 124 p
2 Anisimov VI Quantum-chemical study of the hydrogen bonds between molecules tertiary butyl
hydroperoxide VI Anisimova IA Suvorov NN Batirshin VI Sokolov KE Kharlampidi
Vestnik Bashkir University - 2008 - v 13 -3 (1) - p 793-797
The work was supported by Russian Ministry of Education and Science within the framework of
basic part (PNIL 0214)
Fig 1 ndash PES of internal rotation of BHP
1- around О-О bond 2 ndash around С-О bond
Fig 2 ndash Molecule of TBHP
153
P42
SUPRAMOLECULAR INTERACTION OF CAFFEINE MOLECULES WITH
EACH OTHER WATER MOLECULES AND OXYGEN ATOMS OF
TETRAOXIDOANIONS IN THE NEW COMPOUND COBALT
HEXAHYDRATE DIPERRHENATE CAFFEINE
KE German1 MS Grigoriev
1 GV Kolesnikov
2 YuA Ustynyuk
2 OI Slyusar
3 YaA
Obruchnikova3 OS Kryzhovets
3 MN Glazkova
3
1 - AN Frumkin Institute of Physical Chemistry and Electrochemistry RAS Moscow Russia
Medical Institute REAVIZ Moscow Russia
2 - Lomonosov Moscow State University Moscow Russia
3 - Medical Institute REAVIZ Moscow Russia
Recently the antitumor and radiosensitizing drugs being caffeine derivatives that penetrate easily
through blood brain barrier have been developed They are effective with radiation and
chemotherapy treatment for cases of brain tumors Results of these studies has shown the caffeine
derivatives as perspective source for receiving therapeutic agents to be used in a combined therapy
for primary and metastatic brain tumors Anyhow the mechanism of caffeine interaction was not
clear To provide the proper understanding of caffeine action the precise structural data are
necessary To increase the accuracy of the structural date and to simulate the interaction of caffeine
with tetraoxidoanion and hydration water molecules the synthesis of caffeine cobalt hexahydrate
perrhenate was carried out from saturated water solutions and the single crystal thus obtained were
subjected to X-ray structural study at Bruker KAPPA APEX II diffractometer
Supramolecular interactions of caffeine molecules with each other water molecules and oxygen
atoms of tetraoxidoanions as in a new compound of Co(H2O)6[ReO4]2 caffeine are analyzed in
these study through comparison of the new precise structural data with quantum chemical analyses
The reasons for alterable orientation of caffeine molecules to each other and for the H-bonds
network formation has been evaluated
1 Vartanyan LP Kolesova MB Gornaeva GF Pustovalov YuI Caffeine derivatives mdash
perspective method of the search for anticancer and radiomodifying drugs in combined therapy
for malignant brain tumors Psychopharmacol Biol Narcol mdash 2005 mdash Vol 5 N 4 mdash P
1093ndash1095 Central Research Institute of Roentgenology and Radiology Saint Petersburg
154
P43
EFFICIENT CONVERSION OF ALKENYNONES TO 2-
METHYLENEDIHYDROPYRROLONES
PR Golubev AS Pankova
St Petersburg State University Institute of chemistry St Petersburg Russia
Earlier we have developed a method for the synthesis of cross-conjugated ketones 2 and
investigated their interaction with common binucleophiles ndash hydrazines and amidines [12] Our
next goal was to study the reaction of enynones 2 with amines
It was shown earlier [12] that the ethoxymethylene group is the most active center of ketones 2 in
reactions with nucleophiles In line with this enamines 3 were obtained on the first stage in
reactions with amines Various solvents were used successfully in this reaction but diphenyl ether
was considered to be the most convenient since in this case both synthetic steps could be performed
in a one-pot fashion without isolation of intermediate enamines 3
We proposed that thermolysis of enamines 3 could lead to their cyclization via Michael-type
intramolecular addition of amine nitrogen atom to a triple bond We have found that this reaction
proceeds smoothly at 200 degC as a 5-exo-dig cyclization leading to pyrrolinones 4 as single products
in good to excellent yields Various amines with alkyl aryl or heteroaryl substituents were used
Thus monoalkylamines are predictably the most active coupling partners but in this case steric
factors play a crucial role Nevertheless even tert-butylamine was employed successfully in this
reaction along with n-alkyl- and (hetero)benzylamines In case of anilines the reaction outcome was
fully consistent with nucleophilicity of the amine used Generally anilines with electron-donating
substituents reacted more readily and provided higher yields than electron-deficient ones and a
slight decrease of yield was observed when para-substituted aniline was replaced with an
ortho-substituted analogue Finally pyrrolidinones 4 with various heteroaromatic substituents at
nitrogen atom can also be obtained
In conclusion we offer a straightforward and high-yielding method for the synthesis of previously
unknown 2-methylenedihydropyrrolones
[1] AS Pankova PR Golubev IV Ananyev MA Kuznetsov Eur J Org Chem 2012 30
5965-5971
[2] PR Golubev AS Pankova MA Kuznetsov Eur J Org Chem 2014 17 3614-3621
Authors thank the Russian Scientific Fund for a research grant No 14-13-00126
155
P44
THEORETICAL INVESTIGATION OF PALLADIUM-CATALYZED
DIMERIZATION OF ALKYNES HYDROPALLADATION VS
CARBOPALLADATION PATHWAYS
EG Gordeev VP Ananikov
ND Zelinsky Institute of Organic Chemistry of the Russian Academy of Sciences
Catalytic dimerization of terminal alkynes is a waste-free process that allows preparation of enynes
within atom-economic transformation The key question for practical utilization of the dimerization
approach is to understand the factors responsible for rendering regioselective transformation and
lead in a to a single poduct
The studied catalytic dimerization of terminal alkynes may involve two mechanisms
hydropalladation and carbopalladation which results in two types of products - head-to-head and
head-to-tail dimers Experimentally it has been found that the presence in the reaction mixture of
carboxylate anion direct the reaction to head-to-tail product only [1] To reveal the mechanistic
picture we have carried out the quantum-chemical modeling (B3LYP6-311G (d) amp SDD) of the
catalytic dimerization of phenylacetylene including participation of the carboxylate anion
Theoretical calculations have shown that in the absence of carboxylate anion the reaction proceeds
as hydropalladation and forms head-to-head product since potential barrier of the hydropalladation
rate-determining step is much smaller than the barrier of the carbopalladation rate-determining step
The predominant formation of head-to-head product was also determined by kinetic factor the
energy of the corresponding transition state was smaller as compared to the transition state of
carpbopalladation pathway
When carboxylate anion (acetate ion was used for modeling) was added to the reaction mixture the
H lignad at the metal center was blocked that and only carbopalladation pathway become possible
Indeed coordination of the carboxylate ion to the palladium atom leading to the formation of the
ion pair destabilized head-to-head intermediate complex As a result the second phenylacetylene
molecule was not able to enter into the metal coordination sphere In the case of head-to-tail
intermediate complex such destabilization did not take place
Theoretical study of complete potential energy surface and comparison with experimental data will
presented and discussed
References [1] Zatolochnaya OV Gordeev EG Jahier C Ananikov VP Gevorgyan V Carboxylate
Switch between Hydro- and Carbopalladation Pathways in Regiodivergent Dimerization of
Alkynes Chem Eur J 2014 DOI 101002chem201402809
Acknowledgement Cooperation with V Gevorgyan (UIC Chicago) and his group is greatly
acknowledged in this project The support of the Russian Foundation for Basic Research (RFBR 14-
03-31752) is gratefully acknowledged
156
P45
CROSS-METATHESIS OF POLYNORBORNENE AND POLY(1-
OCTENYLENE) AS A NEW ROUTE TO NORBORNENE AND
CYCLOOCTENE MULTIBLOCK COPOLYMERS
ML Gringolts YuI Denisova GA Shandryuk LB Krentsel AD Litmanovich YaV
Kudryavtsev ESh Finkelshtein
AV Topchiev Institute of Petrochemical Synthesis Russian Academy of Sciences Russia
Norbornene (NB) and cyclooctene (COE) are well-known objects in ring-opening metathesis
polymerization (ROMP) Their homopolymers synthesized by ROMP are important commercial
products [1] Polynorbornene (PNB) which is sold under the trademark Norsorex has various
special applications Poly(1-octenylene) (PCOE) known as Vestenamer or polyoctenamer
possesses unusual properties for an elastomer At the same time the ROMP synthesis of NB-COE
copolymers is rather difficult because of considerably different polymerization activities of the
comonomers This problem can be solved by catalyst modification [2] or using NB with
substituents decreasing its activity [3]
We propose a new approach to the synthesis of NB-COE multiblock copolymers via interchain
cross-metathesis of PNB and PCOE That approach enabled us to obtain new copolymers using the
1st generation Grubbsrsquo catalyst Cl2(PCy3)2Ru=CHPh which is not suitable for copolymerization of
NB and COE
+[R u = C H P h ]
6n ba c
mC O E - C O E
P C O E
N B - N B
P N B
N B -N B N B -C O E C O E -C O E
C H C l3
Cross-metathesis between PNB and PCOE has been successfully realized New NB-COE
multiblock copolymers were identified and characterized by NMR spectroscopy GPC and DSC
methods It was found that in the course of the reaction the average lengths of PNB and PCOE
blocks were decreased as well as the copolymer molecular weight and crystallinity For copolymer
of 11 composition Tg is about -30 oC which is higher than for PCOE (- 80
oC) and lower than for
PNB (39 o
C) The exchange degree (conversion) reached approximately 40-50 in 24 h
Copolymer characteristics can be controlled by varying concentration of the catalyst
The work was supported by RFBR (project 14-03-00665)
1 KJ Ivin JC Mol (1997) Olefin Metathesis and Metathesis Polymerization Academic Press
London
2 Marc Bornand und Peter Chen Angew Chem 2005 117 8123 ndash8125
3 CS Daeffler and RH Grubbs Macromolecules 2013 46 3288minus3292
157
P46
SELECTIVE C=O HYDROGENATION OF ENONES ENALS AND
ENOATES
DG Gusev D Spasyuk
Wilfrid Laurier University Department of Chemistry Waterloo Canada
In the past three years1-4
we developed catalysts 1 - 3 for the reduction of esters under hydrogen
gas Complexes 2 and 3 are todayrsquos most efficeint catalysts for this process and have recently
become commercially available (Aldrich catalogue numbers 746339 and 746347)
Here we disclose the synthetic structural and catalytic details of our newest robust practical and
efficient H2 hydrogenation catalyst distinguished by excellent carbonyl selectivity The air-stable
osmium complex from our laboratory OsHCl(CO)(NNNP-tBu) (4) is todays most successful
general catalyst for production of unsaturated alcohols from enals enones and alkyl enoates under
H2 at 25 - 100 degC while using 001 - 005 mol [Os] preferably without solvent
References
1 Goussev D G Spasyuk D PCT Patent Application WO 2013023307 A1
2 Spasyuk D Smith S Gusev D G Angew Chem Int Ed 2013 52 2538 - 2542
3 Spasyuk D Gusev D G Organometallics 2012 31 5239-5242
4 Spasyuk D Smith S Gusev D G Angew Chem Int Ed 2012 51 2772-2775
158
P47
OVERCOMING SELF-DESTRUCTIVE REACTIVITY IN
ORGANOLANTHANIDE COMPLEXES
PG Hayes KRD Johnson BL Kamenz
University of Lethbridge Department of Chemistry Lethbridge Canada
In an effort to prepare organometallic lanthanide complexes that feature new and unusual
properties we have designed and synthesized several families of pincer ligands comprised of
phosphinimine donors attached to rigid aromatic cores Rare earth complexes of the ligands have
been prepared and notably diverse reaction behavior such as cyclometalative CndashH bond activation
dearomatization and functionalization of ligand pyrimidine rings by 15-alkyl migration and ring-
opening insertion has been observed Notably the evolution of the design of these pincer ligands
has recently yielded a series of thermally stable organolanthanide species that are resistant to
cyclometalation The synthesis as well as the reaction chemistry of the corresponding
organometallic complexes will be presented
159
P48
METALLOPORPHYRIN-INCORPORATED DIPHOSPHINE LIGANDS FOR
METAL ION-BINDING
G-A Yu K-M Wong J-S Huang N Zhu C-M Che
The University of Hong Kong Department of Chemistry Hong Kong
Diphosphine ligands have been widely used in organometallic chemistry and catalysis1 By
incorporation of functional units such as metallomacrocycles the resulting functionalized
diphosphines could exhibit unusual properties or binding behavior In this study we prepared
several examples of ruthenium porphyrin phosphine complexes [RuII(Por)(dppm)2] (1 Por = TTP
4-MeO-TPP F20-TPP dppm = bis(diphenylphosphino)methane) by a similar method to that
previously reported for their congeners2 Reaction of complexes 1 with a number of metal
complexes MLn afforded [(LmM)( -dppm)RuII(Por)( -dppm)(MLm)] (2 M = Ag Au) which have
been characterized by spectroscopic methods including 1H NMR
31P NMR and UVVis
spectroscopy and also by X-ray crystal structure determination The formation of complexes 2 from
complexes 1 demonstrates the role of complexes 1 as a unique type of diphosphine ligands
functionalized with metalloporphyrins (which constitute a large family of metal complexes that
resemble heme cores in biological systems and exhibit a wide variety of applications3) Studies are
underway to explore the properties of this new type of metalloporphyrin-incorporated diphosphine
complexes of transition metals
References
1 (a) Genet J-P Ayad T Ratovelomanana-Vidal V Chem Rev 2014 114 2824 (b) Broda
H Hinrichsen S Tuczek F Coord Chem Rev 2013 257 587 (c) Birkholz M-N Freixa
Z van Leeuwen P W N M Chem Soc Rev 2009 38 1099 (d) Freixa Z van Leeuwen P
W N M Coord Chem Rev 2008 252 1755 (e) Tuczek F Adv Inorg Chem 2004 56 27 (f)
Bessel C A Aggarwal P Marschilok A C Takeuchi K J Chem Rev 2001 101 1031
2 Ball R G Domazetis G Dolphin D James B R Trotter J Inorg Chem 1981 20 1556
3 (a) Handbook of Porphyrin Science Kadish K M Smith K M Guilard R Eds World
Scientific 2010 (b) The Porphyrin Handbook Kadish K M Smith K M Guilard R Eds
Academic Press 2000
160
P49
SYNTHESIS OF NOVEL ACCEPTOR MOLECULES OF MONO- AND
MULTIADDUCT FULLERENE DERIVATIVES FOR IMPROVING
PHOTOVOLTAIC PERFORMANCE
HB Liu C Liu
Institute of Chemistry Chinese Academy of SciencesCAS Key Laboratory of Organic Solids
Beijing PR China
Fullerene derivatives are extensively used in organic photovoltaics (OPVs) because of their high
electron affinity and high mobility1 and remarkable properties on photoinduced electron transfer in
which [66]-phenyl C61-butyric acid methyl ester (PC61BM) is the most widely employed material2
We have successfully synthesized and separated a series of tert-butyl 4-C61-benzoate (t-BCB)
organofullerenes including monoadduct diadduct and triadduct compounds and investigated their
photophysics electrochemistry thermal properties and high-performance liquid chromatography
analysis3 The photovoltaic devices were fabricated based on monoadduct diadduct and triadduct
products and the devices based on them exhibited power conversion efficiencies of 243 048
and 168 respectively Methyl 4-C61-benzoate series fullerene materials with low cost and high
yield including monoadduct and bisadduct compounds were also synthesized and the photovoltaic
devices based on them showed power conversion efficiency of 348 and 016 respectively4 This
was the first time to study the dependent relationship on the device performance and the different
isomer numbers This work supplied new route to design fullerene materials as PCBMrsquos alternative
References
1 Yu G Gao J Hummelen J C Wudl F Heeger A J Science 1995 270 1789
2 Liu C Xiao S Shu X Li Y Xu L Liu T Yu Y Zhang L Liu H Li Y ACS Appl
Mater Interfaces 2012 4(2)1065
3 Liu C Xu L Chi D Li Y Liu H Wang J ACS Applied Materials amp Interfaces 2013 5
1061
4 Liu C Li Y J Chi D Chen S H Liu T F Wang J Z Liu H B Li Y L Fullerenes
Nanotubes and Carbon Nanostructures 2014 22 277
161
P50
THE FIRST EXAMPLE OF THE SYNTHESIS AND STUDY OF 2-[(Z)-1-
(FERROCENYLMETHOXY)PROP-1-ENYL]-5-ETHENYLIDENE-45-
DIHYDRO-13-THIAZOLES BY METHOD OF MALDI MASS
SPECTROMETRY
OV Inozemtseva OA Tarasova NA Nedolya LV Klyba ER Sanzheeva BA Trofimov
A E Favorsky Irkutsk Institute of Chemistry Siberian Branch of the Russian Academy of Sciences
1 Favorsky St Irkutsk 664033 Russian Federation
Earlier unknown 2-[(Z)-1-(ferrocenylmethoxy)prop-1-enyl]-5-ethenylidene-44-dimethyl-45-
dihydro-13-thiazole (1) the first representative of ferrocenyl-substituted functionalized 2-
thiazolines was obtained in two preparative steps from (ferrocenylmethoxy)allene isopropyl
isothiocyanate and propargyl bromide (through synthesis and structural reorganization of
conjugated 2-aza-135-triene 2 under action of t-BuONa) in 33 yield (not optimized)
It was shown that the matrix-assisted laser desorptionionization (MALDI) mass spectrometry can
be appropriate for the study of the low molecular weight thiazoles in particular such as compound
1 (with 25-dihydroxybenzoic acid as a matrix) In the gas phase under the experiment conditions
the generation of [2M] and [2M ndash H2O] ions (M is molecule of thiazole 1) was detected The
analysis of the fragmentation of these ions in field-free region showed that their decay was mainly
due to both the degradation of thiazole ring and the formation of the ion [FcCH2]+ at mz 199
Mass spectrum MALDI (under the positive mode) of thiazole 1 registered in the mode reflectron
On the inserts А ndash the МS2 spectrum of ion at mz 768 B ndash the МS
2 spectrum of ion at mz 786
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No 13-03-00691a)
786182
768312
784186
0
1000
2000
3000
4000
5000
Inte
ns [a
u]
7675 7700 7725 7750 7775 7800 7825 7850 7875 7900mz
199044
768338
473156313149
000
025
050
075
100
1254x10
Inte
ns [a
u]
200 400 600 800mz
2M - H2O
2M
A
786469
199130
473353313201 6433920
1
2
3
4x10
Inte
ns [a
u]
200 400 600 800mz
B
162
P51
SYNTHESIS AND MASS SPECTRA OF ELECTRON AND CHEMICAL
IONIZATION OF 2-[(Z)-1-METHOXYPROP-1-ENYL]-5-ETHENYLIDENE-
45-DIHYDRO-13-THIAZOLE
OV Inozemtseva LV Klyba ER Sanzheeva NA Nedolya OA Tarasova BA Trofimov
A E Favorsky Irkutsk Institute of Chemistry Siberian Branch of the Russian Academy of Sciences
1 Favorsky St Irkutsk 664033 Russian Federation
The behavior of 2-[(Z)-1-methoxyprop-1-enyl]-5-ethenylidene-45-dihydro-13-thiazoles 1ndash4
synthesized for the first time from methoxyallene isothiocyanates and propargyl bromide1 under
electron ionization (EI 70 eV) and positive ion chemical ionization (PICI methane) has been
studied
Principal fragmentation routes of the 45-dihydro-13-thiazoles 1ndash4 after EI include a thiazole ring
cleavage (pathway 1) and the loss of alkyl substituent mainly at position 4 (pathway 2)
For PICI of the compounds 1ndash4 are typical processes of protonation and electrophilic addition
followed by the loss of the 2-methoxybut-2-enenitrile molecule
The authors are grateful for the financial support from the Russian Foundation for Basic Research
(Grant No 13-03-00691a)
1 Nedolya N A Tarasova O A Albanov A I Trofimov B A Tetrahedron Lett 2014 55
2495ndash2498
163
P52
FLUORESCENCE PHOTOSENSITIVE MATERIALS FOR INFORMATION
OPTICAL RECORDING
VF Traven IV Ivanov SM Dolotov DA Cheptsov
D Mendeleev University of Chemical Technology of Russia
In the modern world computer and information technology continue to develop with increasing
speed that increases the requirement for higher performance systems that are capable of
preservation reproduction and processing of information at very high speeds An actively
developing area allowing to obtain a carrier with high density recorded information is to
manufacture fluorescent multilayer disks (FMD) Use of the information recording FM-discs is
based on photochemical conversion of compounds that change their fluorescent properties whether
it is shift of the maximum fluorescence appearance of fluorescence or its attenuation [1]
N N
R 1
R 3
R 2
h
C C l4
N N
R 1
R 3
R 2
+ H+
O
O
O
N
C H 3
C H 3
N
C H 3
CH 3 O
O H
O
N+
C H 3
C H 3
N
C H 3
CH 3
H+
Previously we have studied new reaction photodehydrogenation 3-pyrazolinylcoumarines and
found it be accompanied by increased acidity [2] In this report we consider an application of this
reaction for opening of the lactone form of rhodamine dye These two reactions are accompanied by
the formation of the fluorophore with a high fluorescence quantum yield and high light resistance
As we have found both these reactions undergo easily both in organic solvents and in polymer
matrixes For example the irradiation of the polymethylmethacrylate film which contain dissolved
pyrazoline hexachloroethane and lactone of Rhodamine B by light in a wavelength range of 360-
400 nm leads to the appearance coloration of the film with irradiated areas exhibits fluorescent
properties We have used these results for optical data recording with fluorescent readout [3]
1) C M Rudzinski DG Nocera In Optical Sensors and Switches KS Schaze Ed Marcel
Dekker New York USA 2001 (Chap 1)
2) IV Ivanov SM Dolotov OI Kobeleva TM Valova V A Barachevskii VF Traven
IzvRAN Serkhim 2012 2290-2300
3) V F Travenacute S M Dolotov I V Ivanov V A Barachevsky O I Kobeleva T M Valova I
V Platonova A O Ait Patent application no 3011109935 of March 17 2011
164
P53
RING OPENING OF DONOR-ACCEPTOR CYCLOPROPANES WITH
AZIDE ION ndash STRAIGHTFORWARD ACCESS TO AZA-HETEROCYCLES
KL Ivanov EV Villemson EM Budynina OA Ivanova IV Trushkov
Moscow State University Department of Chemistry Moscow Russia
Nucleophilic ring opening of donor-acceptor (DA) cyclopropanes is an efficient approach to various
polyfunctional structures including natural products and medicines1-4
Currently a wide range of
nucleophiles was introduced into reactions with DA cyclopropanes however a number of
nucleophilic reagents still remains unexplored In this research we have found optimal conditions
for DA cyclopropanes 1 ring opening with azide ion leading to the formation of -azidocarbonyl
compounds 2 Moreover we developed one-pot process consisting of ring openingKrapcho
dealkoxycarbonylation which allowed us to achieve a simple approach to the GABA precursors 3
The concurrent presence of azide function activated methine or methylene group EDG and EWG
substituents in compounds 2 and 3 makes them convenient building blocks for the streamlined
synthesis of wide range five- and six-membered N-heterocyclic frameworks which are ubiquitous
structural units of numerous natural and synthetic bioactive molecules We designed approaches to
pyrrolidones pyrroles piperideines triazolopyridines tetrazolopyridines etc based on simple
synthetic sequences including Staudingeraza-Wittig cascade or [3+2] cycloaddition as key steps
These strategies were successfully used in formal syntheses of nicotine and atorvastatin
1 Reissig H-U Zimmer R Chem Rev 2003 103 1151-1196
2 Carson CA Kerr MA Chem Soc Rev 2009 38 3051-3060
3 Cavitt MA Phun LH France S Chem Soc Rev 2014 43 804-818
4 Schneider TF Kaschel J Werz DB Angew Chem Int Ed 2014 53 5504-5523
165
P54
NATURAL GAS HYDRATE FORMATION IN THE PRESENCE OF
SURFACTANTS
IK Ivanova1 ME Semenov
2 II Rozhin
2
1 - Ammosov North-Eastern Federal University
2 - Institute of Oil and Gas Problems Siberian Branch Russian Academy of Sciences
The aim of the work is determination of the temperature and pressure of formation and
decomposition (melting) of the natural gas hydrate synthesized from natural gas of the Sredneviluy
gas and condensate field (GCF) and distilled water also in the systems based on it in the presence
of sulfonic of 01 by weight as well as with artificial nucleating agent (sand) by differential
scanning calorimetry
Fig 1 Calculated equilibrium conditions of the gas hydrate formation for natural gas of the
Sredneviluy GCF and methane
The experimental data (Fig 1) are identical to those calculated by the method of E Dendy Sloan for
the used natural gas hydrate equilibrium conditions It should be noted that against the background
stands out experimental points obtained by the decomposition of natural gas hydrate which was
synthesized from a 01 solution of sulfonic Comparing the equilibrium conditions of the
individual components of natural gas it is found that this point corresponds to the equilibrium
conditions of the methane hydrate It is known that natural gas hydrates are a mixture of hydrates of
different gases with complex structure This study suggests the possibility of separation of this
mixture on the hydrates of individual gases Furthermore it was found that the use of surfactants
leads to an increased conversion of water into the gas hydrate (gt 70) compared with 23 of the
gas hydrate formation in distilled water
166
P55
CONTROL OF THE REACTION SELECTIVITY IN Pd AND Ni-
CATALYZED HYDROPHOSPHORYLATION OF ALKYNES
JV Ivanova1 LL Khemchyan
1 SS Zalesskiy
1 VP Ananikov
1 IP Beletskaya
2 ZA Starikova
3
1 - Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Lomonosov Moscow State University Chemistry Department Moscow Russia
3 - Nesmeyanov Institute of Organoelement Compounds RAS Moscow Russia
Nowadays transition-metal-mediated carbon-heteroatom (C-E E=S Se Si P Te O) bond
construction has drawn great attention due to well-recognized advantages high selectivity
quantitative yields and mild reaction conditions [1][2][3] The study of metal-catalyzed
phosphorus-carbon (P-C) bond formation has led to significant progress in organic synthesis and
established numerous synthetic procedures for the synthesis of new valuable compounds [1]
We developed two switchable synthetic protocols allowing us to obtain the products of choice via
subtle change in the catalytic system (Scheme 1) The palladium-based catalyst demonstrated high
sensitivity to the number and position of substituent in the aromatic rings of the phosphine ligand
Application of two different phosphines selectively directed the catalytic reaction either to linear or
branched product formation [4] The Ni(acac)2DIBAL-H precatalyst was the first example of
nickel-based system which allowed to synthesize vinylphosphonates bisphosphonates or
alkyltetraphosphonates without any ligands or solvents [5][6] Slight variations of Ni precatalyst
loading routed the selectivity of the hydrophosphorylation reaction Mechanistic study with ESI-MS
and NMR methods revealed the key nickel intermediates involved into the catalytic cycle [6]
Scheme 1
[1] VP Ananikov M Tanaka (Eds) Hydrofunctionalization Springer 2013 Heidelberg ISBN
978-3-642-33734-5 DOI 101007978-3-642-33735-2
[2] IP Beletskaya VP Ananikov Chem Rev 2011 111 1596
[3] F Alonso IP Beletskaya M Yus Chem Rev 2004 104 3079
[4] VP Ananikov JV Ivanova LL Khemchyan IP Beletskaya Eur J Org Chem 2012
3830
[5] YuV Ivanova LL Khemchyan SS Zalesskii VP Ananikov IP Beletskaya Rus J Org
Chem 2013 49 1099
[6] LL Khemchyan JV Ivanova SS Zalesskiy VP Ananikov IP Beletskaya ZA Starikova
Adv Synth Catal 2014 356 771
167
P56
Cu-CATALYZED AEROBIC OXIDATIVE TRANSFORMATION OF
KETONE-DERIVED N-TOSYL HYDRAZONES A NEW ENTRY INTO
ALKYNES
X-W Li W-Q Wu H-F Jiang
South China University of Technology School of Chemistry and Chemical Engineering
Guangzhou P R China
Alkyne moiety is a fundamental structural element and functional group occurring in various
bioactive molecules functional materials and natural products1 Sonogashira reaction and
electrophilic alkynylation2 are the most widely used methods for the construction of alkynes still
some formidable challenges remained to be resolved3 On the other hand the field of alkyne retro-
hydration that is deprotonation of ketone derivatives for the alkynes synthesis however is still in
its infancy 4
In our continuing efforts toward the development of green chemistry on selective oxidation of
unsaturated hydrocarbons5
we have developed an efficient copper-catalyzed aerobic
dehydrogenation of ketone-derived N-tosyl hydrazones which were carbene precursors to the
corresponding alkynes Further cross-couplings of N-tosyl hydrazones with halides or terminal
alkynes were also performed delivering to functionalized alkynes or asymmertric diynes A
mechanism involved aerobic oxidation of Cu-carbene intermediate was proposed for this C-C triple
bond formation
Reference
1 Modern Acetylene Chemistry Stang P J Diederich F Eds VCH Weinheim Germany
1995
2 Dudnik A S Gevorgyan V Angew Chem Int Ed 2010 49 2096
3 Negishi E Anastasia L Chem Rev 2003 103 1979
4 Negishi E King A O Klima W L Patterson W Silveira A J Org Chem 1980 45
2526
5 Wu W Jiang H Acc Chem Res 2012 45 1736
168
P57
[Co]-СATALYZED [6+2]-CYCLOADDITION OF 12-DIENES TO 1357-
CYCLOOCTATETRAENE
VA Dyakonov1 GN Kadikova
1 GF Gazizullina
2 UM Dzhemilev
1
1 - Federal State Institution of Science Institute of Petrochemistry and Catalysis Russian Academy
of Sciences Laboratory catalytic Synthesys Ufa Russia
2 - Ufa State University of Economics and Service Ufa Russia
Eight-membered carbocycles are found in many natural compounds exhibiting high biological
activity [1] The catalytic cycloaddition based on 1357-cyclooctatetraene (COT) are an effective
method for the synthesis of such carbocycles [2] [Co]-Catalyzed cyclodimerization of COT with
alkynes leading to the formation of bicyclo[422]deca-2479-tetraenes 1 [3]
R
R
C o I2d p p e Z n Z nI
2
4 0 oC C2H
4C l
2
1 It should be noted that in literature have no examples of catalytic codimerization of 1357-
cyclooctatetraene with 12-dienes In the development of this work and our ongoing research [4ab]
we carried out [6π+2π]-cycloaddition of COT with 12-dienes in the presence of 10 mol
CoI2dppeZnZnI2 (C2H4Cl2 40 deg C 20 h) The corresponding bicyclo[422]deca-247-trienes 2
were obtained in high yields
R
RC o I
2d p p e Z nZ nI
2
4 0 oC C2H
4C l
2
2R = P h A lk
This work was performed under financial support from the Russian Foundation for Basic Research
(Grant 13-03-00167 and Grant of RF President (Sci Sh ndash 213620143))
1 Plemenkov VV Introduction to the chemistry of natural compounds Kazan 2001 376 p
2 Yu ZX Wang Y Wang Y Transition-metal-catalyzed cycloadditions for the synthesis of eight-
membered carbocycles Chem Asian J 2010 1072-1088
3 Achard M Mosrin M Tenaglia A Buono G Cobalt (ΙΙ)-Catalyzed [6+2] Cycloadditions of
Cyclooctatetra(tri)ene with Alkynes JOrgChem 2006 71 2907 -2910
4 a) Dyakonov VA Kadikova GN Dzhemilev UM Ti-catalyzed [6π +2 π]-cycloadditions of
allenes with 135-cycloheptatriene Tetrahedron Lett 2011 52 2780-2782 b) Dzhemilev UM
Kadikova GN Kolokoltsev DI Dyakonov VA Catalytic [6π+2π]-cycloaddition of alkynes
12- and 13-dienes to 135-cycloheptatrienes involving Ti complexes Tetrahedron 2013 69
4609-4611
169
P58
MOBILE NANODEFECTS AS COMPLEXING AGENTS IN SOLID PHASE
CHEMISTRY
AM Kaplan NI Chekunaev
NNSemenov Institute of Chemical Physics Russian Academy of Sciences
Put forward by one of the authors the idea about the possible role of mobile nanodefects as
complexing agents allowed to explain for the first time a number of non-trivial effects of solid-
phase chemistry These are 1 the effect of greatly acceleration of catalytic processes induced by
high energy impacts on heterogeneous catalysts [1] 2 the phenomena of freezing of polymer
chains at constant temperatures and reanimation of such chains at temperatures increasing of
investigated samples in solids [2] 3 the effect of exceeding by several orders of the rate of
affiliation of monomer molecules to the active centers in glass monomers samples compared to
crystalline samples of the monomer [3] 4 the phenomenon of the abnormal logarithmic time
dependence of the polymer yield for unterminated solid-state polymerization at low conversions [4]
In contrast to gas and liquid phases very low orientation mobility of microparticles in solid phase
frequently does not allow to perform chemical interaction even particles of reagents which are in
contact with each other for prolonged time This effect is a consequence of unacceptable for
chemical interaction starting mutual orientation of the particles and impossibility to improve the
situation at insufficient space close to them Furthermore structural nanodefects (mobile vacancies
polyvacancies dislocations nanoincontinuity etc) present in the real solid bodies may in case of
their sufficient mobility lead to pair of potentially chemically capable but unreacting due to
orientational immobility of adjacent reagents particles in quite dense areas of solid bodies
sufficient free space Remobing by this the steric barrier for the interactions of such particles
Consequently as it was for the first time mention by the presenter real (lsquolivingrsquo) active center (A)
of solid phase reactions should be considered not the experimentally detectable traditional active
centers (A) (radical and ions) but a peculiar complex of such centers with the carrier of excess of
volume mdash with mobile nanodefects The concentration of [A]ltlt[A] It should be pointed out the
special role of mobility of nanodefects in formation of real cative centers A In case of presence of
in the system of only motionless nanodefects ldquochemicalrdquo diffusion leads in time to the removal of
reacting particles from such defects turming these particles to inactive state In heterogenous
catalysis this effect is similar to the effect of catalyst poisoning Movable nanodefects which
activated during some time a group of reagent particles move to another such group and also
activate it This process of activation of chemical process takes places until meeting of moving
nanodefects leading to sticking of defects and decrease of their concentration Based on concept of
moving nanodefects with excessive free volume as complexing agents authors using computer
calculations in papers [1-4] explained the effects previously considered anomalous mentioned
above
1 AMKaplan VVLunin NIChekunaev Book of abstracts of VII Voevodsky conference
laquoPhysics and Chemistry of elementary chemical processesraquo P 191-192 Chernogolovka 2007
2 AM Kaplan NI Chekunaev Doklady Physical Chemistry Vol 425 Part 1 pp 51-53 2009
3 AM Kaplan NI Chekunaev Russian Chemical Bulletin No 8 pp 677-683 2009
4 AM Kaplan NI Chekunaev Polymer Science Series B Vol 52 No 1-2 pp 57-62 2010
170
P59
SYNTHESIS OF OLIGOSACCHARIDE FRAGMENTS OF CANDIDA
ALBICANS MANNAN CORRESPONDING TO ANTIGENIC FACTOR 6
AA Karelin YE Tsvetkov NE Nifantiev
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Laboratory of
Glycoconjugate Chemistry Moscow Russia
The yeast-like fungi of the genus Candida are opportunistic pathogenic microorganisms capable of
causing severe infections in immunocompromised patients The main surface antigen of Candida
responsible for its antigenic specificity is mannan which represents the carbohydrate part of the cell
wall mannoprotein The determinants of antigenic factor 6 are represented by several β-D-Man-
(1rarr2)-residues attached to short α-(1rarr2)-linked chains
Here we report synthesis of oligosaccharides 1 and 2 containing two and three β-linked residues
The presence of the amino group in the aglycones of the synthetic oligosaccharides allows their
subsequent covalent binding to high-molecular carriers and labels of various types
We utilized a convergent approach based on glycosylation of known α-(1rarr2)-linked mannosyl
acceptor with β-(1rarr2)-linked donors
The preparation of required donors was started from compound 3 The thiomannoside was
transformed into sulfoxide 4 Then these monosaccharides were coupled to give required
disaccharide donor Here we used the fact that conditions of sulfoxide activation donrsquot affect
thioglycosides Oxidation of dimanosyl donor 5 followed by glycosylation of 3 allowed obtaining
trisaccharide donor 7 Glycosylation of α-(1rarr2)-linked mannosyl acceptor with donors 5 and 7 and
subsequent removal of protecting groups gave target olygomannosides 1 and 2
Acknowledgments
This work was supported by the Russian Foundation for Basic Research under grant 14-03-31583
171
P60
NANOSTRUCTURED NICKEL ORGANOSULFIDES SYNTHESIS
CHARACTERIZATION AND APPLICATION IN THE CATALYTIC
CARBON-SULFUR BOND FORMATION REACTION
AS Kashin VP Ananikov
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
Over the last decades nanostructured metal chalcogenides have made an outstanding contribution to
the nanotechnology microelectronics optics and material science However their application in
organic synthesis and catalysis remains largely unexplored [1]
In our work we focused on the nickel organosulfides ndash [Ni(SAr)2]n These nanostructured nickel
complex salts can be easily prepared by the reaction between nickel acetylacetonate and aryl thiols
Rapid ligand substitution accompanied with the self-organization in solution leads to formation of
polymeric structures where nickel atoms are linked by μ2-SAr groups Tuning of the reaction
conditions or changing of the substituent in the aromatic ring of thiol allows to generate [Ni(SAr)2]n
particles of various shapes and sizes (Figure 1)
Figure 1 FE-SEM images of [Ni(SAr)2]n particles Ar = Ph (A) p-BrPh (B)
We have demonstrated that synthesized nickel aryl sulfides can be utilized as a source of SAr
groups for the carbon-sulfur bond formation in the cross-coupling reaction with aryl halides [2]
Reaction in the presence of palladium- or copper-based catalytic system results in the diaryl sulfides
formation with the yield up to 95 (Scheme 1)
Scheme 1 Catalytic C-S bond formation reaction between nickel organosulfides and aryl halides
A unique effect of morphology control of the SAr group donor reactivity in cross-coupling reaction
was found Mechanistic studies have shown that cross-coupling reaction with Cu catalyst proceeds
in the liquid phase and involves leaching whereas the same reaction with Pd catalyst is more
complex and may involve both ndash homogeneous and heterogeneous pathways
[1] VP Ananikov IP Beletskaya Dalton Trans 2011 40 4011
[2] AS Kashin VP Ananikov Top Catal 2013 56 1246
172
P61
SYNTHESIS OF DERIVATIVES OF 6-ACETYL-2-CYCLOHEXENONE AND
THEIR BORON CHELATE COMPLEXES
DS Khachatryan1 II Boyko
2 AA Vardapetyan
1 AL Razinov
1 KR Matevosyan
3
1 - FGU IREA Moscow Russia
2 - ООО TEHNOLOG Pereslavl-Zalessky Russia
3 ndash DI Mendeleev RHTU Moscow Russia
In some cases reactions of enolates obtained using conventional basic reagents (alcoholates
amides metal hydrides) afford products in very low yields12
In the late 70s we first succesfully
used patassium carbonate in Michael reaction for the synthesis in preparative quantities of
derivatives of 2-cyclohexenone 2-4
ndash synthons for construction of physisologically active molecules
including steroids1
The present work follows the studies in the field of synthesis of new derivatives of 2-cyclohexenone
by Michael reaction in the presence of patassium carbonate Of special interest are derivatives of 2-
cyclohexenone containing acetyl substituent in position 6 ndash analogues of 13-diketones which can
complex transition and rear yearth metals 5-7
We studied prepartion of 35-disubstituted 6-acetyl-2-cyclohexenones based on cyclocondensation
reaction of acetylacetone (1) with αβ-unsaturated ketones 2а-h in the presence of catalytic amount
of patassium carbonate at reflux in different solvents
M e M e
O OR
1R
O
R1
O
R
O
M e
M e
O
O O
M e
R1
R
+
1 2 a -h 3 a -h 4 a -h а R=MeOC6H4CH=CH R
1=MeOC6H4 b R=R
1=Ph c R=2-тиенил R
1=Ph
d R=24-Cl2C6H3CH=CH R1=BuOC6H4 e R=4-BuOC6H4CH=CH R
1=4-BuOC6H4
f R=4-AmOC6H4CH=CH R1=4-AmOC6H4 g R=4-lC6H4CH=CH R
1=4-ClC6H4
h R=4-MeC6H4CH=CHR1=4-MeC6H4
In 1Н NMR spectra of all diketones 4a-h the doubling of all expected signals is observed that as
known7 is due to keto-enol tautomerism ie 6-acetyl-2-cyclohexenones behave in solution as
classic 13-diketones
Based on these data the chelating ability of compounds 4a-h was evaluated It was shown that they
can form chelate complexes with boron ndash 13-dioxaborines which possess photosensibilizing
properties5 as well as (with compound 4b as an example) complexes with metals (Сu
2+ Ni
2+ Со
2+
Еu3+
) 46
1 ED Bergmann DGinsburg RPappo in Organic Reactions v10 Wiley New York 1959
2 NMMorlyan DS Khachatryan ShO Badanyan Arm Chem J 1978 31 (2) 866
3 DS Khachatryan AA Vardapetyan GA Panossian RG Mirzoyan NM Morlyan ZhOrH 1990 26
(10) 2092
4 DS Khachatryan AA Vardapetyan VN Tkachenko NM Morlyan Proc Conf laquoIII All-Union
Conference on Chemical reagents Ashgabat 1989 p 107
5 II Boyko TI Boyko AA Vardapetyan GV Nowicka DS Khachatryan NM Morlyan and KK
Koshelev As1704446 USSR Bull Izobr 2000 9
6 VIZelenov Russian JGenChem 200979 (1) 142
7 JKFGeirsson ADGudmundsdottir Synthesis 1990 11 993
173
P62
TRITERPENOID SAPONINS FROM THE ROOTS OF
ACANTHOPHYLLUM GYPSOPHILOIDES REGEL AS POTENTIAL
IMMUNE-MODULATING TOOLS FOR DENDRITIC VACCINE DESIGN
EA Khatuntseva1 VM Menrsquoshov
1 AS Shashkov
1 YE Tsvetkov
1 RN Stepanenko
2 R Ya
Vlasenko2 EE Shults
3 GA Tolstikov
3 TG Tolstikova
3 DS Baev
3 VA Kaledin
4 NA
Popova4 VP Nikolin
4 PP Laktionov
5 AV Cherepanova
5 TV Kulakovskaya
6 EV
Kulakovskaya6 NE Nifantiev
1
1 - N D Zelinsky Institute of Organic Chemistry RAS Leninsky pr 47 Moscow RF
2 - Institute of Immunology Ministry of Health and Social Development of RF Kashirskoe Ch
242 Moscow RF
3 - N N Vorozhtsov Novosibirsk Institute of Organic Chemistry Siberian Branch of RAS pr Acad
Lavrentrsquoeva 9 Novosibirsk RF
4 - Institute of Cytology and Genetics Siberian Branch of the RAS 10 pr Acad Lavrentrsquoeva
Novosibirsk RF
5 - Institute of Chemical Biology and Fundamental Medicine Siberian Branch of the RAS 8 pr
Acad Lavrentrsquoeva Novosibirsk RF
6 - G K Skryabin Institute of Biochemistry and Physiology of Microorganisms RAS Pushchino
Despite significant effort the development of effective vaccines inducing strong and durable T-cell
responses against cancer cells has remained a challenge It is anticipated that the main target of
vaccination are dendritic cells the principal antigen presenting cells whose main function is to
identify exogenous structures and present them to naiumlve CD4+ and CD8+ T cells in lymph nodes A
current strategy to enhance the effectiveness of vaccination is to deliver antigens directly to
dendritic cells which are readily accessible within the well-established in vitro procedure Anti-
cancer dendritic vaccines are intended to activate cytotoxic antigen-specific CD8+ T cells which are
activated via complexes with MHC class I molecules of DCs with the only possibility of
exogenous antigen presentation on those to be done by cross-presentation This process includes
translocation of the antigen from the endosome to the cytosol and is known to be efficiently
promoted by saponins which are part of saponin-based adjuvants QS21 and ISCOMATRIX
Amphiphilic nature of most saponins enables the formation of nano-sized micelles and among
them immune-stimulating complexes (ISCOM) which are currently used as adjuvant systems
These particles are known to be readily engulfed by DCs and the optimal uptake of this type of
vesicles by DCs was reported to be achieved when particle size is 05 ndash 5 μm which corresponds to
conventional size of saponin-based micelles in water solutions
The objective of the present work was to isolate new individual saponins from readily available
routs of Acanthophyllum gypsophiloides with the view to further investigation of their vesicle
formation potential and in vitro effect of saponin-containing ISCOM s on dendritic cells
1 R = OH 2 R = H
Two new triterpenoid saponins 1 and 2 were isolated from the methanol
extract of the roots of Acanthophyllum gypsophiloides Regel These sapo-
nins have quillaic acid or gypsogenin moieties as aglycon and both bear
similar sets of two oligosaccharide chains which are trisaccharide -L-
Ara-(1rarr3)-[ -D-Gal-(1rarr2)]- -D-GlcA and pentasaccharide -D-Xyl-
(1rarr3)- -D-Xyl-(1rarr3)- -L-Rha-(1 2)-[ -D-Qui-(1rarr4)]- -D-Fuc
connected to C-28 The structures were elucidated by the combination of
mass spectrometry and 2D NMR spectroscopy methods Reference EA Khatuntseva et al Beilstein J Org Chem 20128763-75
174
P63
NMR SPECTROSCOPY AND ESI-MS AS EFFECTIVE RAPID METHODS
FOR MONITORING BIOMASS CONVERSION INTO 5-HMF IN IONIC
LIQUIDS
EA Khokhlova VV Kachala VP Ananikov
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Unprecedented selectivity for biomass and cellulose conversion to 5-HMF has opened outstanding
opportunities for sustainable chemical industry 5-HMF was identified as a platform chemical for
production of biofuels solvents resins liquid alkanes (C7 - C15) and monomers for plastics
However in spite of complete conversion more detailed studies have shown moderate product
yields (40-60) and later formation of by-products (humins) has been identified The main
stumbling block to studying cellulose processing in ionic liquids is the absence of an analytic tool
for monitoring reaction yields in ionic liquids[1]
Our research has been focused on real-time carbohydrate conversion monitoring using a new NMR
based approach for quantitative measurements A practical application of the developed approach
was demonstrated directly in the NMR tube Our latest study revealed the ways to characterize
molecular transformations in IL systems and to detect reaction intermediates using a special reactor
that eliminates microheterogeneity[2] Transformation of carbohydrates to 5-HMF with various
promoters was investigated and discrepancy between conversions and yields was observed High-
quality NMR spectra suitable for integration of individual signals were measured after removing the
intrinsic heterogeneity of ionic liquid samples below the spectroscopic detection level
Moreover we have disclosed a new opportunity of using the MS2 mode in reaction monitoring
frameworks that make it possible to obtain both qualitative and quantitative information A
combined use of the developed NMR and mass spectrometry approaches for analyzing components
of IL solutions will expand the frames of promising chemistry in ILs
[1] VPAnanikov Chem Rev 2011 111 418
[2] EAKhokhlova VVKachala VPAnanikov ChemSusChem 2012 5 783
175
P64
Rh(III) CATALYZED SYNTHESIS OF ISOQUINOLINE DERIVATIVES BY
ANNULATION OF BENZYLAMINES WITH ALKYNES
D-S Kim C-H Jun
Yonsei University Department of Chemistry Seoul Korea
Rh(III)-catalyzed C-H bond cleavage is one of efficient ways to make N-heterocyclic compounds1
In particular ortho-alkyl- or alkenylation provides an efficient synthetic method for preparing
ortho-substituted aromatic ketones2 During the course of our studies on the Rh(III)-catalyzed N-
annulation reaction we found synthetic method of pyridine derivatives from primary allylamines
with alkynes3 In this poster we report a new protocol for the preparation of isoquinoline from
benzylamine and internal alkyne using Rh(III)-catalyst with Cu(II) as an oxidizing agent For
example the N-heterocyclic annulation reaction of 2-methoxybenzylamine with 4-octyne was
carried out at 100 oC for 4 hours in the presence of [Cp
RhCl2]2 (25 mol [Rh]) and
Cu(OAc)2H2O to produce corresponding pyridine in 92 yield The proposed mechanism of this
annulation reaction is also discussed4
1 Song G Wang F Li X Chem Soc Rev 2012 41 3651-3678
2 Murai S Kakiuchi F Sekine S Tanaka Y Kamatani A Sonoda M Chatani N Nature
1993 366 529-531
3 Kim D-S Park J-W Jun C-H Chem Commun 2012 48 11334-11336
4 Kim D-S Park J-W Jun C-H Adv Synth Catal 2013 355 2667-2679
176
P65
A NOVEL BRANCHED MONOSACCHARIDE 36-DIDEOXY-4-C-[(S)-12-
DIHYDROXYETHYL]-D-XYLO-HEXOSE FROM A POLYSACCHARIDE
OF A BACTERIUM OF THE GENUS PHOTORHABDUS
NP Arbatsky1 AS Shashkov
1 NA Kirsheva
2 AN Kondakova
1 RZ Shaikhutdinova
2 SA
Ivanov2 AP Anisimov
2 YA Knirel
1
1 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - State Research Center for Applied Microbiology and Biotechnology Obolensk Moscow Region
Russia
The genus Photorhabdus from the family Enterobacteriaceae includes three species of
entomopathogenic bioluminescent bacteria Photorhabdus temperata Photorhabdus luminescens
and Photorhabdus asymbiotica They all have a mutualistic relationship with entomophagous
nematodes from the family Heterorhabditis
These bacteria synthesize an S-form
lipopolysaccharide which consists of lipid A core oligosaccharide and O-specific polysaccharide
(O-antigen) and is important for both pathogenicity and symbiosis Recently aiming at creation of
the chemical basis for classification of Photorhabdus species structures of the O-polysaccharides of
representatives of P asymbiotica subsp asymbiotica and subsp australis1 and P luminescens
subsp laumondii2 have been elucidated In this work we established the O-polysaccharide structure
of P temperata subsp temperata XlNachT and identified a novel branched monosaccharide as its
component
The O-polysaccharide was obtained by mild acid hydrolysis of the lipopolysaccharide isolated from
bacterial cells by phenol-water extraction In addition to monosaccharides that are rather common in
nature (glucose mannose galactose and N-acetylgalactosamine) sugar analysis of the
O-polysaccharide revealed a branched octose called photorhabdose The new sugar was isolated as
a 12rsquo-anhydro furanose derivative by reversed-phase HPLC after full acid hydrolysis of the
O-polysaccharide (Scheme) and its structure as 36-dideoxy-4-C-[(S)-1rsquo2rsquo-dihydroxyethyl]-D-xylo-
hexose was determined by one- and two-dimensional 1H and
13C NMR spectroscopy
Photorhabdose has not been hitherto found in nature and differs from the known branched octoses
36-dideoxy-4-C-[(S)- and (R)-1-hydroxyethyl]-D-xylo-hexoses (yersinioses A and B respectively)
in deoxygenatation of the terminal carbon (C-2rsquo) of the side chain
Scheme Isolation of photorhabdose (Sug) by full acid hydrolysis of the O-polysaccharide Arrows
indicate HH correlations observed in the NOESY spectrum
1 Kondakova A N Kirsheva N A Shashkov A S Shaikhutdinova R Z Arbatsky N P
Ivanov S A Anisimov A P Knirel Y A Carbohydr Res 2011 346 1951-1955
2 Kondakova A N Kirsheva N A Shashkov A S Shaikhutdinova R Z Ivanov S A
Anisimov A P Knirel Y A Carbohydr Res 2012 351 134-137
177
P66
EVOLUTION AND INTERLAYER DYNAMICS OF ACTIVE SITES OF
PROMOTED TRANSITION METAL SULFIDE CATALYSTS UNDER
HYDRODESULFURIZATION CONDITIONS
VM Kogan1 PA Nikulshin
2 NN Rozhdestvenskaya
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - Samara State Technical University Samara Russia
According to the suggested dynamic model [1] neighboring layers of the multilayered MoS2
crystallite exchange sulfur between Mo- and S-edges placed one under another in the course of
permanent reductionndashsulfidation processes under hydrogen atmosphere When the sulfur atoms
bonded to Co atoms leave the reduced edge of the layer the atoms of the promoter also move along
the sulfur atoms from one layer to an adjacent layer of higher sulfidation state Then the process
reverses Such oscillations occur until the sulfur organic compound adsorbs on the vacancy on the
reduced edge The frequency of the oscillations determines catalytic activity of the CoMoS slab
Thiophene adsorption makes transfer of a promoter to the neighboring slab improbable because the
electron density of thiophene sulfur compensates the extra positive charge on the Mo atom appeared
after H2S removal When thiophene adsorbs on the vacancy of the CoMoS site the proton linked to
Co moves to the SH group of the neighboring layer forming the H2S which desorbs from this layer
and new vacancy is formed This model explains the reasons of the electron transfer from atom of
promoter to Mo and different locations of the active sites responsible for hydrogenation and
desulfurization on a promoted Mo-sulfide slab A method to evaluate the efficiency of CoMoS
catalysts for HDS of various types of crudes has been developed Now these findings obtain their
explanations within the developed dynamic model (Fig 1)
Fig 1 Dynamic model of
transformations of the active
sites of promoted TMS
catalysts in the course of
thiophene HDS
The suggested model gives a basis to develop criteria to evaluate the efficiency of the catalyst
activity in hydrotreating of various types of crude oil
1 VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
178
P67
THE CONCEPT OF INTERLAYER DYNAMICS AND THE MECHANISMS
OF HDS AND ALCOHOL SYNTHESIS ON THE ACTIVE SITES OF
PROMOTED TMS CATALYSTS
VM Kogan1 PA Nikulshin
2 VS Dorokhov
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
2 - Samara State Technical University Samara Russia
A new mechanistic model for molybdenum sulfide catalysts with cobalt and nickel promoters under
hydrodesulfurization (HDS) reaction conditions is proposed that includes dynamic migration of
sulfur and promoter atoms between adjacent sulfide layers [12] These migrations are caused by
heterolytic dissociation of gas-phase hydrogen and formation of hydride hydrogen on a promoter
atom Hydride hydrogen adsorbed on a promoter induces electron density transfer from the bonding
promoter to Mo changing its catalytic activity Adsorbed hydrogen induces migration of sulfur and
promoter atoms between adjacent clusters This dynamic migration causes transformation of
lsquolsquorapidrsquorsquo into lsquolsquoslowrsquorsquo sites and vice versa and therefore influences catalytic activity Migration of
Co or Ni promoter atoms to Mo sites on the rim is more likely than to Mo sites on the edge of
Co(Ni)MoS layers because the former can accept promoter atoms from both upper and lower layers
A method to evaluate the efficiency of CoMoS catalysts for HDS of various types of crudes has
been developed The proposed model provides crutial information for rational design of improved
hydrotreating catalysts and selection of preferred catalytic reaction conditions for various types of
hydrocarbon feedstock via optimization of the density and ratio of lsquolsquorapidrsquorsquo and lsquolsquoslowrsquorsquo catalyst
active sites
Application of the dynamic model to the investigation of the mechanism of the mixed alcohol
synthesis (MAS) over TMS catalysts modified by potassium gives us ground to assume that the
reaction of alcohol formation from synthesis gas proceeds on almost the same types of active sites
as it takes place for HDS Unlike HDS sites responsible for hydrogenolysis of CS bond the MAS
sites responsible for alcohol formation are modified by potassium (Fig 1)
Fig 1 TEM images of the CoMoSAl2O3 catalyst modified by 5 10 and 15 of K and the models of
intercalation of K+
ions between the layers of the MoS2 crystallites
The TEM data witness that K addition increases stacking number The catalytic examinations show
that potassium promotes alcohol yield Basing on these data we suppose that K ions intercalate
between neighbouring MoS2 layers affecting the active phase morphology and (AS)rsquos selectivity in
MAS The Co-promoted catalyst is more selective to alcohols than the non-promoted one
Promoting activity Co in MAS and HDS lets us suppose that the nature of the active sites operating
in both reactions is similar [1] VM Kogan PA Nikulshin Catal Today 149 (2010) 224
[2] VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
[3] VM Kogan NN Rozhdestvenskaya IK Korshevets Appl Catal A Gen 234 (2002) 207
1100 KK 1155 KK 55 KK
179
P68
RELATIONSHIP BETWEEN ACTIVE PHASE MORPHOLOGY AND
CATALYTIC PROPERTIES OF THE CARBON-ALUMINA-SUPPORTED
Co(Ni)Mo CATALYSTS IN HDS AND HYD REACTIONS
PA Nikulshin1 VA Salnikov
1 AA Mozhaev
1 PP Minaev
1 VM Kogan
2 AA Pimerzin
1
1 - Samara State Technical University Samara Russia
2 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
Effects of activated carbon of a carbon-coated alumina (CCA) support and active phase morphology
of transition metal sulfide (TMS) catalysts in hydrotreatment (HDT) of S-containing compounds
were studied The catalysts were synthesized from Anderson-type heteropolycompounds and
characterized with multiple methods X-ray powder diffraction N2 physisorption temperature-
programmed desorption of ammonia pyridine-adsorbed Fourier transform infrared spectroscopy
H2 temperature programmed reduction and high resolution transmission electron microscopy The
catalysts were tested in hydrodesulfurization (HDS) of thiophene dibenzothiophene and HDT of
diesel To interpret the obtained results we used an interlayer dynamics concept developed recently
[1] The TPR measurements indicate hydrogen uptake by the C-coated support at reaction
temperatures It witnesses that CCA accumulates gas-phase hydrogen and could be a source of
hydrogen for HDT reactions Carbon affects active phase morphology changing the carbon content
it is possible to vary a stacking numberlinear size ratio of the active phase particles and thereby to
control hydrogenation to direct desulfurization (HYDDDS) selectivity (Fig 1)
Average stacking num
ber
L
N
Average length nm12
1416
1820
2224
2628
3032
3032
3436
3840
4244
46В
06
08
10
12
14
16
18
20
22
24
26 24
18
15
06
)(s10 TOF14
SHYDDS
Average length nm Ave
rage
sta
ckin
g num
ber
L
N
12
14
16
18
20
22
24
26
28
30
32
Var130
3234
3638
4042
4446
Var2
03
04
05
06
07
08
09
Var3
07
06
05
04
03
(a) (b)
1
2
3
4
1rsquo
2rsquo
3rsquo
4rsquo
2 - 2rsquo
1 - 1rsquo4 - 4rsquo
3 - 3rsquo
(c)
Fig 1 3D dependences of TOF number (a) and HYDDDS selectivity (b) in DBT HDS on average
length and average stacking number of Co(Ni)MoS2 particles in the catalysts schematic
visualization of the morphology of promoted MoS2 slabs variation depending on the number of the
active sites on the edges and rims of the slabs (c)
An increase in the average linear size of the slab leads to a drop of HDS and HYD activities The
longer layers in the slabs the fewer solid angles are and so the higher the effect of the support On
the contrary in the multilayered structure the support effect diminishes The observed high
HYDDDS selectivity of the catalysts synthesized from AHM and nickel nitrate may be caused by
low edge surface Ni on the MoS2 slab which should also form the unpromoted Mo-sites responsible
for the HYD reactions on the edges The results suggest that the catalytic activity in HDS and HYD
reactions depends on the shape of crystallites of the active phase The results are interpreted using
recently proposed concepts of interlayer dynamics These concepts are helpful in establishing
structure-activity relations for TMS 1 VM Kogan PA Nikulshin NN Rozhdestvenskaya Fuel 100 (2012) 2
180
P69
GENESIS OF HDT CATALYSTS PREPARED WITH THE USE OF
Co2Mo10HPA AND COBALT CITRATE STUDY OF THEIR GAS AND
LIQUID PHASE SULFIDATION
PA Nikulshin1 AV Mozhaev
1 KI Maslakov
2 AA Pimerzin
1 VM Kogan
3
1 - Samara State Technical University Samara Russia
2 - MV Lomonosov Moscow State University Chemistry Department Moscow Russia
3 - ND Zelinsky Institute of Organic Chemistry RAS Laboratory of catalysis by trasition metals
and their compounds Moscow Russia
Production of clean fuels with less than 10 ppm sulfur content is one of the most important and
claiming the attention problem in recent petroleum refinery The countermeasures for the ultra deep
desulfurization are to apply novel highly active catalysts and to optimize the operation condition of
the hydrodesulfurization (HDS) process The development and application of more active and stable
catalysts could enhance the productivity and improve the product quality without negative impacts
on capital investment
Genesis of alumina supported hydrotreating (HDT) catalysts prepared with the use of
decamolybdodicobaltate heteropolyanion (Co2Mo10HPA) and cobalt citrate during their sulfidation
processes and deactivation in diesel HDT has been investigated The sulfidation stage was studied
for two procedures gas phase sulfidation by H2SH2 and liquid phase treatment by a mixture of
dimethyldisulfide in diesel at various temperatures and durations The catalysts have been studied
by N2 adsorption thermogravimetric analysis X-ray photoelectron spectroscopy and high-
resolution transmission electron microscopy methods The catalysts were tested in HDT of mixture
of 70 wt straight run gas oil with 16 wt light cycle oil and 14 wt light coker gas oil
Mechanisms of the active phase formation in the course of gas and liquid phase sulfidation
processes have been established (Fig 1)
Fig 1 CoMoS phase formation
mechanisms during gas and liquid phase
sulfidation of the Co3(CA)45-
Co2Mo10Al2O3 catalyst (S ndash average
stacking number L ndash average length
were found from TEM Co content in
CoMoS phase and (CoMo)slab were
found by XPS)
It was found that gas phase sulfidation led to formation of the CoMoS active phase with higher
cobalt content comparing to liquid sulfidation of the catalyst and initial activity of the gas phase
treated catalysts in diesel HDT was also higher than catalysts subjected to liquid sulfidation
Catalytic examination after accelerated deactivation conditions showed that the liquid phase
sulfided sample was more resistant to the deactivation Probably it is due to stabilization of active
phase particles by coke formed intensively during liquid phase sulfidation In liquid phase
sulfidation both metals are sulfided simultaneously with the formation of nuclei of CoMoS phase II
type at low temperature (2300C) At high temperature (340
0C) the increase of particle size of
CoMoS phase is occurred
181
P70
SYNTHESIS OF HEPTASACCHARIDE FRAGMENT CORRESPONDING
TO α-(1-3)-GLUCAN OF ASPERGILLUS FUMIGATUS
MV Orekhova BS Komarova NE Nifantiev
Laboratory of Glycoconjugate ChemistryND Zelinsky Institute of Organic Chemistry Russian
Academy of Sciences Leninsky Prospect 47 119991 Moscow Russia
For immunocompromised individuals Aspergillus fumigatus is the most important and life
threatening pathogen [1] In the cell walls of this ubiquitous fungus -(1rarr3)-glucan constitutes the
main polysaccharide [2] which forms biofilms and is a cause of permanent infection [3] Previously
a synthesis of spacer armed -(1rarr3)-pentaglucoside conjugates with BSA and biotin was achieved
These derivatives were used for obtaining and characterization of antibodies recognizing α-(1rarr3)-
glucan which were used for tracing A fumigatus cells However for the final goal of the project the
development of a vaccine against A fumigatus the five glucosyl units in the chain is not enough
In the present report a synthesis of 3-aminopropyl -(1rarr3)-pentaglucoside 1 (Scheme) is
described The success of convergent scheme toward the target compound relied on the use of
disaccharide 2 which was modified by orthogonal levulinoyl (Lev) and p-methoxyphenyl (pMP)
groups The ability to remove Lev and pMP groups independently made it possible to prepare
disaccharide donor 5 and acceptor 3 from one precursor and then to combine them to get
tetrasaccharide 6 Glucosylation of the trisaccharide acceptor 9 with tetrasaccharide donor 8
proceeded smoothly to give heptasaccharide backbone Stereoselectivity of each -glucosylation of
the whole scheme was controlled by -stereodirecting benzoyl group at O-6 [4] While high yields
of all glucosylations were attained due to the choice of N-phenyl-trifluoracetidoyl leaving group and
MeOTf as a promoter [5] Free heptasaccharide 1 was converted to BSA and biotin conjugates
using amino group of the spacer
1 A Gastebois C Clavaud V Aimanianda J P Latgeacute Future Microbiology 2009 4 583
2 D Maubon S Park M Tanguy M Huerre C Schmitt M C Preacutevost D S Perlin J P Latgeacute A
Beauvais Fungal Genetics and Biology 2006 43 366
3 A Beauvais C Schmidt S Guadagnini P Roux E Perret C Henry S Paris A Mallet M C Preacutevost
J P Latgeacute Cellular Microbiology 2007 9 1588
4 B S Komarova M V Orekhova Y E Tsvetkov N E Nifantiev Carbohydrate Research 2014 384
70
5 B S Komarova Y E Tsvetkov Y A Knirel U Zaumlhringer G B Pier N E Nifantiev Tetrahedron
Letters 2006 47 3583
182
P71
SUPRAMOLECULAR STRUCTURES IN ADDUCTS OF
CYMANTRENECARBOXYLIC ACID WITH FIVE- AND SIX-MEMBERED
AROMATIC N-BASES
PS Koroteev AB Ilyukhin ZhV Dobrokhotova VM Novotortsev
N S Kurnakov Institute of General and Inorganic Chemistry of Russian Academy of Sciences
One of the goals of supramolecular chemistry is the search for new molecules that are potentially
capable of self-assembly owing to nonvalent interactions The molecule of
cyclopentadienyltricarbonylmanganese (η5-C5H5)Mn(CO)3 (cymantrene) which has the ldquopiano
stoolrdquo shape besides of many other peculiarities has specific properties as a potential building
block for supramolecular architectures both due to its special geometry and the nature of its
constituent moieties Earlier we have studied the crystal-chemical behavior of anions of
cymantrenecarboxylic acid (η5-C5H4COOH)Mn(CO)3 (HL) and more sterically hindered β-
cymantrenoylpropionic acid (η5-C5H4CO(CH2)2COOH)Mn(CO)3 combined with alkaline metals
cations and with protonated molecules of polytopic nitrogen bases which have various geometries
and provide opportunities for supramolecular interactions [1]
New derivatives of HL and polytopic aromatic N-bases imidazole (I) pyrazole (II) 3-amino-124-
triazole (III) 4-amino-124-triazole (IV) 2-aminopyridine (V) 3-aminopyridine (VI) 4-
aminopyridine (VII) 24-diamino-6-hydroxypyrymidine (VIII) were obtained and characterized by
X-ray diffraction
It has been shown that two- and three-dimensional supramolecular structures of these derivatives
are formed owing to special properties of the cymantrene moiety in particular its ability to form
COhellip
H hydrogen bonds (HBs) but the type of the structure is mostly determined by the geometry of
the cation and by its capability of HBs formation (Fig1) The possibility of organic molecules of
various nature to self-organize due to protonation andor HBs formation and with regard to specific
geometries is discussed
Fig 1 Fragments of the structures of VIImiddotHL (left) and VIIImiddotHL (right)
[1] AB Ilyukhin PS Koroteev MA Kiskin ZhV Dobrokhotova VM Novotortsev Journal of
Molecular Structure 1033 (2013) 187ndash199
Acknowledgements This study was financially supported by the RFBR (No 13-03-12428 14-03-00463) the
Council on Grants of the President of the RF (NShshy171220143) and the Presidium of the Russian
Academy of Sciences
183
P72
NUCLEOFILIC BROMO- AND IODODIFLUOROMETHYLATION OF
ALDEHYDES
MD Kosobokov VV Levin MI Struchkova AD Dilman
IOC RAS Moscow Russia
Nowadays RuppertminusPrakash reagent (Me3SiCF3)1 and its functionalized analogues
2 3 are widely
applicable fluorinated reagents in organic synthesis Indeed these air stable silanes are convenient
agents for nucleophilic fluoroalkylation reactions They exhibit their nucleophilic reactivity under
silaphilic Lewis base activation generating a pentacoordinate intermediate which could react with
a suitable electrophile (eg aldehydes) Reactions of the RuppertminusPrakash reagent (X =F) and
chloro-substituted analog (X = Cl) as well as many other functionalized silanes follow this
pathway
However reactions of a bromo-substituted silane (X = Br) with aldehydes mediated by a fluoride
ion have been unsuccessful presumably owing to facile decomposition of anionic intermediate to
difluorocarbene Indeed silane Me3SiCF2Br can generate difluorocarbene even in the presence of
weak Lewis bases such as chloride and bromide ions While (bromodifluoromethyl)trimethylsilane
(1a) can be readily obtained from the RuppertminusPrakash reagent iodinated silane (1b) has not been
known We prepared silane 1b from silane 1a in 70 yield by the brominezinc exchange followed
by iodination
Then we developed a method for nucleophilic bromo- and iododifluoromethylation of aldehydes
using bromo- and iodo-substituted difluoromethyl silicon reagents (Me3SiCF2X) The reaction is
performed in the presence of a combination of tetrabutylammonium and lithium salts Bu4NXLiX
(X = Br or I) in propionitrile4
It is believed that in this process a short-lived halodifluoromethyl carbanion serves as nucleophile
which is reversibly generated from difluorocarbene and a halide anion
This work was supported by the Russian Science Foundation (project 14-13-00034)
[1] Liu X Xu C Wang M Liu Q Chem Rev 2014 ASAP doi101021cr400473a
[2] Kosobokov M D Dilman A D Struchkova M I Belyakov P A Hu J J Org Chem
2012 77 2080minus2086
[3] Kosobokov M D Dilman A D Levin V V Struchkova M I J Org Chem 2012 77
5850minus5855
[4] Kosobokov M D Levin V V Struchkova M I Dilman A D Org Lett 2014 16 3784
184
P73
NEW REGIOSELECTIVE ROUTE TO 5-CARBOXY-123-TRIAZOLES VIA
PALLADIUM-CATALYZED CARBONYLATION OF 5-IODO-123-
TRIAZOLES
YN Kotovshchikov GV Latyshev NV Lukashev IP Beletskaya
Chemistry Department Lomonosov Moscow State University Moscow Russia
Various compounds containing 123-triazole moiety are of great importance in coordination and
supramolecular chemistry medicine polymer and materials sciences [1] In particular some 5-
carboxy-123-triazoles were shown to be kinases inhibitors as well as to exhibit antiviral and
antibacterial effects [2] So far the only synthetic route to these compounds was thermal [3+2]-
cycloaddition of organic azides to propiolic acid derivatives The main drawback of the method is
low regioselectivity Formation of two regoisomers diminishes yields of desired 5-carboxy-123-
triazoles and complicates isolation of the products Since 5-iodo-123-triazoles can be prepared
from 1-iodoalkynes and azides under Cu(I) catalysis [3] the subsequent carbonylation reaction
could became a new regioselective approach to 5-carboxy-123-triazoles
We have shown that alkoxycarbonylation of 5-iodo-123-triazoles could be performed under mild
reaction conditions with 1 atm of CO in the presence of 5 Pd(OAc)2 Various functional groups
(ester hydroxyl ketone nitro) were tolerated and a number of 5-methoxycarbonyl-123-triazoles
were obtained in good to excellent yields The transformation appeared sensitive to steric effects
and bulky substituents led to decrease in reaction rate andor yield
This work was supported by RFBR (grant 11-03-00265-а)
1 (a) M Meldal C W Tornoslashe Chem Rev 2008 108 2952 (b) J E Hein V V Fokin Chem Soc Rev
2010 39 1302
2 (a) H Cheng J Wan M-I Lin Y Liu X Lu J Liu Y Xu J Chen Z Tu Y-S E Cheng K Ding J
Med Chem 2012 55 2144 (b) G S Gadaginamath M G Bhovi Indian J Chem Sect B Org Chem
Incl Med Chem 2005 44 1068
3 J E Hein J C Tripp L B Krasnova K B Sharpless V V Fokin Angew Chem Int Ed 2009 48
8018
185
P74
A GENERAL APPROACH TO THE SYNTHESIS OF THIOPHENE-
CONTAINING ELECTRON-DONOR AND -ACCEPTOR FRAGMENTS FOR
CONJUGATED POLYMERS FOR SOLAR PHOTOVOLTAIC CELLS
IO Konstantinov1 MM Krayushkin
1 ML Keshtov
2 SA Kuklin
2 VS Kochurov
3 NA
Radychev4 AR Khokhlov
2
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - AN Nesmeyanov Institute of Organoelement Compounds RAS Moscow Russia
3 - MV Lomonosov Moscow State University Physical Department Moscow Russia
4 - Carl von Ossietzky University of Oldenburg Physical Department Oldenburg Germany
The goal of this work was developing a general method for creating both electron-donor and
electron-acceptor moieties in terms of dithienylethenes to use them for preparation of new
conjugated polymers as an electroactive material for solar cells Bis(trimethylstannyl)-2-dodecyl-
benzotrithiophene monomer (1) as a donor in DndashA copolymers was synthesized for the first time
from the corresponding dithienylethene with thiophene bridge [1]
B r
R
N N
SS
C8H
1 7
B r SS
N
S
H3 1
C1 5
B r B r
S
SS
C1 2
H2 5
A r n
S S
S
C1 2
H2 5
S n S n
SS
SN
C1 7
H3 5
B r B r
SS
SN
B r B r
R1
O C1 0
H2 3
C8H
1 7
C1 0
H2 3
C8H
1 7
S
O Et
B u
1
2
P
3 R =
4
5 R 1 =
6 R 1 =
Dibromides 2-6 were synthesized also analogously from dihetarylethenes [12] and used as
monomers of the electron-acceptor nature
New narrow-band conjugated polymers of type P with a rigid alternation of donor and acceptor
units were prepared on the basis of these monomers under the Stille reaction conditions in the
presence of tetrakis(triphenylphosphine)palladium as a catalyst [34]
The thermal optical electrochemical and photovoltaic properties of the copolymers were studied
[5]
1 MM Krayushkin and MA Kalik Syntheses of Photochromic Dihetarylethenes In Katritzky
editors Advances in Heterocyclic Chemistry Vol 103 Oxford Academic Press 2011 p 1-59
2 Shirinian VZ Lonshakov DV Kachala VV Zavarzin IV Shimkin AA Lvov AG
and Krayushkin MM J Org Chem 2012 vol 77 p 8112
3 Keshtov ML Marochkin DV Kochurov VS Komarov PV Parashchuk DYu
Trukhanov VA and Khokhlov AR Vysokomol Soedin Ser B 2014 vol 56 no 1 p 1
4 Keshtov ML Toppare L Marochkin DV Kochurov VS Parashchuk DYu Trukhanov
VA and Khokhlov AR Vysokomol Soedin Ser B 2013 vol 55 no 6 p 723
5 ML Keshtov SA Kuklin VS Kochurov IO Konstantinov MM Krayushkin NA
Radychev and AR Khokhlov Doklady Chemistry 2014 Vol 454 Part 2 pp 25ndash31
186
P75
PHOTOCHEMICAL REARRANGEMENT OF CHROMONES AND
BENZOFURANS
KS Chudov1 KS Levchenko
1 VN Yarovenko
1 MM Krayushkin
1 OI Kobeleva
2 TM
Valova2 VA Barachevsky
2 EP Grebennikov
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - Photochemistry Center Russian Academy of Sciences Moscow Russia
At present optical information recording in the existing ODs is based on thermoinduced
transformation processes of substances that change the reflection properties under the action of
light Prospects for increasing the information capacity of ODs are related to the development of
multilayered photosensitive detection media based on organic compounds that being irradiated
undergo irreversible photochemical transformations of the initial non-fluorescing compounds into
fluorescent photoproducts It has recently been shown that UV-irradiated acylchromones I that do
not manifest fluorescence are irreversible rearranged to fluorescent furano[34-b]chromenones II
Based on the latter we are developing multilayered detection media for ODs of the WORM archive
type [12]
O
O
R
O
O
R1
O
O
O
R
OR
1
R2 R
2U V
I II
R R 1 R 2 = H F G A r H e ta r
We synthesized a set of benzofurans IV with a highlighted furylpropenonic fragment and
demonstrated that they under UV-illumination also transformed into tricondensed derivatives V
that is the photorearrangement by all appearances has a common character It is worthy noted that
initial compounds IV did not possess fluorescence whereas the products V did
O
O
R2
O
R1
R1
O
O
O
H
O
R1
O
R2
O
R 1= M e B r R 2 = P h A r
III
IV
R 1= M e B rV
U VB rC H2C O R 2
The fluorescence properties of the compounds due to irreversible photochemical transformations of
chromones and benzofurans in toluene were studied The quantum yields of the photoproducts were
measured Some relationships between the fluorescence properties of the photoproducts and their
structure were revealed
A part of the compounds are characterized by a high Stokes shift and other profitable properties that
provide their practical application in photosensitive detection media with nondestructive
fluorescence reading optical information
1 VA Barachevsky OI Kobeleva TM Valova AO Ait AA Dunaev AM Gorelik MM
Krayushkin KS Levchenko VN Yarovenko VV Kyiko EP Grebennikov Opt Mem amp
Neur Networks 19 (2010) 187
2 VA Barachevsky MM Krayushkin VV Kyiko EP Grebennikov Phys Status Solidi C 8
(2011) 2841
187
P76
NEW CHROMONE-CONTAINING LIGANDS
KA Myannik1 VN Yarovenko
1 KS Levchenko
2 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
2 - Central Research Technological Institute ldquoTekhnomash Moscow Russia
Chromone derivatives are of doubtless interest as bioactive compounds and elements of detecting
media for multilayer optical discs of superhigh capacity We showed the possibility to synthesize
chromone-containing ligands containing fragments of thiohydrazides of oxaminic acids 1-9
1 2 3
4 56
7 8 9
O
O NN H
SO
NH
F
O
O NN H
SO
NH
F
F
O
O NN H
SO
NH
N H 2 O
O NN H
SO
NH
F
N H 2
S
O
O NN H
SO
NH
F
C O O E t
S
O
O NN H
SO
NH
N H 2
C O O E t
O
O NN H
SO
NH
OH O
O NN H
SO
NH
F
OH
S
O
O NN H
SO
NH
N H 2
C O O E t
OH
188
P77
NEW COMPLEX STRUCTURES BASED ON OXAMINIC ACID
THIOHYDRAZIDES
MM Krayushkin VN Yarovenko IV Zavarzin
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
It is known that among thiohydrazides there are many drugs of different action which is enhanced
in many cases in the presence of metal cations We showed a possibility to synthesize complexes
from the ligands containing fragments of oxaminic acid thiohydrazides 1-3
2 3
1
The geometric parameters of synthesized complex 1 were studied by X-ray diffraction analysis (Fig
1)
Fig 1 Fig 2
The square-planar coordination mode of nickel is attained due to two additional atoms Si with a
distance of 3407(2) Aring and Oii with a distance of 3451(4) Aring (symmetry transform i x y+1 z and i
x y-1 z ) with the formation of a distorted octahedron around the nickel atom An infinite chain is
thus formed (Fig 2)
189
P78
THREE-COMPONENT CONDENSATION OF IMINOAZOLIDINONES
WITH ALDEHYDES AND MELDRUM`S ACID SYNTHESIS AND STUDY
OF PROPERTIES OF THE IMIDAZOPYRIDINE-25-DIONES
KS Krylov AN Komogorttsev BV Lichitsky AA Dudinov MM Krayushkin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Multicomponent reactions are indispensable tools which are used for the construction of different
heterocyclic systems The marked advantage of such a reactions are the versatility and efficiency of
synthesis of the new organic materials The diversity of the multicomponent reactions allows to
create a broad set of compounds without using the methodology of the complicated multistage
synthesis The present work devoted to the development of our previously elaborated method based
on multicomponent reaction of the heterocyclic enamines carbonyl compounds and the Meldrum`s
acid We have proposed the versatile method of preparation of the previously unknown 7-aryl-1-
phenyl-1677-tetrahydro-4H-imidazo[45-b]pyridine-25-diones 1 based on the three component
condensation of iminoazolidines 2 aldehydes 3 and the Meldrum`s acid 4
N
NNH
O
A r
O
P h
N
NH
NH
O
P h
O O
O O
Ar C H O
Et O H
ON
+ +
2 3 4 1
The properties of the obtained imidazopyridine-25-diones 1 were investigated It is demonstrated
that compounds of type 1 undergo the acid hydrolysis with formation of previously unknown 5-
substituted 1-phenylimidazolidine-24-diones 5
N
NNH
O
A r
O
P h
A c O HN
NH
O
O
P h
NH2
OA r
1 5
References
1 B V Lichitsky R M Belyi A N Komogortsev A A Dudinov M M Krayushkin Russ
Chem Bull Int Ed 2013 62 1026-1031
190
P79
RADICAL CROSS-DEHYDROGENATIVE C-O COUPLING OF 13-
DICARBONYL COMPOUNDS WITH HYDROXYLAMINE DERIVATIVES
IB Krylov AO Terent`ev BN Shelimov GI Nikishin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian
Federation
Cross-dehydrogenative coupling as a rule is a reaction in which two different starting molecules
are connected by a new bond with the elimination of one hydrogen atom from each of the
molecules In the last decade these reactions have attracted great attention because they can be used
to form a new bond with almost the maximum possible atom economy and do not require additional
synthetic steps for the introduction of functional groups (Hal OTf BR2 SiR3 SnR3 ZnHal etc)
that are necessary in other approaches to the cross-coupling
The cross-dehydrogenative С-С coupling was studied in most detail the C-N C-P and C-O cross-
coupling reactions are less well developed It is difficult to achieve high selectivity in the oxidative
C-O coupling because the starting compounds are prone to side oxidation and fragmentation
reactions giving for example alcohols and carbonyl compounds
In the present work the cross-dehydrogenative СndashO coupling of β-dicarbonyl compounds with
oximes[1]
N-hydroxyimides[2]
and N-hydroxyamides[2]
was performed for the first time
The reaction proceeds in the presence of the different metal-containing oxidants KMnO4
Mn(OAc)2KMnO4 Co(OAc)2KMnO4 Mn(OAc)3bull2H2O MnO2 Mn(acac)3 Fe(ClO4)3
Cu(ClO4)2bull6H2O Cu(NO3)2bull25H2O and (NH4)2Ce(NO3)6 yields are 27ndash94 The synthesis can
be easily scaled up to gram quantities of the target products The method is applicable for a wide
variety of β-diketones and β-keto esters 2-substituted malonic esters and heteroanalogues of
β-dicarbonyl compounds 2-substituted malononitriles and cyanoacetic esters are substantially less
reactive in the cross-dehydrogenative coupling with tested hydroxylamine derivatives
Apparently the oxidant serves two functions in the cross-dehydrogenative coupling reaction the
generation of N-oxyl radicals from hydroxylamine derivatives and the one-electron oxidation of
β-dicarbonyl compounds The formation of N-oxyl radicals was confirmed by ESR spectroscopy
Acknowledgements This work was supported by the Russian foundation for Basic Research (Grant
13-03-12074)
1 I B Krylov A O Terentrsquoev V P Timofeev B N Shelimov R A Novikov V M
Merkulova G I Nikishin Iminoxyl Radical-Based Strategy for Intermolecular C-O Bond
Formation Cross-Dehydrogenative Coupling of 13-Dicarbonyl Compounds with Oximes Adv
Synth Catal 2014 356 2266ndash2280 DOI 101002adsc201400143
2 A O Terentrsquoev I B Krylov V P Timofeev Z A Starikova V M Merkulova A I
Ilovaisky G I Nikishin Oxidative C-O Cross-Coupling of 13-Dicarbonyl Compounds and
Their Heteroanalogues with N-Substituted Hydroxamic Acids and N-Hydroxyimides Adv
Synth Catal 2013 355 2375ndash2390 DOI 101002adsc201300341
191
P80
THE FIRST ENANTIOSELECTIVE ORGANOCATALYTIC REACTION IN
SUPERCRITICAL CARBON DIOXIDE ASYMMETRIC MICHAEL
ADDITION OF DIPHENYLPHOSPHITE TO α-NITROALKENES
EV Kryuchkova IV Kuchurov AG Nigmatov AS Kucherenko SG Zlotin
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky prospekt 47
119991 Moscow Russia
Recently we discovered [1] that asymmetric organocatalytic reactions can be efficiently carried out
in liquid carbon dioxide We have expected that the use of CO2 in the supercritical state (sc-CO2) as
a reaction medium may be even more promising as it is characterized by higher diffusion rates and
a unique capability of dispersing poorly soluble reagents thus enhancing the reaction scope rates
and selectivity
Herein we report that α-nitroalkenes 2 enantioselectively accept diphenylphosphite (1) in sc-CO2 in
the presence of bifunctional tertiary amines 4 and 5 (5 mol )) bearing the squaramide fragment to
afford corresponding β-nitrophosphonates 3 in high yields and with enantiomeric access of up to
94 ee [2] In this way enantiomeric β-nitrophosphonates 3 and ent-3 which are precursors of
optical antipodes of β-amino phosphonic acid derivatives that occur in nature and possess valuable
biological activities were synthesized Furthermore we disclosed a significant potential of sc-CO2
for the fractional extraction of products and recovery of precious chiral catalyst The obtained
results contribute to green chemistry as they eliminate toxic organic solvents originated from
exhausting hydrocarbon resources and facilitate separation and purification steps that usually have
the highest environmental impact in chemical processes
References
1 AG Nigmatov IV Kuchurov DE Siyutkin SG Zlotin Tetrahedron Lett 2012 53 3502
2 IV Kuchurov AG Nigmatov EV Kryuchkova AA Kostenko AS Kucherenko SG
Zlotin Green Chem 2014 16 1521
192
P81
SYNTHESIS OF NEW CLASS OF ORGANIC PEROXIDES
IODOPEROXIACETALS BY TREATMENT OF ENOLE ETHERS WITH
IODINE-HYDROPEROXIDE SYSTEM
AN Kulakova AT Zdvizhkov AO Terentev RA Novikov GI Nikishin
N D Zelinsky institute of organic chemistry Laboratory for Studies of Homolytic Reactions
Moscow Russia
Organic peroxides are very common for development of antitumor and antiparasitic drugs
However effectiveness of drugs reduces due to the mobilization of cells defense mechanisms with
respect to specific substances This problem is solved by the development of new classes of
biological compounds as well as their chemical modifications
In the present work we studied the interaction of mono-and bicyclic enol ethers with a system of I2
hydroperoxide This system allows getting number of new peroxide compounds containing an
iodine atom which makes possible further modification of the peroxide molecule
Commercially available monocyclic enole esters of 23-dihydrofuran and 34-dihydro-2H-pyran
were selected as starting materials as well as their bicyclic analogs that can be synthesized by a
known method
Firstly we studied the interaction of monocyclic enol ethers with the system I2-ButOOH (TBHP)
and I2-tetrahydropyranyl hydroperoxide (THPHP) We have proposed a method to obtain
iodoperoxide with yields up to 90 The reaction is carried out in diethyl ether at 0 deg C in the
presence of 4-fold excess hydroperoxide and an equivalent amount of iodine
Having developed iodoperoxidation method we investigated the reaction of the bicyclic enole
ethers with the I2-H2O2 system Iodoperoxides were obtained with yield of 80 The reaction was
carried under the action of iodperoxidation monocyclic enole ethers at - 40 deg C When using a more
bulky t-BuOOH were obtained addition products the peroxide to double bond not containing iodine
atom In the case of THPHP reaction did not proceed at all
In this work the methodology of synthesis of a new class of organic peroxides - vicinal
iodperoxyacetals and ketals based on mono-and bicyclic enole ethers was developed These
compounds may be useful for inventing new anticancer and antiparasitic drugs
Acknowledgements
This work was supported by the Russian Science Foundation (Grant 14-23-00150)
193
P82
APPLICATION OF AZA-COPE-MANNICH REACTION FOR HIGHLY
EFFICIENT STEROSELECTIVE SYNTHESIS OF DERIVATIVES OF (2SR
3ASR 8ASR)-3A-METHYLOCTAHYDROCYCLOHEPTA[B]PYRROL-
4(1H)-ONE
IN Myasnyanko ER Lukyanenko AV Kurkin
MV Lomonosov Moscow State University
Saturated heterocyclic compounds are much more attractive objects for the development of new
drugs compared to traditionally used in medicinal chemistry heteroaromatic compounds since they
as a rule possess better solubility pharmacokinetic properties and bioavalability [1 2] In this
regard development of efficient stereoselctive methods for the syntheis of such compounds (having
patent purity) is an important task for scientists working in drug discovery field
Earlier we developed highly efficient steroselective synthesis of cis- and trans-fused 3-substituted
octahydrocyclohepta[b]pyrrol-4(1H)-ones using aza-Cope-Mannich reaction as a key step [3 4] In
the presnt work we present simple highly efficient steroselective synthesis of 2-substituted cis-fused
octahydrocyclohepta[b]pyrrol-4(1H)-ones starting from cheap cyclohexene oxide using tandem of
aza-Cope and Mannich reactions as a key step
Amino ketones 1 were obtained as sole stereoisomers in high overall yield their structures were
confirmed by X-ray (for R = Ph and i-Pr)
This work was supported by Russian Foundation for Basic Research (projects 14-03-31685 14-03-
31709 14-03-01114)
1 Ritchie T J Macdonald S J F Young R J Pickett S D Drug Discov Today 2011 16 164-
171
2 Meanwell N A Chem Res Toxicol 2011 24 1420-1456
3 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A Tetrahedron 2011 67
9214-9218
4 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125-10134
194
P83
SYNTHESIS AND TRANSFORMATIONS DERIVATIVES OF AMINO ACID
CONTAINING NITROGENOUS HETEROCYCLE
DR Latypova1 VA Dokichev
1 YuV Vahitova
2
1 - Institute of Organic Chemistry Ufa SC RAS
2 - Institute of Biochemistry and Genetics Ufa SC RAS
The achievements of modern pharmacology and clinical medicine are largely determined by the
synthesis of new groups of physiologically active compounds Compounds containing amino acid
pyrrolidone and hexahydropyrimidine moieties are natural and important group of biologically
active compounds A lot of them have a variety of pharmacological effects (anti-tumor anti-
platelet anti-bacterial and anti-arrhythmic etc)
In order to develop effective regio- and stereoselective methods of synthesis of the biologically
active amino acids derivatives containing nitrogen heterocycle studied the interaction of CH-acids
(acetone benzyl acetone ethyl acetoacetate and 13-acetonedicarboxylic acid diethyl ester) with
formaldehyde primary amines and amino acids in the Mannich reaction conditions On the basis of
the synthesized 13-hexahydropyrimidines containing in the 5-position the acetyl and the ester
group 5-methyl-24-dihydro-3H-pyrazol-3-ones with amino acid moieties are obtained It has been
established that the splitting of 13- hexahydropyrimidine cycle with hydrazine hydrate which
follow with retention of configuration of the optically active centers
3-Diazopyrrolidin-2-ones that are of interest as structural fragments for production analogies of γ-
aminobutyric acid - the chief inhibitory neurotransmitter in the mammalian central nervous system
are synthesized A method of obtaining inaccessible heterocyclic compounds containing a
pyrazolo[15-c]pyrimidine moiety based on the van Alphen-Huettel rearrangement of products of
13-dipolar cycloaddition 3-diazo-4-phenylpyrrolidone with dimethyl acetylenedicarboxylate and
5-diazo-exo-3-azatricyclo[521026
]decan-4-one with quinone is proposed
Among the investigated groups of substances novel compounds that have cytotoxic properties
against both cell HEK293 and SH-SY-5Y are discovered
195
P84
METALPOLYMER NANOCATALYSTS FOR HYDROGEN-OXYGEN
MICRO-POWER ENERGY SOURCES
MV Lebedeva1 NA Yashtulov
2 NE Minina
1 KS Smirnov
2 SS Gavrin
2
1 - Lomonosov Moscow state university of fine chemical technologies Moscow Russia
2 - National research university Moscow power engineering institute Moscow Russia
Development of highly active and stable nanoelectrocatalysts for micro-power energy sources
(MPES) on the basis of fuels conversion is one of the fundamental problems of modern science and
energy The modification of solid polymer membranes (SPM) by metal nanoparticles of not only
the surface but also the volume is used to create efficient catalytically active stable and cheap
materials for energy sources of new generation The introduction of inorganic components makes it
possible to enhance the exploitation characteristics of the solid polymer membranes [1-3]
At present time the most relevant and promising energy sources are fuel cells with solid polymer
electrolyte (SPE) due to their extensive use in stationary applications and mobile electronic
equipment Electrolyte in such system is proton exchange perfluorinated polymer with ionogenic
sulfo groups (ndashSO3H) of the Nafionreg type (Du Pont) that provides unipolar conductivity on
hydrogen ions [12]
As nanostructured matrix-substrate in our work it was used the Nafion type solid polymer
membrane (SPM) with a thickness of less than 02 mm The modification by one-component and
bimetallic nanoparticles of platinum and base metal of the SPM surface and volume promotes
additional catalytic oxidation of hydrogen-containing fuels (H2 C2H5OH HCOOH CH3OH and
others) Due to introduction of nano-sized metal in the polymer matrix and application of bimetallic
systems there is an increasing of the catalytic and functional activity of metal-polymer
nanocomposites and reduced the consumption of expensive Pt and Pd catalysts [12]
The aim of the present study was to establish the influence of the metalpolymers PtNf and PdNf
synthesis parameters on the catalytic activity of platinum nanoparticles in the hydrogen oxidation
and oxygen reduction reactions
The platinum metal nanoparticles solutions were prepared by the radiation chemical reduction 60
Co
in reverse micelle solutions [12] By varying the synthesis conditions one can control the
nanoparticles size content and functional properties By means of the modern physico-chemical
research methods as electron microscopy x-ray phase analysis cyclic voltammetry it was
performed the investigation of nanoparticle and nanocomposite functional properties It was found
that when reducing the size of metal nanoparticles (less than 8 nm) catalytic activity of
metalpolymer nanocomposites (current density catalytically active surface area) increases [12]
The work was supported by RFBR (grant 13-08-12407 ofi_m2)
References
[1] Yashtulov NA Flid VR Russ Chem Bull 2013 V 62 6 Р 1332-1337
[2] Yashtulov NA Revina AA Lebedeva MV Flid VR Kinetics and catalysis 2013 V 54
3 P 336-339
[3] Limpattayanate S Hunsom M Renewable Energy 2014 V 63 5 P 205-211
196
P85
TROumlGER BASE AS A SINGLE SOURCE OF CHIRALITY IN A NEW
BIS(SALICYLALDIMINATO) CATALYST FOR RING-OPENING OF
PROPYLENE OXIDE
DA Lenev1 RG Kalinin
1 VA Kardash
1 AV Kiselyova
1 IO Konstantinov
2
1 - NIOST LLC Tomsk Kuzovlevskii trakt 2 str270
2 - Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospekt 47
Moscow
Recently many privileged catalysts variations of C2-symmetric Schiff base salen ligands of
Jacobsen and Katsuki modified by pendant ammonium arms with nucleophilic counterions and
corresponding cobalt catalysts have been developed[1][2][3] They have been intensively used in
the popular field of stereoregular co-polymerization of alkene oxides with carbon dioxide to yield
regular polymers ndash polyalkene carbonates such as polypropylene carbonate PPC or
polycyclohexene carbonate PCHC Stereotacticity and stereointegrity of PCHC influences its
crystallinity melting point and thermal stability which is higher in the case of stereocomplex ndash
polymeric racemate[1] Co-polymerization of (rac)-propylene oxide with CO2 yields stereogradient
racemic stereocomplex PPC with improved thermal stability and thus processability[2] The PPC
material has been commercialized and the molecular formulas of the respective catalysts have been
patented heavily[3]
Troumlger base (TB)[4] could represent valuable asset for its practical use in asymmetric catalysis In
order to rely upon TB not only as fascinating but also as privileged structure we followed an
algorithm in building a molecule with a single C2 axis for the single TB diamine and single salen
core aligning sequentially the carbon of NCN bridge the metal ion and the center of (N)CC(N)
bond of unsubstituted 12-ethylenediamine
In this preliminary report we present an approach to the synthesis of the newly designed salen
complex 1 with chirality solely due to asymmetric N atoms of enantiopure TB and we report the
preparation of the system capable of efficient catalysis of cycloaddition of propylene oxide with
CO2 to yield cyclic propylene carbonate with high TON and TOF
1
1 X-B Lu W-M Ren G-P Wu Acc Chem Res 2012 45 1721-1735 G-P Wu W-M Ren Y Luo
B Li W-Z Zhang X-B Lu J Am Chem Soc 2012 134 5682-5688
2 K Nakano S Hashimoto M Nakamura T Kamada K Nozaki Angew Chem Int Ed 2011 4868-
4871 B Y Lee A Cyriac Nature Chem 2011 3 505-507
3 A Tullo Capturing Carbon in Chem Eng News June 23 2008 vol 86(25) p21 Novomer Inc WO
2011163133 2011 (S D Allen A E Cherian C A Simoneau J J Farmer)
4 F Voumlgtle Fascinating molecules in Organic Chemistry Wiley Chichester UK 1992 B Dolenskyacute M
Havliacutek VKraacutel Chem Soc Rev 2012 41 3839-3858
197
P86
GEMINAL SILICONZINC REAGENT AS AN EQUIVALENT OF
DIFLUOROMETHYLENE BIS-ANION
VV Levin AA Zemtsov MD Kosobokov AD Dilman
IOC RAS lab8 Moscow Russia
Elaboration of new methods for the synthesis of fluoroorganic compounds is important owing to
unique effect of fluorine atoms on their biological activity Synthetic methods based on the
introduction of fluorinated fragments into organic substrate are most widely presented While
various methods for the introduction of the CF3-group have been documented approaches for the
synthesis of compounds bearing CF2-fragment notably less abundant At the same time this
fragment is isosteric to ethereal oxygen which makes compounds with this moiety highly attractive
as promising pharmaceuticals Typically Synthesis of CF2-containing products involves
deoxofluorination reaction or relies on building block approach Also we recently described a
strategy for assembling these compounds from difluorocarbene nucleophile and electrophile1
We present a germinal siliconzinc binucleophilic reagent (1) for coupling with two electrophilic
spesies2 This reagent conveniently prepared by cobalt-catalyzed brominezinc exchange in
Me3SiCF2Br using isopropylzinc iodide
Under the copper catalysis reagent 1 smoothly reacts with allylic halides with formation of
fluorinated silanes 2 This silanes were employed as nucleophilic reagents with a range of
aldehydes provides after work-up the fluorinated alcohols 3 In this products both nucleophilic sites
of initial reagent 1 successively replaced by two electrophiles
Acknowledgements This work was supported by the Ministry of Sience (project MD-
475020133) Russian Foundation tor Basic Reseach (projects 13-03-12074 14-03-00293 14-03-
31253_mol_a 14-03-31265_mol_a)
[1] Levin VV Zemtsov AA Struchkova M I Dilman AD Org Lett 2013 15 917ndash919
[2] Kosobokov M D Levin VV Zemtsov AA Struchkova M I Korlyukov A A
Arkhipov D E Dilman AD Org Lett 2014 16 1438ndash1441
198
P87
THERMAL AND ALUMINUM OXIDE INDUCED GAS-PHASE RING-
OPENING TRANSFORMATION OF GEM-DIFLUORO- AND GEM-
FLUOROCHLOROCYCLOPROPANES WITH FORMATION OF 2-
FLUORO- OR 2-CHLOROBUTA-13-DIENES
NV Volchkov MB Lipkind MA Novikov OM Nefedov
ND Zelinsky Institute of Organic chemistry of Russian Academy of Sciences Leninsky prospect
47 119991 MoscowRussian Federation
It was found that gem-fluorochlorocyclopropanes 1a-d are converted into corresponding 2-
fluorobuta-13-dienes 3а-d under gas-phase pyrolysis in flow tube-reactor at 400-450degС as result of
thermal cyclopropyl-allylic ring opening transformation and dehydrochlorination Under analogous
conditions gem-difluorocyclopropanes 2a-d undergo only thermal fragmentation with elimination
of difluorocarbene to give alkenes
F F
R
R1
R2
C H 3
1 7 0 -2 5 0 degC
A l2O 3
C l
R2
R
R1
F C l
R
R1
R2
C H 3
1 a -d 3 a -d (3 5 -7 5 )
1 7 0 -2 5 0 deg C
R = R1 = H R
2 = C H 3 (a ) R
1 = R
2 = H R = C H 3 (b )
R = R2 = H R
1 = C H 3 (c ) R = R
1 = H R
2 = C l (d )
A l2O 3 F
R2
R
R1
flo w flo w
4 0 0 -4 5 0 deg C
4 0 0 -4 5 0 deg CR
R1
R2
C H 3flo w
flo w
2 a -d
4 a -d (4 5 -6 5 )
C F 2+
The character of thermal transformation of 1a-d and 2a-d is changed if the pyrolysis carry out in the
presence of Al2O3 In this case gem-difluorocyclopropanes 2a-d can be converted into 2-fluorobuta-
13-dienes 3а-d at 170-250degС as result Al2O3 promoted breaking of very strength carbone-fluorine
bond that induce cyclopropyl-allylic transformation and dehydrofluorination The ability of Al2O3
to activate the breaking С-F-bond cause also the promotion and the alteration of selectivity for ring-
opening transformation of gem-fluorochlorocyclopropanes 1a-d In contraste to homogeneous
pyrolysis heterogeneous thermolysis of 1a-d in the presence of Al2O3 at 170-250degС gave 2-
chlorobuta-13-dienes 4а-d
199
P88
AN IMPROVEMENT OF THE CATALYTIC PERFORMANCE IN THE
ASYMMETRIC MICHAEL REACTION OF PRIMARY AMINE TAGGED
TO AN N-(CARBOXYALKYL)IMIDAZOLIUM CATION
VG Lisnyak AS Kucherenko SG Zlotin
IOC RAS Laboratory 11 Moscow Russia
A (1S2S)-12-diphenylethane-12-diamine derivative modified with an N-(4-
carboxybutyl)imidazolium cation and PF6ndash anion has been developed and applied as a recyclable
organocatalyst of the asymmetric 14-conjugate addition of 4-hydroxy-2H-chromen-2-one to 1-
substituted buten-3-ones or cyclohexen-3-one to afford corresponding Michael adducts in high
yields (up to 97 ) and enantioselectivities (up to 90 ee) [1]
The most active (S)-enantiomer of
the clinically useful anticoagulant warfarin was prepared in this way The catalyst exhibited better
recyclability than its known analog [2]
which does not contain a carboxy group it could be recycled
5 times in the reaction without a significant decrease in product yield or ee values Gradual
deactivation of the catalyst was caused by leaching during workup rather than by off-cycle reactions
between the catalyst and reagents
The work was financially supported by the Russian Foundation of Basic Research (project 12-03-
00420)
[1] A S Kucherenko V G Lisnyak A O Chizhov S G Zlotin Eur J Org Chem 2014 3808
[2] A S Kucherenko D E Siyutkin A G Nigmatov A O Chizhov S G Zlotin Adv Synth
Catal 2012 354 3078
200
P89
SYNTHESIS AND SPECTRAL FEATURES OF NOVEL PHOTOCHROMIC
DIARYLETHENES OF AZOLE SERIES
AG Lvov1 EYu Bulich
2 AM Yanina
2 AM Kavun
3 VZ Shirinian
1 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - DI Mendeleev University of Chemical Technology of Russia Moscow Russia
3 - Higher Chemical College DI Mendeleev University of Chemical Technology of Russia
Moscow Russia
Diarylethenes with heterocyclic aromatic moieties are widely studied to develop different
electronics devices such as optical memory and molecular switches [1] To develop new
photochromic systems with improved spectral properties we have proposed a new type of the
photochromic diarylcycloalkenones of azole series Various novel photochromic diarylethenes
bearing cyclopentenone or cyclohexenone rings as ethene bridge and azole residues (oxazole
imidazole pyrazole and thiazole derivatives) as aryl moieties have been synthesized Ketoesters 1
are the key compounds in these syntheses which were prepared from commercially available
reagents in two stages To introduce diverse functional groups in ethene bridge and aryl moieties
the various synthetic methods (C-alkylation Nazarov Michael and Knoevenagel reactions) have
been used
Ar1
Ar2
O
Ar1
Ar2
O Ar3
O
Ar1
Ar2
P h
O
N
M e A r N
N
M e A r
R
N
NM e
P h
N
S
M e P h
SM e M e
Ar2
O
B r
H Ar2
O
Ar2
O
P h
Ar1
O
C O2Et
H Ar3
O
A r1 2 3 =
1
1
1
A lky la tio n + K n o e ve n a g e l co n d e n sa tio n
K n o e ve n a g e l co n d e n sa tio n + N a za ro v cyc liza tio n
M ich a e l a d d it io n + K n o e ve n a g e l co n d e n sa tio n (o n e -p o t)
2
3
4
1
1 2
The spectral characteristics of the obtained photochromic compounds as well as some features of
their preparation methods will be also discussed
Acknowledgments
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871)
References
[1] M Irie Chem Rev 2000 100 1685
201
P90
NEW PHOTOINDUCED REARRANGEMENT OF DIARYLETHENES
AG Lvov1 AM Kavun
2 VZ Shirinian
1 VV Kachala
1 MM Krayushkin
1
1 - ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
2 - Higher Chemical College DI Mendeleev University of Chemical Technology of Russia
Moscow Russia
Diarylethenes (stilbenes) are one of the most reactive systems in photochemistry Their cistrans
isomerization [2+2] cycloaddition and photocyclization reactions are widely known Among them
the photocyclization of diarylethenes is a subject of long standing interest This process proceeds in
accordance with the Woodward-Hoffmann rule by conrotatory 6π-electrocyclization mechanism of
the cis-form of stilbenes I leading to the formation of the thermodynamically less stable isomer
4a4b-dihydrophenanthrene II which is used in different transformations depending upon the
structure nature and on the reaction conditions including photochromic switching and the synthesis
of polyarenes
X X
R3
R4
R1
R2
X X
R3
R4
R1
R2
I I
X C H = C H O N S
h
I
N e w p ro d u c ts
h
In a continuation of our studies on the photochromic properties of diarylethenes we have found a
new skeletal rearrangement resulting in the formation of polycyclic aromatic systems [1] It was
found that the photoreaction of 12-diarylethenes 1 comprising oxazole and phenyl rings under UV
light yields to amido-substituted polyarenes 3 with high efficiency
O
N
M e A r
H
O
N
M e A r
H
H
N
M e
O
A r
h (3 6 5 n m )
3 (4 5 -8 0 )1 2
C H C l3 0 1 M
The synthetic features and possible mechanism of the new photorearrangement will be discussed
Acknowledgments
This work was financial supported by Russian Foundation for Basic Research (Grant 14-03-31871)
References
[1] A G Lvov V Z Shirinian V V Kachala A M Kavun I V Zavarzin M M Krayushkin
Org Lett 2014 accepted
202
P91
FRIEDEL-CRAFTS ALKYLATION OF FURANS WITH BENZYL
ALCOHOLS CATALYZED BY COPPER(II) SALTS
AS Makarov MG Uchuskin AV Butin
Perm State University Department of Chemistry Perm Russia
Friedel-Crafts reaction is known to be one of the most powerful tool for introduction of variety of
alkyl groups into furan ring however the use of strong Bronsted acids or hard Lewis acids leads
often to partial destruction of furan substrates due to their acidophobic nature Nevetheless
utilization of π-activated alcohols under mild catalytic conditions allows for products to be isolated
in reasonable yields [1] Various expensive Lewis acids are usually used for activation of alcohols
[2 3] Although several benzyl-substituted furans were synthesized by these procedures in
moderate to excellent yields the substrate scope has not been explored adequately Thus the
development of a general catalytic procedure for alkylation of furans with benzyl alcohols
employing inexpensive catalysts remains an important challenge
Recently we reported a copper vitriol-catalyzed domino-reaction of o-aminobenzyl alcohols with
different furfurylamines which provides a simple route to 2-acylvinyl-substituted indoles [4] Our
continuing interest in C-C bond forming reactions led us to examine other copper(II) salts in the
alkylation step We found that some copper(II) salts might be used as catalysts for the alkylation of
furans 2 with substituted benzyl alcohols 1 Resulting benzyl furans 3 were isolated in good to
excellent yields under optimized reaction conditions
O H
R1
R2
OR
3
R1
O
R3
R2
C u II
R 1 = H A lk A lk O H a l
R 2 = A lk A r
R 3 = A lk A r
+
1 2 3
Herein we report a novel copper(II)-catalyzed Friedel-Crafts alkylation protocol allowing for
synthesis of a large variety of substituted benzylfurans
We thank Russian Foundation for Basic Research (RFBR grant 14-03-31278) and Ministry of
Education and Science of Russian Federation (42462014K) for the financial support
1 M Bandini M Tragni Org Biomol Chem 2009 7 p 1501
2 S Roy S Podder J Choudhury J Chem Sci2008 120 p 429
3 M Noji et al Synthesis 2008 23 p 3835
4 Uchuskin M G Molodtsova N V Lysenko S A Strelnikov V N Trushkov I V Butin A V
Eur J Org Chem 2014 p 2508
203
P92
CATALYTIC CROSS CYCLOMAGNESIATION OF 12-DIENES IN THE
SYNTHESIS OF ZZ-DIENOIC ALCOHOLS AND 5Z9Z-DIENOIC ACIDS
VA Dyakonov AA Makarov EKh Makarova UM Dzhemilev
Institute of Petrochemistry and Catalysis Russian Academy of Sciences Laboratory Catalytic
Synthesys Ufa Russia
Intermolecular cross cyclomagnesiation of terminal aliphatic 1 and oxygenated 12-dienes 2 was
performed for the first time by means of Grignard reagents and Cp2TiCl2 to give after acid
hydrolysis of the reaction mixture oxygenated hydrocarbons containing a 1Z5Z-diene moiety 4 in
the molecule in up to 94 yields
The developed reaction formed the basis for elaboration of a new effective method for the synthesis
of 5Z9Z-dienoic acids in view of the published data concerning a broad range of biological
activities of these compounds including antimalarial antimicrobial antitumor and antiviral
activities Along with low toxicity of С20-С30 acids this makes these compounds fairly attractive
as a base for development of modern medical drugs
We suggested that the developed approach to the synthesis of oxygenated dienes by means of cross
cyclomagnesiation could serve as the basis for a new approach to the synthesis of 5Z9Z-dienoic
acids
Thus according to the scheme we proposed the first step is Cp2TiCl2-catalyzed cross
cyclomagnesiation of terminal aliphatic allenes 6 with the tetrahydropyran ether of hepta-56-dien-
1-ol 5 by EtMgBr under conditions developed above The subsequent hydrolysis of the reaction
mixture results in oxygenated dienes 7 The removal of pyranyl protection and oxidation of the
5Z9Z-diene alcohols 8 thus formed leads to target 5Z9Z-dienoic acids 9 in 45-48 yields and 98
stereoselectivity
This work was performed under financial support from the Russian Science Fondation (Grant 14-
13-00263)
204
P93
CYCLOALUMINATION OF ALKENES AND ALKYNES IN THE
SYNTHESIS OF PHOSPHOLANES AND PHOSPHOLENES
AL Makhamatkhanova VA Dyakonov RA Agliullina UM Dzhemilev
Institute of Petrochemistry and Catalysis of RAS Laboratory of catalytic synthesis Ufa Russia
Aluminacyclopentanes 1 and aluminacyclopentenes 2 generated in situ from the cycloalumination
reaction of olefins and acetylenes with Et3Al catalyzed by 5 mol Cp2ZrCl2 (toluene ~ 20 оС 12
h) were found to undergo the phenyl dichlorophosphine-mediated exchange reaction between
aluminum and phosphorus giving rise to practically important 3-alkyl(phenyl)-substituted 1-phenyl
phospholanes 3 and 23-dialkyl-substituted 1-phenyl 2-phospholenes 4 in high yields after
hydrolysis of the reaction mixture The resultant phosphanes 3 and 4 corresponding readily form
oxides and sulfides on treatment with hydrogen peroxide in chloroform or elemental sulfur
The structure of the synthesized compounds has been established by one- (1H
13C Dept 135) and
two-dimensional (HSQC HMBC и HH COSY) NMR techniques The effect of the reagent ratio
duration and temperature of the reaction on the yield of the desired phosphacarbocycles is
discussed
This work was supported financially by the Russian Foundation for Basic Research (Grants 12-03-
31259 14-03-31084) and NSh-213620143
1 UM Dzhemilev AG Ibragimov AP Zolotarev RR Muslukhov and GA Tolstikov Bull
Acad Sci USSR Div Chem Sci 1989 38 194
2 VA Drsquoyakonov Dzhemilev Reactions in Organic and Organometallic Synthesis NOVA Sci
Publ New-York 2010 96 p
3 UM Dzhemilev Mendeleev Commun 2008 18 1
205
P94
PIONEERING IONIC LIQUID-PROMOTED NUCLEOPHILIC AROMATIC
CINE-SUBSTITUTION OF HYDROGEN
NN Makhova MA Epishina AS Kulikov
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Rissia
The nucleophilic substitution of hydrogen in electron-deficient arenes (SNH) is a general process of
great practical value1 Over the past decades several variants of SN
H processes were opened and
investigated in details the oxidative nucleophilic substitution of hydrogen the vicarious
nucleophilic substitution (VNS) the cine- and tele-substitution the ANRORC substitution The
cine-substitution is a process in the course of which the entering nucleophilic group takes up a
position adjacent to that occupied by the leaving group One of the cine-substitution example is
conversion of substituted nitrobenzenes into benzoic acids under the action of KCN excess in
aqueous EtOH (the von Richter reaction) The carboxylic group always enters in orto-position to
leaving nitro group This transformation occurs by heating of different substituted nitrobenzenes in
the presence of the KCN excess in refluxing 48 aqueous ethanol during 48-50 h or in a sealed
tube at 150-180 oC during 1-2 h Yields of final benzoic acids were as a rule low or the expected
benzoic acids were not generated at all In addition the reaction is accompanied by a large amount
of acidic tar apparently polymeric by nature
In this work we have found that transformation of electron-deficient arenes (nitrobenzene 1a and 4-
Cl- (1b) 4-Br- (1c) 4-F- (1d) 4-I- (1e) and 4-MeO- (1f) nitrobenzenes) to corresponding benzoic
acids 2a-f under the action of the KCN excess in aqueous EtOH (von Richter reaction) was
promoted by ionic liquids (ILs) Our research team has great expertise and successful experience in
the performance of various reactions in Ils2
Screening of the conditions for the synthesis of m-
chlorobenzoic acid 2b from of 4- chloronitrobenzene 1b shown that the optimum molar ratio ionic
liquid [bmim]BF41b is 1751 or 175 mol of [bmim]BF4 All tested cases of the von Richter
reaction of nitroarenes 1a-f in the presence of ionic liquids proved successful and produced those
results which were not possible in before described conditions The influence of nature of the
substituents in nitrobenzenes on the reaction results was revealed ndash the stronger electron-donating
properties of substituents the slower the reaction This finding is the first case of the nucleophilic
aromatic cine-substitution of hydrogen promoted by ionic liquids
1 F Terrier Modern Nucleophilic Aromatic Substitution Wiley-VCH Weinheim 2013 488 pp
2 N N Makhova M I Pleshchev M A Epishina AS Kulikov ldquoSynthesis and transformation
of nitrogen-containing heterocycles in iionic liquidsrdquo Khim Heterocycl Soedin 2014 (5) 690-
703 (in Russian)
This work was supported by Russian Foundation for basic Research (grant 13-03-00153a)
206
P95
REACTIONS OF ADDITION OF THIOPHENOL TO PROPARGYL
SYSTEMS AND BIOCHEMICAL ACTIVITY OF OBTAINED COMPOUNDS
VM Farzaliyev PSh Mammadova ER Babayev HSh Aliyeva IM Eyvazova
AMGuliyev Institute of Chemistry of Additives of Azerbaijan National Academy of Sciences
(ANAS) Beyuk-Shor Str Block 2062 AZ1029 Baku Azerbaijan
High reactivity of thiols allows to easily conduct thiylling of multiple carbon-carbon bonds These
reactions are convenient methods of synthesis of the various derivatives possessing practically
interesting properties and also they can be considered as modelling ones for some physiologically
important processes occurring in live organisms
The research of reactions of nucleophylic radical and non-catalytic addition of aromatic tiols to
acetylene alcohols with account of structure properties of initial reagents gives an opportunity to
establish theoretic bases at purposeful synthesis of practically interesting compounds
We synthesized phenyl thioalkenols at the condition of nucleophylic radical and non-catalytic
addition and carried out comparative analysis of results obtained for all three types of reactions
taking into account structure of initial acetylene alcohols (propargyl methyl - dimethyl- and
methylethylethynilcarbinols) and thiophenol The basic parameters such as molar rate of initial
reagents duration and temperature for these reactions remained to be unchanged
Isomer content and rate of cis- trans-conformers were established by H1 NMR-spectra
Identification of α and β- isomers was carried out on resonance signals of =CH2- and CH=CH-
groups but rate of cis- trans-conformers was determined by analysis of results of integration with
account of constant of spin-spin interaction H1
NМR-research of reactionary mixture was carried
out till its separation to exclude the influence of isomer processes as far as possible Part of β-
isomer (cis- + trans-) was used as quality measure of influence of factors of initial reagents structure
on regioselectivity Under these conditions the part of cis- trans-conformers was the measure of
influence on stereo specificity
Composition structure and yield of products of reaction of nucleophylic radical and non-catalytic
addition of thiophenol to propargyl systems are determined by electronic (to a lesser degree) and
steric factors of the structure of the reacting compounds mainly acetylene ones The direction of
the attack (regiodirectivity) is controlled by space difficulties formed by both reagents at their
direct interaction but stereoselectivity depends on the steric factors of the structure mainly thiol
compounds
It has been shown that reaction of non-catalytic addition of arylthiols to propargyl systems is a
convenient and technologically accessible method for purposeful synthesis of arylthio - and
cyclohexylthioamines with high yields The reaction proceeds basically on nucleophylic
mechanism and with partial participation of thiyl radicals
There has been revealed high antimicrobial effectiveness of series of the synthesized sulphides in
lubricating oils fuels and cutting liquids
207
P96
AN EXPERIMENTAL APPROACH FOR THE ESTIMATION OF CRYSTAL
LATTICE ENERGY OF CO-CRYSTAL
AN Manin AP Voronin GL Perlovich
GA Krestov Institute of solution chemistry of the Russian academy of scienses Physical
Chemistry of Drugs department Ivanovo Russia
The creation of pharmaceutical co-crystals is an area of expanding growth These materials offer a
possible route for the modification of the physicochemical properties of APIs such as solubility
physical and mechanical properties thermodynamic stability etc without changing the
pharmacological activity The key design tool used to select a suitable compound (a co-crystal
former) for a given substance is the concept of supramolecular synthon [1] Several types of
supramolecular synthon are usually realized in two-component crystals and are characterized by
intermolecular hydrogen bonds (H-bonds) of different types and strengths The energy of these
interactions was evaluated in a number of papers [2] A lot less attention has been paid to the
quantitative description of the intermolecular interactions of homo- and heterodimers with the
neighbor molecules which play an important role in the successful co-crystal phase formation The
cumulative characteristic of the intermolecular (noncovalent) interactions in solids is the
sublimation enthalpy ΔHsub This value extrapolated to 0 K corresponds to the crystal lattice energy
Elatt Despite the active investigation of various physicochemical properties of co-crystals no papers
concerning co-crystal sublimation have been published until now
The aim of our study is to provide an experimental validation of the transpiration method for co-
crystal enthalpy of sublimation estimation The present research work considers the co-crystal of 2-
hydroxybenzamide (salicylamide A) with 4-acetamidobenzoic acid (acetamidobenzoic acid B)
This co-crystal is chosen for the following reasons (i) The acidminusamide heterosynthon is a persistent
H-bond motif in co-crystal structures (ii) Salicylamide is an active pharmaceutical ingredient while
acetamidobenzoic acid is safe for human consumption (iii) The thermodynamic functions of
sublimation for both components have been obtained by us earlier
A novel 11 co-crystal of salicylamide and 4-acetamidobenzoic acid was obtained by DSC
screening procedure as well as grinding (both neat and solvent-drop) and solvent evaporation
techniques A complete thermal analysis performed by DSC TG and hot stage microscopy
revealed that the co-crystal remains stable in its solid form until the melting point at 1824 degC
where it breaks down into components To determine the optimal conditions of single crystal
growth a triangle phase diagram for the object system with ethanol was built An X-ray diffraction
experiment with complete solving of the crystal structure was carried out for the co-crystal For the
first time in literature the sublimation thermodynamics of a multicomponent crystal was studied
experimentally by the transpiration method in a quasi-equilibrium mode A presumable mechanism
of the sublimation process was proposed with the heterodimer sublimating and eventually
dissipating into separate molecules
1 Desiraju G R Crystal Engineering From Molecule to Crystal J Am Chem Soc 2013 135
27 9952minus9967
2 Dunitz J D Gavezzotti A Supramolecular Synthons Validation and Ranking of
Intermolecular Interaction Energies Cryst Growth Des 2012 12 5873minus5877
This work was supported by the Russian Scientific Foundation (14-13-00640) We thank ldquothe
Upper Volga Region Centre of Physicochemical Researchrdquo for technical assistance with DSC and
XRPD experiments
208
P97
SELECTIVE C-H ALKENYLATION OF ARYL ETHERS AND
THIOETHERS IN MIXTURES
AN Marjanov1 KV Luzyanin
1 VP Ananikov
2
1 - Laboratory of Cluster Catalysis Saint Petersburg State University Universitetsky pr 26 Stary
Petergof 198504 Russia
2 - Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Leninsky Prospekt 47
Moscow 119991 Russia
Direct CndashH alkenylation of arenes assisted by the directing group represent one of the most atom-
economic approaches for the preparation of 12-disubstituted olefines1ndash5
While the alkenylation of
single starting material is a well-established strategy the selective alkenylation of a sole component
in a mixture of substrates is not known
S
N
2-(phenylthio)pyridine
S
N
2-(phenylsulfinyl)pyridine
O
O
N
2-phenoxypyridine benzyl(phenyl)sulfane
S
A B
Y
X
CO2Et
oxidant catalystsolvent D
Y
X
CO2Etmixtures of three or four substrates
single product
Scheme 1 Substrates used for this study (A) and a selective CH alkenylation of a mixture of
substrates with ethyl acrylate (B)
In pursuit of our studies we discovered that careful optimization of reaction conditions for CndashH
alkenylation eg solvent oxidant catalyst reaction temperature and ratio of substrates turns out
possible a selective alkenylation of a single component in a mixture of substrates Indeed several
different mixtures of aromatic ethers and thioethers were studied toward ethyl acrylate as
alkenylating source (Scheme 1) For each mixture only a sole component was a subject of
alkenylation while all others remained intact
In the current report we summarize obtained data regarding CndashH alkenylation of mixtures of ethers
and thioethers making a particular emphasis on improving the selectivity of the process and
understanding its driving forces
Acknowledgements This work has been partially supported by the Saint Petersburg State
University (research grant from Laboratory of Cluster Catalysis) and the Russian Fund for Basic
Research (grant 14-03-01005)
[1] Garciacutea-Rubia A Fernaacutendez-Ibaacutenez M A Goacutemez Arrayaacutes R Carretero J C Chem Eur J
2011 17 3567ndash3570 [2] Yu M Xie Y Xie C Zhang Y Org Lett 2012 14 2164ndash2167 [3]
Zhang X-S Zhu Q-L Zhang Y-F Li Y-B Shi Z-J Chem Eur J 2013 19 11898ndash11903
[4] Shi B-F Zhang Y-H Lam J K Wang D-H Yu J-Q J Am Chem Soc 2010 132 460ndash
461 [5] Liu B Jiang H-Z Shi B-F J Org Chem 2014 79 1521ndash1526
209
P98
SYNTHESIS AND CHARACTERIZATION OF DENDRIMERS DERIVED
FROM GLYCEROL
B Menot J Stopinski S Bouquillon
Institut de Chimie Moleculaire de Reims CNRS UMR 7312 Universite de Reims Champagne
Ardenne ndash UFR Sciences Exactes et Naturelles BP 1039 51687 Reims Cedex 2 France
For several years the laboratory was interested in the development of dendrimers using various
organic biosourced by-products the valuation of which being a real interest for our region One of
the first explored strategies was based on the decoration of nitrogen-based dendrimers
(commercially available polypropyleneimines (PPIs)) [1] with by-products of glycerin The toxicity
of these decorated nitrogenous-based dendrimers was evaluated [2] and their potential in catalysis
or in encapsulation demonstrated [13]
The synthetic strategy envisaged now by our team is to apply our decoration strategy to
commercially available polyamidoamines (PAMAMs) and to synthesize directly from the glycerin
new families of dendrimers The preparation of these last dendrimers directly from biobased
building blocks should improve their biodegradation and decrease their toxicity what is essential
for environmental applications
The objective of this presentation is to present our preliminary results concerning the development
of these new glycerodendrimers [4]
[1] S Balieu A El Zein R De Soussa F Jeacuterocircme A Tatiboueumlt S Gatard Y Pouilloux J
Barrault P Rollin S Bouquillon Adv Synth Catal 2010 352 1826
[2] S Balieu C Cadiou A Martinez J-M Nuzillard J-B Oudart F-X Maquart F Chuburu S
Bouquillon J Biomed Mater Res Part A 2013 101A (3) 613-621
[3] K Fhayli S Gatard A Mohamadou L Dupont S Bouquillon Inorg Chem Comm 2013
27 101
[4] B Menot J Stopinski A Martinez S Bouquillon publication in preparation
210
P99
PALLADIUM-CATALYZED HIGHLY REGIOSELECTIVE
PHOSPHONATION OF MESO-UNSUBSTITUTED PORPHYRINS VIA
C(sp2)-H FUNCTIONALIZATION
EA Mikhalitsyna ES Podyacheva IP Beletskaya
MSU Faculty of Chemistry Moscow Russia
Synthesis of new artificially modified porphyrins has received much attention as a very attractive
and promising goal for catalysis medicine light-absorbing materials mimicking the antenna
complexes of photosynthetic system photovoltaics etc1 In our work we are focused on the
development and optimization of high regioselective C-H phosphonation of porphyrins and their
metal complexes in meso-position via oxidative Pd(II)-catalyzed dehydrogenative cross-coupling
(CDC) Surprisingly to the best of our knowledge there are very few catalytic examples regarding
the C(sp2)ndashP bond formation through direct phosphonation of the CndashH bond with phosphite ester
including a limited class of compounds with acid C-H bond such as coumarins azoles terminal
alkynes and α‑ amino ketones2-5
We herein report the first example of the catalytically oxidative
phosphonation of meso-unsubstituted porphyrins which has attracted great attention for excellent
atom economy and an enviromentally friendly approach in opposite to classical tremendous
multistep synthesis6
To study the influence of structural factors on the reactivity of porphyrin substrates the target series
of meso- tris- di- and mono-mesityl substituted porphyrins and their Ni(II) and Zn(II) metal
complexes were synthesized by condensation of corresponding dipyrrylmethanes with
mesitylaldehyde in the presence of an acid catalysts and oxidant7 Pd(II)-catalyzed C-H
posphonation of Ni(II) 5-mesitylporphyrin (NiPMes) was successfully carried out with 40 mol
Pd(OAc)2 as catalyst 12 eq of 44rsquo-bipyridine as ligand 6 eq of K2S2O8 as oxidant and excess of
diethyl phosphite in refluxed dioxane under air atmosphere during 24 hours (Fig 1) Target mono-
phosphotated product were obtained and separated by column chromatography in good 80 yield
along with 14 of bis-phosphonated product The same conditions were used for phosphorylation
of bis-510-dimesityl and tris-51015-trimesitylporphyrins to prepare in 42 and 29 mono- and
diphosphonated porphyrins correspondingly
Fig 1 Pd-catalyzed C-H phosphonation of 5-mesitylporphyrin
1 J Mack Z Shen N Kobayashi In Handbook of Porphyrin Science Kadish K M Smith K M Guilard R Eds
World Scientific Publishing Singapore 2012 Vol 23 pp 281minus373
2 X Mi M Huang J Zhang Ch Wang and Y Wu Organic Letters 2013 15 pp 6266ndash6269
3 Ch Hou Yu Ren R Lang X Hu Ch Xia and F Li Chem Commun 2012 48 pp 5181ndash5183
4 Y Gao G Wang L Chen P Xu Y Zhao Y Zhou and L-B Han J Am Chem Soc 2009 131 7956-7957
5 B Yang T-T Yang X-A Li J-J Wang and S-D Yang Org Lett 2013 15 19 5024ndash5027
6 Yu Y Enakieva A G Bessmertnykh Yu G Gorbunova Ch Stern Y Rousselin A Y Tsivadze and R Guilard
Organic Letters 2009 17 pp 3842-3845
7 Ch Bruumlckner J J Posakony C K Johnson R W Boyle B R James and D Dolphin J Porphyrins
Phthalocyanines 1998 2 pp 455ndash465
211
P100
SYNTHESIS AND REACTIVITY OF 7-AMINO-4-OXO-3-R-8-Rrsquo-6H-
PYRAZOLO[51-C][124]TRIAZINES
LM Mironovich DV Shcherbinin AY Podolnikova
Southwest State University Basic Chemistry and Chemical Technology Kursk Russia
Reactivity of the 124-triazine derivatives containing pyrazole ring in the structure is now
intensively studied 7-Amino-4-oxo-3-R-8-Rrsquo-6H-pyrazolo[51-c][124]triazines (23) has been
synthesised by refluxing compound (1) with malononitrile and ethyl cyanoacetate in the medium
pyridine [1]
Boiling of compound (2) with KOH in the alcoholic medium has led to hydrolysis with isolation of
compound (4) it was treated with HCl and received pyrazolo[51-c][124]triazine-8-carboxylic acid
(5) Decarboxylation at high temperatures leads to isolation of compound (6) Pyrazolo[51-
c][124]triazine-8-carbohydrazide (7) obtained by boiling compound (2) with N2H4 in the alcoholic
medium
Refluxing of compound (3) in the alkaline medium has led to carbamide (8)
Boiling of compound (8) with formic acid has led to pyrimido[4rsquo5rsquo34]pyrazolo[51-
c][124]triazines (10) The structure of compound (10) was determined by X-ray crystallography
For fant of reflux P2S5 in pyridine with compound (10) leads to 411-dithioxo-3-R-6H10H-
pyrimido[4rsquo5rsquo34]pyrazolo[51-c][124]triazine (11) and 11-oxo-4-thioxo-3-R-6H10H-
pyrimido[4rsquo5rsquo34]pyrazolo[51-c][124]triazine (12) N-(3-tert-butyl-48-dithioxopyrazolo[51-
c][124]triazin-7-yl)аmid metadithiophosphorous acid (9) (348 [M+]) was received from the
responding compounds (3)
The structures of the synthesized compounds are confirmed with spectral methods (IR H1-NMR-
mass spectra) and elemental analysis data
Compounds show weak antimicrobial activity
[1] Mironovich LM and Kostina MV Russian Journal of Organic Chemistry 2011 vol 47
12 P 1917
212
P101
HYBRID MATERIALS BASED ON COPPER AND PALLADIUM
COMPLEXES OF (110-PHENANTHROLYL)PHOSPHONATES FOR
CATALYSIS
AYu Mitrofanov1 AG Bessmertnykh-Lemeune
2 R Guilard
2 NS Goulioukina
1 IP
Beletskaya1
1 - AN Frumkin Institute of Physical Chemistry and Electrochemistry of RAS 31-4 Leninskiy p
Moscow 119071 Russia
2 - Institut de Chimie Moleculaire de Universite de Bourgogne (ICMUB) UMR CNRS 6302 9
avenue A Savary 21078 Dijon Cedex France
Considerable attention has been attached recently to the immobilization of transition metal
complexes onto solid supports to prepare advanced catalytic systems [1]
Using this approach it is
expected to increase catalyst stability and allow for catalyst recycling and product separation
Organophosphonates are of interest for this field due to their simple synthesis and high reactivity
towards various metal salts and alkoxides In fact different ligands can be easily decorated by the
phosphonate group for immobilization onto thermally and mechanically stable metal oxide
matrices Herein we describe the results of our studies on the functionalization of titania by
copper(I) and palladium(II) complexes with (110-phenanthrolyl)phosphonates (Pphen) recently
described by us (Figure)[2]
Figure Copper(I) and palladium(II) complexes with Pphen
The covalent grafting of the complexes was performed according to two routes The first one so-
called lsquolsquoone-potrsquorsquo synthesis involves a co-condensation step between a complex with an inorganic
precursor (titanium isopropoxide) according to the sol-gel technique In the second one so-called
lsquolsquopost-functionalizationrsquorsquo а chemical surface modification of a preformed mesoporous titanium(IV)
dioxide (SBET = 650 m2g) through chemical bonds between the hydroxyl groups covering the pore
surface and complexes is used The structural and textural properties of these hybrid materials will
be presented and explained based on a solution behavior of the studied complexes High catalytic
activity of newly synthesized hybrid materials in the palladium-free Sonogashira reaction the
copper-catalyzed boration of alkynes and Suzuki reaction are reported and examples of catalyst
recycling are given
Acknowledgements This work was carried out in the frame of French-Russian Laboratory
ldquoLAMREMrdquo of CNRS and RAS and supported by Russian Foundation for Basic Research (grant
12-03-93114)
[1] Suib S L New and Future Developments in Catalysis Elsevier Amsterdam 2013
[2] (a) Mitrofanov A Yu Bessmertnykh-Lemeune A Stern C Guilard R Gulyukina N S
Beletskaya I P Synthesis 2012 44 3805 (b) Mitrofanov A Yu Manowong M Rousselin
Y Brandes S Guilard R Bessmertnykh-Lemeune A Chen P Kadish K M
Goulioukina N Beletskaya I Eur J Inorg Chem 2014 DOI101002ejic201402161
213
P102
SYNTHESES STABILITIES AND REACTIVITIES OF
ALKYNYL(ARYL)IODONIUM SALTS
WJ Moran
University of Huddersfield Department of Chemistry Huddersfield UK
Iodonium salts are increasingly popular reagents in organic synthesis because of the range of useful
reactivities that they exhibit1 The most investigated iodonium salts are the diaryliodonium salts
which can in principal donate either of their aryl groups in reactions with nucleophiles (Scheme
1)2 In contrast alkynyl(aryl)- and alkenyl(aryl)iodonium salts only donate the alkyne or alkenyl
groups respectively This means that the aryl iodide group is essentially a spectator group in these
two types of iodonium salts However the effect of changing this spectator group on the reactivity
of these salts has not been studied3
Scheme 1 General reactivities of iodonium salts with nucleophiles highlighting the ldquospectatorrdquo role
of the aryl iodide in alkenyl- and alkynyl(aryl)iodonium salts
Our study on the preparation of a range of alkynyl(aryl)iodonium salts directly from terminal
alkynes and aryl iodides and the stabilities and reactivities of these salts will be discussed4
Surprisingly we found a marked increase in the stability and reactivity of iodonium salts derived
from 2-iodoanisole (Scheme 2) I will also present our results on generating alkynyl(aryl)iodonium
salts from alkynylsilanes and reacting them directly resulting in yield augmentations of up to 50
compared to the iodobenzene parent
Scheme 2 Direct syntheses of alkynyl(aryl)iodonium salts and the effect of the aryl iodide
substituents on stabilities and reaction yields 1 For reviews of iodonium salts in organic synthesis see a) M S Yusubov A V Maskaev V V
Zhdankin Arkivoc 2011 i 370 b) E A Merritt B Olofsson Angew Chem Int Ed 2009 48 9052 c)
T Okuyama Acc Chem Res 2002 35 12
2 M Fujita E Mishima T Okuyama J Phys Org Chem 2007 20 241
3 Selected examples of reactions with alkynyl(phenyl)iodonium salts a) B L Williamson P J Stang A
M Arif J Am Chem Soc 1993 115 2590 b) B L Williamson R R Tywinski P J Stang J Am
Chem Soc 1994 116 93 c) M Ochiai K Miyamoto T Suefuji S Sakamoto K Yamaguchi M
Shiro Angew Chem Int Ed 2003 42 2191 examples of reactions with alkenyl(phenyl)iodonium salts
d) M G Suero E D Bayle B S L Collins M J Gaunt J Am Chem Soc 2013 135 5332 e) T
Okuyama M Fujita Acc Chem Res 2005 38 679
4 D J Hamnett W J Moran manuscript submitted for publication
214
P103
MATHEMATICAL MODELING OF DYNAMICS OF PHOTOCHEMICAL
REACTIONS AT THE QUANTUM AND THE CLASSICAL DESCRIPTION
OF THE RADIATION FIELD
VA Morozov ND Chuvylkin EA Smolenskii
N D Zelinsky institute of organic chemistry Leninsky prospekt 47 119991 Moscow Russia
Are examples of differences between the results of using two methods of mathematical modeling of
dynamics of populations of the states of the molecule in photochemical reactions The first method
is based on the solutions of the Schrodinger equation for the probability amplitudes of the
population of states of the molecule and the radiation field is described by quantum theory When
using a three-level model of the molecule these solutions are obtained analytically The second
method is based on numerical solutions of the equations for the density matrix elements of the
molecule interacting with the classically described irradiation and phenomenological decay of
excited states of molecules The differences formalisms used methods and an underlying
conceptions of the physical sense of the light transformation by molecules in photochemical
reactions are discussed
215
P104
SYNTHESIS OF SPIROCYCLOPROPYL MALONYL PEROXIDE FROM
CYCLOPROPYL MALONIC ESTER
OM Mulina VA Vill AO Terentiev
ND Zelinsky Institute of Organic Chemistry of Russian Academy of Sciences Laboratory for
Studies of Homolytic Reactions Moscow Russia
Cyclic diacyl peroxides were in use in oxidation reactions in the 1950-70s [1] At the present time
great attention is attracted to these compounds [2] An unique property of such spirocyclic
diacylperoxides as malonyl and phtaloyl ones is their capability to oxidate unsaturated compounds
without any catalysts alternatively to their linear analogues for example commercially available
benzoylperoxide and succinylperoxide and widespread peroxy cycles ozonides and tetraoxanes
Among malonyl peroxides a spirocyclopropyl malonyl peroxide is the activest and the most
frequently used oxidant It has the lowest molecular weight among familiar malonyl peroxides [2a]
and this fact makes the oxidation process more atom-efficient
The main procedure of synthesis of spirocyclopropyl malonyl peroxide 2 is the reaction of
spirocyclopropyl malonic acid with 90-98 hydrogen peroxide [3] or hygrogen peroxide and urea
hydrogen peroxide [2a] in the presence of methanesulfonic acid (Scheme 1)
In the present work we succeeded in synthesis of peroxide 2 in the reaction between
spirocyclopropyl malonic peroxide 1 which can be easily synthesised by alkylation of diethyl
malonic ester with 12-dichlorethane in high yields 85-88 and hygrogen peroxide and urea
hydrogen peroxide in the presence of methanesulfonic acid
This method makes the synthesis of spirocyclopropyl malonyl peroxide 2 dramatically easier
because it excludes come chemical and procedural steps
1 (a) W Adam J W Diehl J Chem Soc Chem Commun 1972 13 797-798 (b) C L Perrin
T Arrhenius J Am Chem Soc 1978 100 5249-5251
2 (a) J C Griffith K M Jones S Picon M J Rawling B M Kariuki M Campbell N C O
Tomkinson J Am Chem Soc 2010 132 14409-14411 (b) M Schwarz O Reiser Angew
Chem Int Ed 2011 50 10495-10497 (c) C Yuan A Axelrod M Varela L Danysh D
Siegel Tetrahedron Lett 2011 52 2540-2542
3 (a) W Adam R Rucktaumlschel J Am Chem Soc 1971 93 557-559 (b) M J Darmon G B
Schuster J Org Chem 1982 47 4658-4664
216
P105
HYPOTHETICAL REACTION MECHANISM OF H2-ASSISTED N-C6H14-
DENOX OVER AgAl2O3 CATALYSTS
AI Mytareva NA Sadokhina GN Baeva AYu Stakheev
ND Zelinsky Institute of Organic Chemistry Moscow Russia
Since Satokawa et al [1] discovered that the low temperature activity of AgAl2O3 in HC-SCR of
NOx can be boosted by addition of small amounts of H2 the nature of ldquohydrogen effectrdquo has been
studied intensely However the mechanism of H2-assisted HC-SCR of NOx is still debated and
several solutions have been proposed One of the possible pathways involves H2-promoted
formation of NO3oline surface species followed by their transformation to reactive NO2oline species which
further react with activated HCs In the present study in order to evaluate possible contribution of
this pathway into overall H2-assisted HC-SCR over AgAl2O3 we compared the rate of H2-assisted
C6H14 DeNOx in steady-state and the rate of NO3olinesurf reduction by C6H14 in the presence and the
absence of H2
It was repeatedly shown by FTIR and TPD that addition of H2 into reaction mixture results in the
intensive formation of NO3olinesurf located on Ag species and Al2O3 surface This process is very fast
and leads to the complete removal of NOx from the reaction mixture until saturation of the catalyst
surface is attained Surface reaction of NO3olinesurf species with the feed containing 1000 ppm C6H14
revealed their inertness with respect to HC reductant On the other hand surface reaction with NO or
H2 leads to NO3olinesurf rarr NO2olinesurf transformation as evidenced by intensive NO2 evolution and in situ
XPS data It should be noted that NO was found to be more effective in NO3olinesurf rarr NO2olinesurf
transformation as compared to H2 particularly at the reaction temperature below ~ 180degC
Transformation of NO3olinesurf into NO2olinesurf greatly enhances reactivity of surface N-containing
species and NO2olinesurf species are rapidly reduced into N2 in the course of the surface reaction with
300 ppm C6H14 + 1000 ppm H2 It was found that the rate of NO3olinesurf reduction by hydrocarbons in
the presence of H2 is identical to the rate of H2-HC-SCR of NOx in steady state This observation
suggests significant contribution of NO3olinesurf reduction in the rate of the overall HC-SCR mechanism
at 150-300 degC These results appear to be in a good agreement with the literature data on the
transient measurements of H2-assisted DeNOx over AgAl2O3 [2-3]
References
[1] S Satokawa Chem Lett 2000 29 294
[2] JP Breen R Burch and CJ Hill Catal Today 2009 145 34
[3] S Chansai R Burch Ch Hardacre J Breen and FJ Meunier J Catal 2010 276 49
217
P106
DEPENDENCE OF THE SPECIFIC ACTIVITY ON THE PLATINUM
PARTICLE SIZE IN THE DEEP OXIDATION OF C1 - C6 NORMAL
ALKANES
AM Batkin1 AYu Stakheev
1 IE Beck
2 NS Teleguina
1 GO Bragina
1 VI Zaikovsky
2 YuV
Larichev2 VI Bukhtiyarov
2
1 - ND Zelinsky Institute of Organic Chemistry Moscow Russia
2 - Boreskov Institute of Catalysis SB RAS Novosibirsk Russia
The deep oxidation of volatile organic compounds (VOCs) over supported catalysts based on noble
metals (Pt Pd) is among the main exhaust gas aftertreatment technology for mobile machinery and
stationary applications One of the most important factors influencing the efficiency of noble metal
catalyst is the size of metal particles High Pt dispersion improves utilization of noble metal since
increases the fraction of atoms accessible for a reaction On the other hand very small metal
particles may be ineffective in the reactions requiring multi-atomic surface active sites (structure-
sensitive reactions) The influence of the metal particle size on the total and specific catalytic
activity (SCA or atomic activity) in deep oxidation was extensively studied A comparison between
experimental data obtained by independent authors allowed us to suppose that the structural
sensitivity of deep oxidation and the size effect of the platinum particles on the specific catalytic
activity can also be dependent on the structure (first of all on the size) of the hydrocarbon
molecule
In this study we compared the effect of Pt particle size on the activity in catalytic combustion of
normal alkanes with different hydrocarbon chain length (C1 ndash C6) over a series of 08 PtAl2O3
with different average Pt particle sizes ranging from 1 to 12 nm
It was established that the range in which specific catalytic activity changes depends substantially
on the carbon chain length of the n-alkane In the oxidation of CH4 or С2H6 atomic activity
increases approximately 2ndash 3 times as the Pt particle size changes from 1 to 11 nm In propane
oxidation SCA increases approximately by a factor of 5ndash6 whereas in the oxidation of n-C4H10 and
n-C6H14 the specific activity increases 20 and 25 times respectively Thus the structural sensitivity
of the deep oxidation of n-alkanes increases with an increase in the size of the hydrocarbon
molecule being oxidized
It was found that the catalysts with the maximum degree of dispersion of platinum (dPt = 1ndash2 nm)
exhibit the highest total activity in the oxidation of small molecules The catalysts consisting of
larger Pt particles (3ndash6 nm) are most active in the oxidation of longer n-butane and n-hexane
molecules whereas the activity of the finer catalysts is substantially lower
Acknowledgement Financial support by RFBR grant 12-03-01104-a is gratefully acknowledged
218
P107
COMPOSITE CATALYSTS [Fe-BETA + REDOX] FOR COMBINING
CATALYTIC PROCESSES 1) NH3-SCR AND NH3-SLIP REMOVAL
2) NO TO NO2 OXIDATION AND FAST SCR
AI Mytareva1 GN Baeva
1 DA Bokarev
1 AYu Stakheev
1 P Selvam
2
1 - ND Zelinsky Institute of Organic Chemistry Moscow Russia
2 - Indian Institute of Technology-Madras National Centre for Catalysis Research and Department
of Chemistry Chennai India
Combining several catalytic processes over single catalyst is the general trend in modern
heterogeneous catalysis We explored this approach to develop catalytic systems for environmental
protection ndash selective catalytic reduction of NOx by ammonia (NH3-SCR) NH3-SCR is of
theoretical and practical interest for abatement NOx emission from automotive (diesel engines) and
stationary (power plants) sources Recently NH3-SCR can be achieved by using catalytic systems
based on Fe-Beta or Cu-Beta However these catalysts have two main drawbacks 1) insufficient
NOx conversion at ldquocold-startrdquo condition (150-250ordmC) and 2) NH3-slip problem due to incomplete
conversion or exhaust temperature upswings We attempted to solve these problems by using
composite catalysts [Fe-Beta + RedOx] comprising NH3-SCR and RedOx functions
1 Combining NH3-SCR and NH3-slip removal
According to our recent results Fe(Mn)MCM-48 can be used as RedOx components due to high
activity in NH3 oxidation process Therefore composite catalyst was prepared by mechanical mixing
of Fe-Beta and Fe(Mn)MCM-48 components
It was shown that mechanical mixing of Fe-Beta with Fe(Mn)MCM-48 allowed us to combine
favorable NH3-SCR performance of Fe-Beta (1) and activity of Fe(Mn)MCM-48 in NH3
oxidation (2) in one catalytic brick
2 NO + 2 NH3 + frac12 O2 rarr 3 H2O + 2 N2 ndash over Fe-Beta (1)
4 NH3 + 3 O2 rarr 2 N2 + 6 H2O ndash over Fe(Mn)MCM-4 (2)
Varying the ratio of the components optimum SCR and NH3-slip removal performance of
composite catalyst can be achieved Moreover [Fe-Beta + Fe(Mn)MCM-48] demonstrates low N2O
emission
2 Combining NO oxidation and NH3-SCR
CeO2-ZrO2 demonstrates high activity in NO oxidation to NO2 Furthermore it was found that the
activity can be further boosted viz modification by manganese In this study MnCeO2-ZrO2 was
mixed with Fe-Beta for enhancing low-temperature NH3-SCR activity of zeolite component
It was found that mixing of zeolite and RedOx component leads to a significant increase in NOx
conversion at 150-250ordmC This synergistic effect can be attributed to combination of two processes
NO oxidation over MnCeO2-ZrO2 (3) followed by the Fast SCR (4) on Fe-Beta
2 NO + O2 rarr 2 NO2 ndash over MnCeO2-ZrO2 (3)
NO + NO2 + 2 NH3 rarr 3 H2O + 2 N2 ndash over Fe-Beta (4)
Acknowledgments
This work was supported by the Russian Foundation for Basic Research (Grant 13-03-
92711IND_a) and Department of Science and Technology New Delhi (Grant INTRUSRFBRP-
152)
A Mytareva is grateful to Haldor Topsoslashe AS for financial support in the framework of PhD
student support programme
219
P108
NON CATALYTIC EFFICIENT APPROACH TO SUBSTITUTED 2349-
TETRAHYDRO-1H-XANTHEN-1-ONES - A GROUP OF ORALLY ACTIVE
NEUROPEPTIDE Y Y5 RECEPTOR ANTAGONISTS FROM
SALICYLALDEHYDES AND DIMEDONE
RF Nasybullin OO Sokolova MN Elinson
ND Zelinsky Institute of Organic Chemistry Moscow Russia
Functionally substituted tetrahydro-1H-xanthen-1-ones have received considerable attention in the
field of medicinal chemistry due to their useful biological properties and applications [1] Recently
it has been found that tetrahydro-1H-xanthen-1-ones are orally active and selective Y5 antagonists
[2] Known methods for the synthesis of tetrahydro-1H-xanthen-1-ones have its merits and suffer
from disadvantages such as long reaction times moderate yields or complicated work-up
procedures Thus the development of an efficient and facile method for the synthesis of tetrahydro-
1H-xanthen-1-ones is in high demand
In the present study we report our results on thermally induced non catalytic transformation of
salicylaldehydes and dimedone into substituted tetrahydro-1H-xanthen-1-ones (Scheme 1) The
reaction is performed in ethanol under 3 min reflux Corresponding 9-(2-hydroxy-44-dimethyl-6-
oxo-1-cyclohexen-1-yl)-33-dimethyl-2349-tetrahydro-1H-xanthen-1-ones were formed in
excellent 85-95 yields
Scheme 1
In conclusion simple non catalytic system can produce under neutral conditions a very fast
(3 min) and selective transformation of salicylaldehydes and dimedone into tetrahydro-1H-xanthen-
1-ones ndashndash the orally active and selective Y5 antagonists and the promising heterocyclic compounds
for different biomedical applications The procedure utilizes simple equipment it is easily carried
out and is valuable from the viewpoint of environmentally benign diversity-oriented large-scale
processes
Acknowledgements
The authors gratefully acknowledge the financial support of the Russian Foundation for Basic
Research (Project No 14-03-31918)
References
1 H KWang S L Morris-Natschke K H Lee Med Res Rev 1997 17 367
2 S Mashiko A Ishihara H Iwaasa H Sano Z Oda J Ito M Yumoto M Okawa J Suzuki T
Fukuroda M Jitsuoka N R Morin D J MacNeil L H T Van der Ploeg M Ihara T
Fukami A Kanatani Endocrinology 2003 144 1793
220
P109
SOLUBILITY AND STRUCTURE OF CHITOSAN IN AQUEOUS MEDIA OF
VARIOUS ACIDITY MOLECULAR DYNAMIC STUDY
VS Naumov SK Ignatov AG Razuvaev AE Mochalova IA Glazova LA Smirnova
NI Lobachevsky State University of Nizhny Novgorod Russia
Polyaminoglucanes particularly chitosan (poly-14-(N-acetyl)-β-D-2-glucopyranoseamine) are
considered today as promising means for encapsulating the protein-contaning drugs ensuring their
transport inside an organism This task is however complicated by the lack of information about
the structure of the chitosan complexes in aqueous solutions their thermodynamic properties and
kinetics of complexation In particular the structure of chitosan chains in the aqueous solution
based on the data of electron microscopy was a subject of discussion [1] Data on the complexation
constants with various protein agents are virtually absent and the details of dissolution kinetics are
mostly studied on the basis of formal kinetic approach or without adrressing to the protonation
effects [23] In the present study we use the molecular dynamics (MD) simulations in order to
elucidate the details of nanocrystalline chitosan dissolution the influence of amino group
protonation and kinetics of its dissolution at various acidity of aqueous media The model system
was a chitosan nanocrystal surrounded by the water molecules (SPC water model) and counterions
(Cl-) compensating the protonated amino group charges The simulation box size was 124 x 117 x
208 nm (~302000 atoms in total ~100000 water molecules) The nanocrystal was consisted of 8
chains of 20 monomeric units (32 kDa per chain) The initial crystal structure was constructed on
the basis of XRD data [4] Some of amino groups were protonated in the crystal with the
protonation degree (PD) corresponded to the pH values from 53 to ~72 Calculations were
performed with GROMACS 461 using the force field GROMOS 53A6Carbo [5] specially
improved for better polyaminoglycane unit description Force field modification was perfromed on
the basis of quantum chemical calculations (HFSTO-3GB3PW916-31++G(dp)) Simulation
period was up to 10 ns with integration step of 1 fs in the NVT-ensemble at 300K controlled by the
Berendsen thermostat It was found that at the beginning of dissolution process the nanocrystal
undergoes the remarkable twist-like deformation resulting to the compact bunches of chitosan
chains Then at PDgt03 the bunches undergo slow dissociation which rate is determined by the
quantity of protonated amino groups The time-dependency of dissolution degree (measured as an
average distance between chains) is almost linear during 10 ns of simulations The dissolution rate
estimated as the time derivative of average distance between chains is also linearly dependent on
PD with threshold of dissolution about PD=03 (pH~68) which agrees well with available
experimental data The final structures of chitosan after 10 ns of dissolution in aqeous media of
various acidity are shown in Figure
[1] Pedroni VI Schulz PC Gschaider ME Andreucetti N Colloid Polym Sci 2003 282 100
[2] Franca EF Lins RD Freitas LCG Straatsma TP J Chem Theory Comput 2008 4 2141
[3] Franca EF Freitas LCG Lins RD Biopolymers 2011 95 448
[4] Yui T Imada K Okuyama KObata YSuzuki KOgawa K Macromolecules 1994 27 7601
[5] Hansen HS Huumlnenberger PH J Comput Chem 2011 32 998
This work was supported by the RFBR (Project No 14-03-00585 14-03-31981)
221
P110
THE STEAM OSMOTIC ENGINE WITH THE INCREASED EFF TO 50
PA Nazarov
Russian Chemical Technology University named after DI MendeleevChair of Processes and
devices of chemical technology positionMoscowRussia
The evolution of heat osmotic engine [2] on the prototype[1] is to increase the temperature
(T1=380С) of the left part of the circuit(fig1) the engine in changing the phase state of the water
from liquid to gas but also adding a second stage of desalination by electrodialysis
Due to the process steam or osmosis process of rapid diffusion of water vapor molecules through
the membrane into the liquid solution inside the reactor 3(fig1) osmosis increases the specific
power of the engine(Wkgengine) as well as its efficiency
Steam osmotic engine[2] repeats energy cycle thermal power plant but through a process of
steam osmosis and because of the lack of vapor condensation (in the cooler) its efficiency is much
higher
Ideal efficiency manual 2-nd Carnots theorem is(fig1)
EFF= [(T1ndashT2)T1]х100 = [(380Сndash20С)380С]х100=[(653ndash293)653]х100=55 (1)
Given the mechanical losses in the pump Pump1 2 formula for calculating the efficiency takes the
form
EFF мах =(NndashWpumps)∆Q= [(T1ndashT2)T1]ndashWpumps= [(P1osmosisndashP2reverse osmosis)P1osmosis]ndashWpumps (2)
Where N [W] - output power of osmotic (hydraulic) flow ∆Pturbines=2241at ΔQ [W] - The amount
of heat in heat generators 12 to keep the system in a given thermal regime (the left side of the
technological scheme T1=380C=653k right side T2=20C=293k) Wpumps [W] - power pumps12
Steady state operation of the scheme of steam osmotic engine T1=379-380C T2=20-40C
fig1
References
1 Patent of USA 4193267 on 18031980 Metod and apparatus for generating power utilizing
pressure-retarted osmosis Inventor Sydney Loeb the Bulletin 1877989 15021978
2 The application for the patent of the Russian Federation 2014108948 from 11032014
laquoMethod of reception of mechanical energy and the steam osmotic engine for its realisationraquo the
applicant and the legal owner Nazarov P A
222
P111
THE UNSATURATED CARBON-CARBON BOND HYDROGENATION IN
PRESENCE OF NANOPARTICLES OF THE Fe-Ni GROUP
DN Nebykov VM Mokhov YuV Popov
Volgograd State Technical University Chemical Technology Faculty Volgograd Russia
The hydrogenation of unsaturated substances and arenes is a widely used industrial process but it
proceeds in harsh conditions or requires using of expensive catalysts We discovered some methods
giving an ability to carry out the reduction of different substituted alkenes and arenes without using
of high temperatures and pressures or expensive materials by means of using ferrous cobalt or
nickel nanoparticles as catalysts
The advantage of methods is in combination of metal nanoparticles synthesis and organic substance
hydrogenation The nano-catalyst is formed from inexpensive metal salts by their reduction with
complex borohydrides or alumohydrides or by hydrazine hydrate in solutions in some cases
proceeds in situ hydrogenation of unsaturated bonds
The essential interest deserves a method of liquid phase alkenes hydrogenation with gaseous
hydrogen at atmospheric pressure which is a widely used and inexpensive industrial reagent Using
of simply obtained from accessible and inexpensive substances metal nanoparticles is able to
decrease the cost and energy losses comparing to traditional hydrogenation methods
The investigations showed an ability of the carbon-carbon unsaturated bond hydrogenation at very
smooth conditions - atmospheric pressure and near room temperatures Also was found that change
of hydrogenating agent catalyst and its preparing conditions makes possible to direct the process
selectivity and also to reduce some functional groups As starting materials for hydrogenation were
used different derivatives of norbornene styrene linear and cyclic alkenes heterocyclic
compounds
References
1 Colloid and nanodimensional catalysts in organic synthesis I Investigation of hydrogenation
selectivity of unsaturated compounds with hydrazine hydrate and aluminum hydride Popov
YuV Mokhov VM Nebykov DN Russian Journal of General Chemistry - 2014 - Vol 84
No 3 - C 444-448
2 Colloid and nanodimensional catalysts in organic synthesis II The hydrogenation of alkenes
with hydrogen at atmospheric pressure Popov YuV Mokhov VM Nebykov DN Russian
Journal of General Chemistry - 2014 - Vol 84 No 4 - C 622-628
3 Hydrogenation of unsaturated carboxylic acids Mohov VN Popov YV Nebykov DN
Izvestiya VolGTU Series ldquoChemsitry and technology of organoelemnt monomers and polymeric
materialsrdquo Iss 12 MezhvussbnauchstVolGTU ndash Volgograd 2014 N7 (134) ndash C 60-63
223
P112
SYNTHESIS AND INVESTIGATION OF FUNGICIDAL ACTIVITY OF 6-
BROMO-4-HYDROXY-2-PHENILINDOLE
OD Neverova MD Dutov SA Shevelev GV Bastrakova OV Serushkina KE Aisina SV
Popkov
N D Zelinsky institute of organic chemistry Leninsky prospekt 47 119991 Moscow Russia
Recently we showed high fungicidal activity of the 2-aryl-4-hydroxy-6-nitroindoles [1] The
presence of the nitro group in these compounds of course reduces their value as fungicides as in
the case of use as agricultural agents and in the case of drugs Therefore it is very important task to
replace the nitro group to an appropriate electronegative substituent as which by analogy with
Arbidol we have chosen a bromine atom Synthesis of the title compound (1) was carried out as
follows
It is shown that 6-bromo-4-hydroxy-2-phenylindole outperforms standard triadimefon by
fungitoxicity with respect to all the examined fitopatagence not inferior nitro analog
Compound Mycelium growth inhibition (С = 30 μg mL-1
)
Vi Rs Fo Fm Bs Ss
100 92 88 100 95 100
89 100 88 100 100 100
Triadimefon 42 66 60 79 71 47
The authors thank the Russian Foundation for Basic Research (Grant No 13-03-01276) for financial
support
[1] G V Kokurkina M D Dutov S A Shevelev S V Popkov A V Zakharov and V V
Poroikov European Journal of Medicinal Chemistry 2011 46 4374-4382
224
P113
THEORETICAL STUDY OF MULTISTEP MECHANISM OF THERMAL
FRAGMENTATION OF O-NITRO TOLUENE
EV Nikolaeva AG Shamov GM Khrapkovskii
Kazan National Research Technological University Catalisis Department Kazan Russia
A mechanism which is believed to be involved in thermodistruction of o-nitrotoluene (I) and other
nitroarenes bearing hydrogen-containing substituent in ortho-position to nitro group includes the
formation of its aci-form at the first step At the same time significant differences in activation
enthalpies ( H = Ea ndash RT) of thermodistruction of compound I were observed by different authors
Thus in the temperature interval 300-350оС H equals 1728 kJmol[4] 350-420
оС H =
2016 3 kJmol 797-907оС H = 2062 kJmol Results of theoretical investigation of the
thermodistruction mechanism of compound I can be presented as the following scheme
The data on relative enthalpies of formation of transition states of reactions ( Hf enthalpy of
formation of o-nitrotoluene was selected as zero) for this scheme provided in the literature suggest
that it should terminate at the limiting step of hydrogen atom transfer between two oxygens in the
group =N(O)OH (process III VI) Possibility of further reactions remained unclear The
investigation of the specified sequence of transformation of o-nitrotoluene by B3LYP6-
31+G(2dfp) demonstrated that this scheme can be realized if isomerization III IV proceeds as a
rotation of =N(O)OH around С=N bond For this process Hf equals 188 kJmol The limiting
steps are elimination of water (V VII) or hydroxyl radical (V VI) from 21-benzisoxazol-
2(3H)-ole (V) with barriers being equal 1930 and 2049 kJmol respectively That is at lower
temperatures a more probable would be the realization of the process V VII since for it Hf
correlates well with experimental estimation of 2016 3 kJmol At higher temperatures there is an
opportunity for elimination of OH from compound V (V VI) since for it Hf correlates well
with experimental estimation of 2062 kJmol In favor of this conclusion is the systematic character
of deviations (1-9 kJmol decrease) of calculated values of activation enthalpies of primary act and
specified steps from experimental data
1 VG Matveev VV Dubihin GM Nazin Izv Acd Nauk USSR Ser chem 2 474-476 (1978)
2 GMKhrapkovskii AGShamov EVNikolaeva DVChachkov RussChemRev 78 10 903-943
(2009)
3 Y Y Maksimov Zh Phys Chem XLIII 3 725-729 (1969)
4 TB Brill KJ James Chem Rev 93 2667-2692 (1993)
5 W Tsang D Robaugh WG Mallard J Phys Chem 90 5968-5973 (1986)
6 YV Ilrsquoichev J Wirz J Phys Chem A 104 7856-7870 (2000)
7 SC Chen SC Xu E Duau MC Lin J Chem Phys A 110 10130-10134 (2006)
8 G Fayet L Joubert P Rotureau C Adamo J Phys Chem A 113 13621-13627 (2009)
9 EV Nikolaeva DV Chachkov AG Shamov GM Khrapkovskii Vestnik NovGU 2 73 76-82 (2013)
225
P114
OPTICAL ACTIVE BIS-IMINE RHODIUM(I) COMPLEXES IN TRANSFER
HYDROGENATION OF PROCHIRAL C=O BONDS
LO Nindakova AV Khatashkeev NM Badyrova IA Ushakov EKh Sadykov
Irkutsk State Technical University Physical-technical Institute Irkutsk Russia
Rhodium (1+) complexes with bis-aldimine ligands on the basis of (RR)-12-cyclohexanediamine
(1) were tested in the asymmetric transfer hydrogenation of ketones and ketoacids with
isopropanol as hydrogen source under basic conditions The catalystsubstrate ratio was 1170-340
Ligands (1а-1с) were synthesized by the condensation reaction of diamine 1 with aldehides 2-
pyridinecarbaldehyde 2-quinolinecarbaldehyde and 2-thiophene-carbaldehyde following the
scheme
Rrsquo- =
Rhodium complexes were used as catalysts for this reaction it was confirmed by 1Н and
13С HMR
that this complexes were formed in situ from the reaction of [Rh(15-COD)Cl]2 and ligands 1a-1с
TOF and TON values are higher for ligands that synthesize from 2-pyridinecarbaldehyde (250 h-1
340) and from 2-quinolinecarbaldehyde (109 h-1
170) the lowest values were obtained for bis-
aldimine based on 2-thiophene-carbaldehyde (16 h-1
43) The excess formation of R-(+)-
enantiomer of 1-phenylethanol and R-(-)-methyl mandelate is observed for all Rhodium complexes
But the all used catalytic systems are slightly enantioselective (prior to 20 of ee) similar result
was obtained using Ir - and Ru -bis(oxazoline) catalytic system [1]
[1] Goumlmez M Jansat S Muller G Bonnet M C Breuzard J AJ Lemaire M J Organomet
Chem 2002 659 186-195
226
P115
STRUCTURAL ANALYSIS OF IODINE ADDUCTS WITH
HETEROAROMATIC N-OXIDES
VV Romanov1 YP Nizhnik
1 AV Ryzhakov
2 LL Rodina
3
1 - Petrozavodsk State University Petrozavodsk Russia
2 - Karelian Research Center RAS Petrozavodsk Russia
3 - St Petersburg State University St Petersburg Russia
Heteroaromatic N-oxides contain two potential donor centers capable to interact with Lewis acids
such as halogen bond donors -system of the aromatic rings and the oxygen atom of N-oxide
group According to the HSAB principle the iodine as a soft Lewis acid might interact on both
donor centers however the literature and our IR-spectroscopy data unambiguously indicate the
oxygen atom as a donor center
Yet a half-century ago T Kubota [1] questioned the exact geometry of iodine adducts of N-oxides
due to potentially different hybridization types of oxygen atom Actually owing to an ambivalent
character of the group NndashO in the heteroaromatic N-oxides the oxygen atomrsquos hybridization might
be characterized by the two extreme cases ndash sp3 or sp
2
Single X-ray data obtained by us for the adducts of iodine with pyridine 4-methylpyridine and 4-
chloroquinoline N-oxides have clearly demonstrated the sp3-character of the oxygen atom in the
complexes and the absence of any -interaction In the both cases for pyridine N-oxides the
structure of the adducts includes infinite quasi one dimensional chains of alternating D and A
moieties ( IndashI O IndashI O ) In the case of the adduct of 4-chloroquinoline N-oxide with iodine
(see the picture) the individual adduct molecule may be distinguished within the crystal lattice To
estimate the possibility of existing different conformations of the adduct (sp3 or sp
2) on the base of
its crystal structure the energy profile of the structure was calculated in Hyperchem program as the
dependence of the potential energy on the dihedral angle (IndashIndashOndashN) ndash (quinoline ring)
Two distinct barriers have been observed at 0o
( E = 357 Kcalmol corresponds to the structure
where iodine is in a close proximity to H8) and 180o ( E = 37 Kcalmol iodine is in a close
proximity to H2) The real X-ray structure (dihedral angle 117 o
( E = 025 Kcalmol) is similar to
the calculated conformer (dihedral angle 131 o
( E = 0 Kcalmol)) Obtained data indicate that
potential ldquosp2-stereoisomersrdquo are not favorable energetically due to probably the sterical factors and
should not be observed at least in the case of ldquostrongrdquo adducts with bulky Lewis acids
[1] T Kubota J Amer Chem Soc 1965 87(3) P458-468
227
P116
COPPER CATALYZED CYCLOPROPYL-ALLYLIC RING-OPENING
TRANSFORMATIONS OF GEM-CHLOROFLUORO- AND GEM-
BROMOFLUOROCYCLOPROPANES PREPARATION OF 2-
FLUOROALLYL HALIDES
MA Novikov NV Volchkov MB Lipkind OM Nefedov
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russian
Federation
Cyclopropyl-allylic ring-opening transformation of gem-chlorofluoro- and gem-bromofluoro-
cyclopropanes widely available by carbene cyclopropanation of corresponding alkenes is an
attractive tool for preparation of 2-fluoroallylic compounds that are known to possess a wide range
of biological activities
Ability of copper(I) compounds to catalyze cyclopropyl-allylic isomerization of gem-chlorofluoro-
and gem-bromofluorocyclopropanes was found and an effective route to 2-fluoroallyllic chlorides
and bromides was developed
R 2
R 1 R 3
R 4
F X
R 1
R 2
R 3
R 4
C F X
R 2
R 1
F
X
R 3 R 4
X = C l B r
R 1 -R 4 = H C H 3 -(C H 2 )n - (n = 2 -4 ) P h -C H = C H 2 c -C 3H 5 C l
C u X M eC N
o r
(N H C )C u X d io x an e
8 0 -1 0 0 degC
Thus from alkyl- aryl chloro substituted gem-chlorofluoro- and gem-bromofluorocyclopropanes
their bicyclic and spiro-substituted derivatives in presence of CuX or (NHC)CuX (NHC mdash N-
heterocyclic carbene) in MeCN or 14-dioxane at elevated temperatures corresponding 2-
fluoroallyllic chlorides and bromides could be prepared In the case of vinyl substituted gem-
chlorofluorocyclopropane 5-chloro-2-fluoropenta-13-diene forms as a major product Isomerization
of gem-chlorofluoro-11rsquo-bi(cyclopropane) proceeds via successive opening of both cycles leading
to 6-chloro-2-fluorohexa-13-diene as an only product
References
1) N V Volchkov M A Novikov M B Lipkind and O M Nefedov Mendeleev Commun
2013 23 19ndash21
2) M A Novikov N V Volchkov M B Lipkind and O M Nefedov Russ Chem Bull 2013
62 71ndash82
228
P117
DESIGN SYNTHESIS AND BIOLOGICAL EVALUATION OF P-
GLYCOPROTEIN INHIBITORS FOR MODULATION AND PREVENTION
OF MULTIDRUG RESISTANCE
M Sagnou1 X Alexiou
1 ES Kolotova
2 AA Shtil
2 AA Zeifman
3 IJ Titov
3 OV Stroganov
3
VV Stroylov3 IV Svitanko
3 FN Novikov
3 GG Chilov
3
1 - Demokritos National Research Center Greece
2 - Russian Scientific Oncology Center RAS
3 - N D Zelinsky institute of organic chemistry Russia
Multidrug resistance (MDR) mediated by P-glycoprotein (one of ATP-binding cassette (ABC)
transporters) through efflux of antineoplastic agents from cancer cells is a major obstacle to
successful cancer chemotherapy The inhibition of P-glycoprotein (P-gp) is thus a logical approach
to circumvent MDR There has been intensive research effort to design and develop novel inhibitors
for the P-gp and other ABC transporters to achieve this goal Complex in silico P-gp inhibition
model was developed in the present study using the pharmacophore ensemblesupport vector
machine scheme (to take into account the promiscuous nature of P-gp) molecular docking and
molecular dynamics approach (to predict ligand binding pose in huge P-gp hydrophobic cavity) and
free energy perturbation methods (FEP to accurate estimation of ligand-binding affinities) Two
series of novel P-gp inhibitors (based on curcumine scaffold) was designed synthesized and
evaluated in doxorubicin accumulation and cytotoxicity tests on chronic myeloid leukemia cell line
К562Dox with MDR phenotype
During the first round of optimization we discovered novel P-gp inhibitors that bind to the active
site of the enzyme and have activity comparable to clinical P-gp blocker verapamil We showed that
that hydrogen bonds with residues T837 and Q737 and hydrophobic and stacking interactions with
residues P770 Y307 and P994 play significant role in ligand binding We demonstrated that for
correct predictions of relative binding energy by FEP it is necessary to carry out an explicit account
of the solvent since the bridging water molecules significantly contribute to the energy of
formation of the protein-ligand complex
In the second round of optimization we discovered P-gp inhibitors that were to verapamil and
comparable with P-gp inhibitors in clinical trials We demonstrated that these compounds do not
exhibit the toxicity at concentrations up to 50 uM and have more than 100-fold lower IC50 in
doxorubicin cytotoxicity tests on К562Dox with MDR phenotype
229
P118
SELECTIVE HYDROGENATION OF UNSATURATED ALDEHYDES ON
THE COMPOSITE Pt-BASED NANOCATALYSTS A QUANTUM
CHEMICAL STUDY
AI Okhapkin1 OB Gadzhiev
1 AE Masunov
2 S Kunz
3 M Baumlumer
3 SK Ignatov
1
1 - NI Lobachevsky State University of Nizhny Novgorod Chemistry Department Nizhny
Novgorod Russia
2 - University of Central Florida Chemistry Department Orlando USA
3 - University of Bremen Institute for Applied and Physical Chemistry (IAPC) Bremen Germany
Selective hydrogenation of unsaturated aldehydes to alcohols is a key process in fabrication of
fragrance components for the modern cosmetology and perfume industry Since the selective oxo-
group hydrogenation is thermodynamically unfavorable due to the presence of the C=C bond the
industrial process is indirect complicated and expensive Recently a novel type of catalyst was
proposed that shows enhanced selectivity towards unsaturated alcohols It is using metal-oxide
supported Pt-nanoparticles with chemically modified surface In a present work the elementary
steps of such a catalytic reaction ie propenal and croton aldehyde hydrogenation were studied
within the cluster models of Pt surface using the DFT quantum chemical calculations (BLYP and
PBE density functionals in conjunction with the CRENBS or LANL2DZ pseudopotentials for Pt
atoms and 6-31G(dp) basis set for the remaining atoms) The clusters Pt8 Pt13 and Pt25 consisting
of two layers of Pt atoms were used as models for the Pt nanoparticle surface The diameter of the
Pt25 cluster is about 12 Aring which is close to the size estimated for the experimentally studied Pt
nanoparticles (18plusmn3Aring) [1] The different spin states of the clusters were considered (spin
multiplicity up to 11) The adsorption of reagents (H2 and aldehydes) and the organic ligands
working as orienting agents ensuring the reaction selectivity (BuSH Bu = n-C4H9) were studied as
initial steps of the catalytic process The various kinds of adsorption were studied (1) physical
adsorption of H2 on different sites of Ptn clusters (2) dissociative chemisorption of H2 resulting in
the Pt-adsorbed H atoms (3) chemisorption of ligands forming the Ptn-SBu structures and the
neighboring ndashSBuH adsorbed pairs (4) aldehyde adsorption on the neat Pt surface and the surface
partially occupied by the H atoms and the ndashSBu and ndashSBuH groups For all these pre-reaction
surface complexes the molecular structures adsorption energies and vibrational frequencies were
studied It was found that the ground state of the Pt25 clusters is the quintet one with the typical
spread of energies in lower spin states (M=135 and 7) of about 3 kcal mol-1
The H2 physical
adsorption energy is about 06-18 kcal mol-1
depending on the adsorption site The dissociative
adsorption energy of H2 was estimated to be 5-9 kcal mol-1
which is in reasonable agreement with
experimental values (~16 kcal mol-1
)[2] At the same time the ndashSBu group formation energy was
estimated as 30-56 kcal mol-1
depending on the adsorption site Their estimated surface coverage of
about 49 monolayer is in reasonable agreement with the experimentally observed dependence of
hydrogenation kinetics on the surface coverage [1] The kinetic barriers of the surface migration of
adsorbed H atoms and various hydrogenation pathways are discussed on the basis of the different
theoretical estimates
1 L Altmann S Kunz M Baumlumer J Phys Chem C 2014 118 8925-8932
2 PR Norton JA Davies TE Jackman Surf Sci 1982 121 103-110
The work was partially supported by the Russian Foundation for Basic research (project No 14-03-
00585) OBG and AIO are thankful to DAAD for the travel grants support
230
P119
NMR DIFFERENTIATION OF CHIRAL ALCOHOLS AND AMINES USING
SELENIUM-BASED CHIRAL PROBES
NV Orlov VP Ananikov
Zelinsky Institute of Organic Chemistry RAS Russia Moscow Leninsky pr 47 119991
Modern NMR spectroscopy is a powerful tool for structure elucidation of complex organic
molecules including natural products1 An important issue in this field is analysis of complex
mixtures of chiral compounds and determination of enantiomeric composition of each individual
molecule Utilization of chiral auxiliary reagents allows to efficiently differentiate enantiomers in
NMR spectra2 Besides continuous progress in development of chiral auxiliaries and derivatization
protocols made it possible to obtain diastereomers suitable for NMR analysis within minutes
directly in NMR tube excluding isolation and purification steps3 Nevertheless analysis of mixtures
of several chiral compounds is still a complicated task4
Recently we have developed simple synthetic routes to several selenium-based chiral probes which
readily react with chiral alcohols and amines directly in an NMR tube (Scheme 1 left) followed by
determination of their enantiomeric composition using 77
Se NMR spectroscopy5 In this case only
signals of selenium-containing diastereomers formed are observed in the spectra thus simplifying
assignment procedure
Scheme 1 DCC-promoted in tube derivatization of chiral alcohols and amines with chiral probes
R-ArSePA (left) and examples of spectral data - structure relationship using R-(4-
chlorophenylselanyl) propionic acid (right)
Now we have revealed that the diastereomers formed can be efficiently differentiated in 77
Se NMR
spectra depending on the nature of substituents at stereogenic center of analyzed chiral aclohols and
amines (Scheme 1 right) This observation gives possibility to perform preliminary structure
elucidation in several minutes and to analyse complex mixtures using a single 1D NMR experiment
Scope and limitations of this approach to various chiral alcohols and amines will be presented in the
poster
Acknowledgments This work was supported by RFBR (project No 12-03-01094)
1 Breton R C Reynolds WF Nat Prod Rep 2013 30 501
2 Wenzel T J Top Curr Chem 2013 341 1
Chem Rev 2012 112 4603
4 Novoa-Carballal R Fernandez-Megia E Jimenez C Riguera R Nat Prod Rep 2011 28
78
5 Orlov N V Ananikov V P Chem Commun 2010 46 3212
231
P120
NEW LIFE FOR OLD REACTION SYNTHESIS OF THIAZOLIDINES VIA
REGIOSELECTIVE ADDITION OF UNSYMMETRIC THIOUREAS TO
MALEIC ACID DERIVATIVES
AS Pankova MA Kuznetsov
Saint Petersburg State University Insitute of Chemistry Saint Petersburg Russia
Thiazolidine derivatives and in particular thiazolidinylacetic acids are highly valuable scaffolds for
medicinal and bioorganic chemistry as can be exemplified by a central penicillin core that contains
fused -lactam and thiazolidine rings Various substituted thiazolidines feature exclusively broad
range of biological activities that warrants a constant interest in preparing new thiazolidines and
studying their properties
Addition of thiourea derivatives to maleic anhydride or maleimides is used to get a rich
functionalized thiazolidinylacetic acid framework This reactions is classical but at the same time
many questions concerning regioselectivity in case of unsymmetric thioureas remained unclear and
there were problems to be solved Some controversial data and surprising results can be found in the
literature and therefore we decided to thoroughly investigate factors governing the regioselectivity
of this process
We have shown that addition of N-aryl-Nrsquo-ethyl(or methyl)thioureas to N-arylmaleimides proceeds
regioselectively providing 2-(3-ethyl(methyl)-2-arylimino-4-oxo-13-thiazolidin-5-yl)-N-
arylacetamides in good yields It is applicable for a wide range of substituents in aromatic rings and
the product selectivity does not depend on the solvent used A remarkable dependence of the
reaction regioselectivity on the solvent polarity was revealed with more sterically hindered alkyl
thioureas In nonpolar benzene 3-alkyl-2-arylimino-4-oxo-13-thiazolidines are formed
preferentially whereas in polar isopropyl alcohol and acetonitrile the reaction regioselectivity
changes in favor of 2-alkylimino-3-aryl-4-oxo-13-thiazolidines In the case of the most bulky
N-tert-butyl-Nrsquo-phenylthiourea the isomer with exo-cyclic position of an alkyl group is formed
exclusively At the same time addition of sterically hindered N-alkyl-Nrsquo-arylthioureas to maleic
anhydride leads only to 3-alkyl-2-arylimino-4-oxo-13-thiazolidinylacetic acids independent of the
solvent used We have unambiguously established the structures of all obtained thiazolidines (some
of them using X-ray data) and demonstrated the utility of the 15
N-1H HMBC spectroscopy for their
unequivocal assignment
Authors thank the Russian Scientific Fund for a research grant no 14-13-00126
232
P121
MECHANISTIC STUDY OF Cu2O AND CuO-CATALYZED CndashS CROSS
COUPLING REACTION
YS Panova1 VP Ananikov
2
1 - Saint-Petersburg State University Institute of Chemistry Russia Petrodvorets Universitetsky
pr 26
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Russia Moscow
Leninsky pr 47
C-S cross-coupling is a valuable synthetic tool to prepare a diversity of sulfur derivatives with high
yields [12] In spite of various synthetic applications the mechanism of C-S cross-coupling was not
clearly resolved Catalytic reactions mediated with CuO and Cu2O nanoparticles represent a
substantial challenge in this regard
In order to have a better insight of the reaction pathways detailed FE-SEM ESI-MS and NMR
studies were carried out Ligand-free copper oxides (I II)-catalyzed reactions of thiophenol with 4-
iodotoluene were chosen as a model reaction The role of copper centers on the surface of the
nanoparticles and in solution was studied and compared to reported in the literature reaction
pathways
It is interesting to note DFT calculations revealed that strongly polar solvent (like DMSO)
facilitates the formation of the anionic active species [Cu(SPh)2]- [3] This type of intermediates is
favored for halogen atom transfer mechanism as its activation energy barrier much lower (332
kcalmol) then the activation energy barrier of the most often suggested oxidative addition
mechanism (413 kcalmol) according to theoretical study [3]
Based on calculations and experimental data we will discuss the following catalytic pathways 1)
generation of [Cu(SPh)2]- complex by reaction of thiophenol with the base and copper oxides 2)
iodine atom transfer from 4-iodotoluene to Cu-center to form the [Cu(SPh)I]- intermediate and
phenyl radical 3) attack by phenyl radical at S atom of Ph-thiolate affording the formation of
coupling product It is noteworthy that in the absence a base intermediate [CuI2]- was observed by
ESI-MS analysis
References [1] S Ganesh Babu R Karvembu Tetrahedron Lett 2013 54 1677ndash1680
[2] S-W Cheng M-C Tseng K-H Lii C-R Leec and S-G Shyu Chem Commun 2011 47
5599ndash5601
[3] S-L Zhang and H-J Fan Organometallics 2013 32 4944-4951
Acknowledgment PY acknowledges Saint-Petersburg State University for postdoctoral fellowship
(125015602013)
233
P122
TRANSFORMATIONS OF CYCLIC ORGANIC PEROXIDES IN THE
PRESENCE OF TRANSITION METALS
ZY Pastukhova1 IA Yaremenko
1 LG Bruk
2 AO Terentrsquoev
1
1 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences
2 - Lomonosov Moscow State University of Fine Chemical Technologies
Currently organic peroxides are produced by dozens of the largest chemical companies in a large-
tonnage scale Peroxides are the main source of free radicals in chemical practice They are widely
used to initiate radical including chain-radical processes especially in the polymer manufacture In
the past decades the chemistry of organic peroxides has attracted considerable attention from
physicians and pharmacologists due to the detection of these compounds high antimalarial
anthelminthic and antitumor activities
Thermal instability of peroxides because of the presence of weak O-O bonds leads to
decomposition at normal or elevated temperatures Transition metals (Fe Сu Мn Со Сr) and their
salts are effective catalysts of decomposition Usually decomposition of organic peroxides is
nonselective process Decomposition reactions are not limited by the only homolytic decomposition
of O-O bond resulting in a complex product mixture is generated
In our work we found the selective transformations of cyclic organic peroxides in the presence of
transition metals (Scheme 1)
Scheme 1 Transformations of Cyclic Organic Peroxides
Mn+
OO
O
OO
OO
O O
This work is supported by RFBR 14-03-00237
Terentrsquoev AO Yaremenko IA Chernyshev VV Dembitsky VM Nikishin GI J Org Chem
2012 77 1833-1842
Terentev AO Yaremenko IA Vil VA Dembitsky VM Nikishin GI Synthesis 2013 45 (2)
246-250
Ingram K Yaremenko IA Krylov IB Hofer L Terentev AO and Keiser J J Med Chem
2012 55 (20) 8700-8711
234
P123
ENANTIOSELECTIVE HYDROLYSIS OF 3-HYDROXY-14-
BENZODIAZEPIN-2-ONE ESTERS BY PIG LIVER MICROSOMES
VI Pavlovsky1 EA Shesterenko
1 II Romanovska
1 OV Sevastyanov
1 TA Yurpalova
1 SA
Andronati1 VCh Kravtsov
2
1 - AV Bogatsky Physico-chemical Institute National Academy of Sciences of
Ukraine Lustdorfska dor 86 Odessa Ukraine
2 - Institute of Applied Physics Academy of Sciences of Moldova Chisinau Republic
of Moldova
The configuration of chiral biologically active compounds plays an important role in processes of their
biotransformation and binding with biomembranes Methods of asymmetric synthesis and resolution of
enantiomers are fraught to difficulties thus development of economical preparative biotechnological
methods of enantiomers resolution is prospective
Carboxylesterase (EC 3111) is the most studied enzyme which catalyze the enantioselective hydrolysis of
a wide range of acyclic carbocyclic and heterocyclic compounds But the number of publications devoted to
the enantioselective hydrolysis of benzodiazepine derivatives which clinical effects include anxiolytic
anticonvulsant and hypnotic effects muscle relaxation is quite limited
The aim of the present work was the development of a method of the enantioselective hydrolysis of 3-
hydroxy-14-benzodiazepin-2-one esters by pig liver microsomes and investigation of S-enantiomers binding
affinity for central benzodiazepine receptors
Microsomal fraction was isolated by the low speed centrifugation method in the presence of Ca2+
ions
Protein yield was 380 mgg of liver tissue and esterase activity was 1725 Umg protein
The method of enantioselective hydrolysis of 1-unsubstituted-(1) 1-methyl-(2) 1-ethyl-(3) 3-acetoxy-7-
bromo-5-phenyl-12-dihydro-3H-14-benzodiazepin-2-ones using pig liver microsomal fraction was
developed (esterase activity 130- Ucm3 pH 70 t 37 ordmC τ 25 h DMSO concentration 40 (vv))
Enantiomers of 3-hydroxy-14-benzodiazepin-2-one esters were purified by silica gel column
chromatography Enantiomeric excesses of substrates (ees) were determined by HPLC using Shimadzu LC-
8A pump with a chiral column ChiraDex It was shown that the products of the reaction ndash 1-unsubstituted-
(4) 1-methyl-(5) 1-ethyl-3-hydroxy-7-bromo-5-phenyl-12-dihydro-3H-14-benzodiazepin-2-ones (6)
underwent racemization during hydrolysis and subsequent isolation what is consistent with the literature
data [1]
The S-enantiomers of three substrates 1S-3S were obtained with ees gt97 and yields 44-49 their
absolute configurations were determined by X-ray crystallography (fig)
1S
2S
3S(a)
3S(b)
Fig ORTEP view of molecular structure of 1S 2S and two conformers in the structure 3S (a and b)
illustrates their absolute configuration
Values of specific rotation 20
Dof 1S-3S were +1169ordm +1953ordm +1938ordm (c = 10 CHCl3) respectively
With a help of the radioligand binding methods affinity of S-enantiomers 1S-3S and racemates 1-3 for the
CBR of rat brain was determined and values of IC50 were evaluated It was shown that the S-enantiomers
1S-3S are 14-21 times more potent ligands of CBR than the corresponding racemates 1-3
References 1 Oswald P Desmet K Sandra P et al 2002 Determination of the enantiomerization energy barrier of some 3-
hydroxy-14-benzodiazepine drugs by supercritical fluid chromatography J Chromatogr B 779 283ndash295
235
P124
A SIMPLE TECHNIQUE FOR PRODUCING PALLADIUM
NANOPARTICLES ON CARBON SUPPORT AS CATALYST FOR
CROSS-COUPLING REACTIONS
EO Pentsak VP Ananikov
ND Zelinsky Institute of Organic Chemistry RAS Moscow Russia
Recently much attention has been paid to carbon materials modified by metal nanoparticles due to
increasing interest in using of such systems in catalysis material science optics and electronics
Successful application of palladium nanoparticles supported on carbon materials was facilitated
many organic synthesis procedures Efficiency and selectivity of these catalysts was determined by
such characteristics as particles size the uniformity of their distribution on the support surface and
the range of particle size distribution
We have previously shown that the labile behavior in solution and the tendency to form palladium
clusters are inherent in Pd2dba3 complex [1]
Thus we were able to cover carbon material by
nanoparticles with optimum sizes and high monodispersity under mild conditions without the need
of stabilizers and reducing agents using easily available Pd2dba3 complex as a precursor of
palladium
In this study we found that the variation of temperature and concentration of solution allowed
tuning of coverage density of the supported nanoparticles as well as control of diameter of the
nanoparticles from 2 to 15 nm This procedure was found scalable and well reproducible
Dispersion values of the nanoparticles sizes usually did not exceed 1-2 nm Kinetics of the process
was investigated by nuclear magnetic resonance spectroscopy NMR and scanning electron
microscopy (FE-SEM) Study of deposition process by FE-SEM showed that the average particles
size was stabilized quickly during the coating process The particles size depended on the
conditions of the process while the increase of the coating density occurred gradually until
complete consumption of the Pd precursor
The catalytic activity of prepared palladium nanoparticles supported on graphite has been studied
utilizing model Suzuki and Heck reactions The catalyst prepared by our method showed high
efficiency for this type of reactions 100 conversion of the Heck and Suzuki reactions was reached
only in a few hours at low catalyst loadings (02-05 mol )
[1] Zalesskiy S S Ananikov V P Organometallics 2012 V 31 P 2302ndash2309
236
P125
SELECTIVE CLEAVAGE OF GLYCOSIDIC LINKAGES USING
SOLVOLYSIS WITH ANHYDROUS TRIFLUOROACETIC ACID
SN Senchenkova AV Perepelov AV Filatov AS Shashkov YA Knirel
NDZelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
A common approach in structural studies of polysaccharides is the selective cleavage of glycosidic
linkages to give oligosaccharide fragments which usually show better-resolved NMR spectra than
the parent polymer and are readily amenable to MS analysis One of the methods useful for this
purpose is solvolysis with strong acids For instance solvolysis with anhydrous HF has been used in
structural analysis of carbohydrates since early 1980s and later trifluoromethanesulfonic (triflic)
acid was introduced However these reagents have some disadvantages eg HF handling requires
special equipment triflic acid is expensive and both are highly hazardous In search for a better
solvolytic agent we tested anhydrous CF3CO2H in selective cleavage O-polysaccharides of
medically important bacteria Escherichia coli and Enterobacter cloacae and found it to be useful
and convenient CF3CO2H split selectively the α1rarr2- and α1rarr3-rhamno- and -fuco-pyranosidic
linkages as well as the HexpNAc-(1rarr4)-Manp linkage whereas other linkages were not affected
Below are structures of the cleaved O-polysaccharides (O68 at 50degC for 16 h all others at 40degC for
5 h) with the glycosidic linkages sensitive to CF3CO2H shown in rectangles
237
P126
СROSS-COUPLING OF TEREPHTHALONITRILE DIANION AND
AROMATIC NITRILE RESULTING IN SUBSTITUTED DICYANOBIARYLS
RYu Peshkov1 EV Panteleeva
1 VD Shteingarts
2
1 - Novosibirsk State University Novosibirsk Russia
2 - NN Vorozhtsov Novosibirsk Institute of Organic Chemistry Novosibirsk Russia
Cyanobiaryls have a wide area of practical utilization in technology (polymers semiconductors
OLED) as well as in medicine [1] Modern approaches to their synthesis are based on manifold
cross-coupling reactions of preactivated arenes catalyzed by transition metals We suggest a concise
and inexpensive non-catalytic approach applying terephthalonitrile dianion 1 as cyanoarylating
reagent for neutral aromatic nitriles It was found that 1 generated by terephthalonitrile reduction
with alkali metal in liquid ammonia undergoes cross-coupling with benzonitrile as well as 2- and 3-
cyanobiphenyls providing 44`-dicyanobiphenyl and dicyanoterphenyls [2] Present work is aimed
on broadening the scope of neutral substrates applicable for such type of cross-coupling and study
of its mechanism by revealing electronic and structural factors governing regioselectivity and
efficiency of the reaction For the purpose we varied the nature of substrate by introduction of an
extra substituent into benzonitrile (Me MeO F Cl Br) as well as by alteration of aromatic moiety
(cyanonaphthalenes 9-cyanoanthracene 4-cyanopyridine) Besides nitriles electron-deficient
arenes ethylbenzoate 3-methylbenzophenone and nitrobenzene were tested Also experimental and
quantum-chemical modeling of possible reaction pathways were performed We found out that
benzonitriles substituted with o- m-Me -MeO and -F both cyanonaphthalenes and 9-
cyanoanthracene undergo coupling with 1 providing subsequent cyanobiaryls (scheme) Towards all
other substrates 1 acts as reducing reagent The regularities revealed are interpreted in terms of the
reaction scheme with the intermediacy of the charge-transfer complex 2 between 1 and cyanoarene
[2] which further transforms into dimeric dianion 3 either by heterolytic pathway or by successive
single electron transfer and recombination of primary generated radical anions Subsequent
decyanation of 3 forms long-living monoanion 4 capable to be converted into cyanobiarylic product
either through oxidation or alkylation
CN
CN
2-
CN CN
CN
2-
CN CN
CN
CN
+
primary RA-pairCTC
CN
CN
CN
-CN-
CN
CN
CNNC
CN
AlkBr
NC Alk
CN
Alk
-H+
-CN-
[O]
X X X
X X
X X
X
ETin-cage
recombination
heterolytic pathway (SNAr)-Br-
2M+CN
2-
CNNH3
M Li Na K
ArX
CN CNCN CNCN
F
F
F FF
FFF
CN
Bu
CN CN
F CN
CN
CN
CN
CN
CN
CN
CNCN
CNX
CNNC
X
X
cyanobiaryleyield 14-90
X
X H 2- 3-CH3 -OCH3 -F
ArX
CN
CN
X
CN
CN
F F
12
3 4
Bu
CNCN
CN
CN
The financial support of the CMSD of RAS (the project No 26) is acknowledged
[1] Corbet J-P Mignani G Chem Rev 2006 106 2651
[2] a) Panteleeva EV et al Eur J Org Chem 2005 2558 b) Panteleeva EV et al
ARKIVOC 2011 viii 123
238
P127
REARRANGEMENT OF CYCLIC 9-MEMBERS Si-PEROXIDES
RA Pototskiy1 RA Novikov
2 AO Terentev
1 GI Nikishin
1 AV Arzumanyan
1
1 - N D Zelinsky Institute of Organic Chemistry Laboratory for Studies of Homolytic Reactions
Moscow Russia
2 - N D Zelinsky Institute of Organic Chemistry Laboratory of Carbene Chemistry and Small-
Sized Cyclic Compounds Moscow Russia
Among organic peroxides compounds with SiOO moiety are less known than their carbon
analogues As the result there are few examples of reaction of silicon containing peroxides in
literature
In the previous works we reported about successful synthesis of different silicon containing cyclic
peroxides [12]
Now we focused on investigation of treatment of such compounds with different reducers and
Lewis acids (LA)
It has been shown that treatment of the cyclic Si-peroxides with different
reducers leads to contraction of peroxide cycle on two oxygen atoms Notably
each peroxide group lost one oxygen atom giving earlier unknown silyl-
protecting diols Reaction was carried out in diethyl ether medium at ambient
temperature in the presence of 3-fold access of a reducer The best results were
reached with triphenylphosphine Yield of products were 60 to 75 depending
on structure of starting substance Such products may be used as building blocks
bin different bioactive compounds
Treatment of bis-sililperoxides under LA action was studied The reaction was carried out in
different reaction media with 2-fold excess of LA (SnCl4 TiCl4 AlCl3) It has been established that
the way of reaction depends on nature LA catalyst For example formation of lactones yield of 80 ndash
95 was observed (Bayer-Villiger-like reaction) in the presence of SnCl4 In case of TiCl4 the
combination of a regrouping and formation of an appropriate ketone was observed with AlCl3
reaction did not flow past
Summary in this work chemical reactions of cyclic Si-peroxide compounds have been investigated
Organic silicon peroxide compounds can enter various reactions leading to formation of lactones
diols with a trialkylsilyl group depending on reaction conditions that point to their high synthetic
potential
References
[1] Arzumanyan AV Terentrsquoev AO Nikishin GI etal Organometallics 2014 33 2230-2246
[2] Platonov MM Terentrsquoev AO Nikishin GI etal J Org Chem 2008 73 3169-3174
R R
S i
O
S i
O
O O
239
P128
EFFICIENT ONE-POT SYNTHESIS OF DIVERSE BENZO[C[CHROMENE-
6-ONES BY BASE-PROMOTED CASCADE REACTIONS
TN Poudel YR Lee
School of Chemical Engineering Yeungnam University Gyeongsan 712-749 Republic of Korea
Molecules bearing benzo[c]chromen-6-one and its derivatives are extensively distributed in nature1
Some of these molecules exhibit biologically and pharmacologically important antitumor and
antibiotic activities2 promote endothelial cell proliferation and inhibit oestrogene receptor growth
activities3 Due to the importance of these biological and pharmacological activities several
synthetic methods have been devised to produce benzo[c]chromen-6-one derivatives Of these
methods the most useful method involves a Suzuki-Miyaura cross-coupling reaction followed by
metal or Lewis acid mediated lactonization of ester and methoxy groups4
Recently a new reaction
involving a microwave-assisted Diels-Alder reaction betwee 4-cyanocoumarin and 1-oxygenated
dienes followed by elimination and aromatization with a strong base was also described5 However
these synthetic approaches included two-step reactions and required purification of the intermediate
In addition the starting materials used for these transformations were synthesized from
corresponding materials in two or more steps Thus a mild general and efficient one-pot synthetic
route for benzo[c]chromen-6-one derivatives using inexpensive catalysts and reagents is still in
demand especially a route that allows minimization of the steps and access to diverse products
We present herein a novel one-pot synthesis of a variety of benzo[c]chromen-6-one derivatives
using Cs2CO3-promoted reactions of substituted 2-hydroxychalcones and β-ketoesters These
reactions involved cascade Michael addition intramolecular aldol oxidative aromatization
lactonization and provided an efficient synthetic route for the production of biologically interesting
novel benzo[c]chromen-6-one molecules bearing several different substituents on benzene rings As
an application of this methodology several synthesized benzo[c]chromen-6-ones were transformed
into highly functionalized novel terphenyls
References
1 (a) Ya L Garazd A S Ogorodniichuk M M Garazd andV P Khilya Chem Nat Compd
2002 38 424 (b) K Ishiguro M Yamaki M Kashihara S Takagi and K Isoi
Phytochemistry1990 29 1010 (c) H Abe K Nishioka S Takeda M Arai Y Takeuchi and
T Harayama Tetrahedron Lett200546 3197
2 (a) T Hosoya E Takashiro T Matsumoto and K Suzuki J Am Chem Soc1994 116
1004(b) C A James and V Snieckus Tetrahedron Lett1997 38 8149
3 (a) J M Schmidt G B Tremblay M Page J Mercure M Feher R Dunn-Dufault M G Peter
and P R Redden J Med Chem 2003 46 1289(b) J Pandey A K Jha and K Hajela
Bioorg Med Chem2004 12 2239
4 (a) Q J Zhou K Worm and R E Dolle J Org Chem2004 69 5147 (b) G J Kemperman
B Ter Horst D Van de Goor T Roeters J Bergwerff R Van der Eem and J BastenEur J
Org Chem2006 14 3169
5 M EJung and D A Allen Org Lett 2009 11 757
240
P129
PRACTICAL SYNTHESIS OF 124-THIADIAZOLES VIA`
COPPER-MEDIATED HOMO-COUPLING OF THIOAMIDES
Y-D Sun C-R Qi H-F Jiang
South China University of Technology College of Chemistry amp Chemical Engineering Guangzhou
P R China
Thiadiazoles are regarded as an important class of five-membered heterocycles for many bioactive
molecules One general method for the preparation of 124-thiadiazoles containing the same groups
in 3- and 5-positions was oxidative dimerization of the corresponding thioamides using oxidizing
agents One the other hand the transition metal-mediated oxidative transformations to construct
heterocycles have attracted great interest over the past decade In particular copper salts have been
successfully applied in the formation of C-hetero or hetero-hetero bonds which exhibit great
potential for the construction of various heterocycles On the basis of our recent developed Cu-
catalyzed method for synthesis of heterocycles1-5
and increasing interest of oxidative cross-coupling
reactions of two nucleophiles herein we disclose a novel method for 35-disubstituted 124-
thiadiazoles via copper(II)-mediated homo-coupling of thioamides involving C-N and N-S bond
formations (Scheme 1)
Scheme 1 Synthesis of 124-thiadiazoles
References
1 Huang L Jiang H Qi C Liu X J Am Chem Soc 2010 132 17652
2 Li X Huang L Chen H Wu W Huang H Jiang H Chem Sci 2012 3 3463
3 Gao Y Yin M Wu W Huang H Jiang H Adv Synth Catal 2013 355 2263
4 Zeng W Wu W Jiang H Huang L Sun Y Chen Z Li X Chem Commun 2013 49
6611
5 Sun Y Jiang H Wu W Zeng W Wu X Org Lett 2013 15 1598
241
P130
HIGHLY EFFICIENT SYNTHESIS OF TERTIARY α-HYDROXY KETONES
VIA CO2-PROMOTED REGIOSELECTIVE HYDRATION OF
PROPARGYLIC ALCOHOLS
H-T He C-R Qi H-F Jiang
South China University of Technology College of Chemistry amp Chemical Engineering Guangzhou
P R China
-Hydroxy ketones have attracted tremendous interest in biologically active natural product
research and synthetic chemistry However few of methodologies could be applicable for efficient
hydration of propargylic alcohols to form -hydroxy ketones except the Kucherov reaction using
mercury(II) salts as catalysts A wide range of transition metals including Pd Pt Fe Au Ag Ir and
Ru have been investigated for the hydration of alkynes however these catalytic systems either
showed low activity or led to side reactions such as Meyer-Schuster and Rupe rearrangements
Therefore the development of novel processes for the hydration of propargylic alcohols to produce
-hydroxy ketones with high efficiency is highly desirable
Using CO2 as the feedstock a great deal of work in many different fields has been undertaken to
produce cyclic carbonates In our previous work1 2
we found that secondary amine was able to
attack the carbonyl group of the α-methylene cyclic carbonate to give the ring-opening product
Recently we set out to study whether water was capable to proceed the nucleophilic attack instead
of the secondary amines to furnish useful -hydroxy ketone derivatives (Scheme 1)
Scheme 1
References
[1] Qi C Jiang H Green Chem 2007 9 1284
[2] Qi C Huang L Jiang H Synthesis 2010 9 1433
242
P131
UNEXPECTED DIRECT CONVERSION OF FUSED 125-
SELENADIAZOLES INTO 125-THIADIAZOLES
LS Konstantinova EA Knyazeva OA Rakitin
ND Zelinsky Institute of Organic Chemistry RAS
Fused 125-thiadiazoles have attracted much attention because of their interesting chemical
properties and various possibilities for use as antibacterial and antiviral agents agrochemicals and
as π-type building blocks for organic electronics particularly for both low- and high-molecular
organic light-emitting diodes (OLEDs)1 Recently 125-thiadiazole derivatives were recognized as
efficient electron acceptors and successfully used in the preparation of radical-anion salts revealing
antiferromagnetic exchange interactions in their spin systems and conductive charge-transfer
complexes2 Although methods for the preparation of fused 125-thiadiazoles are numerous and
well elaborated there is still a lack of syntheses of derivatives containing electron-deficient
heterocycles
We have found that treatment of 125-selenadiazoles fused with nitrogen heterocycles such as
piperazine and thia(selena)diazole with S2Cl2 in DMF gave unexpectedly corresponding 125-
thiadiazoles in high yields This is the first case of direct substitution of the selenium to sulfur atom
in 125-selenadiazoles The driving force of this reaction is the precipitation of elemental selenium
which was isolated from the reaction mixtures in practically quantitative yield
We gratefully acknowledge financial support from the Russian Foundation for Basic Research
(Project 13-03-00072) from the Presidium of the Russian Academy of Sciences (Programme No 8)
and from the Leverhulme Trust (Project IN-2012-094)
1 Todres ZV Chalcogenadiazoles Chemistry and Applications CRC PressTaylor amp Francis
Boca Raton 2012 290 pp
2 N A Semenov N A Pushkarevsky E A Suturina E A Chulanova N V Kuratieva A S
Bogomyakov I G Irtegova N V Vasilieva L S Konstantinova N P Gritsan O A Rakitin
V I Ovcharenko S N Konchenko A V Zibarev Inorg Chem 2013 52 6654
243
P132
ACTIVATION OF HYDROPEROXIDES BY TETRAALKYLAMMONIUM
BROMIDES
EV Raksha1 YuV Berestneva
1 NA Turovskij
1 MYu Zubritskij
2
1 - Donetsk National University Physical chemistry Department Donetsk Ukraine
2 - LM Litvinenko Institute of Physical Organic and Coal Chemistry National Academy of
Sciences of Ukraine Donetsk Ukraine
The investigation of supramolecular catalysis of organic peroxides decomposition is the actual
direction in the development of peroxide initiators chemistry There are a wide range of catalytic
systems for the radical decomposition of hydroperoxides and quaternary ammonium salts are
occupied an important place among of them The key feature of supramolecular hydroperoxides
decomposition in the presence of Alk4NBr is the complex formation between the reactants [1]
Systematic kinetic investigations of the interaction between hydroperoxides and Alk4NBr have been
carried out [1] Activation energies of the hydroperoxides thermolysis and catalytic decomposition
have shown to be change simbatically Kinetic parameters of the hydroperoxide-catalyst complex
decomposition have been determined Lowering of the activation barrier for the complex-bonded
hydroperoxide decomposition as compared with its thermolysis in acetonitrile is 40 kJmiddotmol-1
The interaction of tert-butyl as well as 113-trimethyl-3-(4-methylphenyl)butyl hydroperoxides
with tetraalkylammonium bromides (Alk4NBr) has been studied by NMR spectroscopy The
complexation between reactants was observed by relative change of the chemical shifts in the NMR 1H spectra The complex formation between the hydroperoxide molecule and corresponded
quaternary ammonium salt has been proved Thermodynamic parameters of complex formation
have been determined
The equilibrium constants of complex formation (KС) between tert-butyl hydroperoxide and
Alk4NBr have been determined both by NMR 1H and
13C spectroscopy The values of the ΔcompH
for the hydroperoxide complex with investigated salts are negative and lie are within -20 divide -9
kJmiddotmol-1
7 in CDCl3 solution that corresponds to the formation of weak hydrogen bonds Similar
effect has been observed in CD3CN solution for the hydroperoxide-Alk4NBr systems
The equilibrium constant values as well as complexation enthalpies decrease with intrinsic
tetraalkylammonium cation volume increasing and this effect is observed over the temperature
range 297-313 K Complexation enthalpies defined by kinetic and NMR spectroscopy methods
coincide
The structural model has been proposed for the complex of hydroperoxides with Alk4NBr It
includes the hydroperoxide molecule salt cation and anion as well as solvent molecule Structural
reorganization of the hydroperoxide fragment is the key factor of the chemical hydroperoxide
activation in the presence of Alk4NBr
[1] NА Тurovskij EV Raksha YuV Berestneva et al in Polymer Products and Chemical
Processes Techniques Analysis and Applications Editors RA Pethrick EM Pearce GE
Zaikov ndash Toronto New Jersey Apple Academic Press 2013 ndash 323 p ndash P 269-284
[2] NА Тurovskij YuV Berestneva EV Raksha et al Polymers Research Journal ndash 2014 ndash
Vol 8 No 2 ndash P 85 ndash 90
[3] NА Тurovskij EV Raksha YuV Berestneva MYu Zubritskij Russian Journal of General
Chemistry ndash 2014 ndash Vol 84 Iss 1 - P 16-17
[4] NА Тurovskij YuV Berestneva EV Raksha et al Monatshefte fuumlr Chemie - Chemical
Monthly DOI 101007s00706-014-1234-5
244
P133
THE AZA-COPE-MANNICH REACTION APPLICATION TO THE
SYNTHESIS OF UNNATURAL L-ALANINE DERIVATIVES
NK Ratmanova DS Belov IA Andreev AV Kurkin
Lomonosov Moscow State University Department of Chemistry Moscow Russia
Unnatural amino acids represent a nearly infinite array of diverse structural elements for the
development of new leads in peptidic and non-peptidic compounds Due to their seemingly
unlimited structural diversity and functional versatility they are widely used as chiral building
blocks and molecular scaffolds in constructing combinatorial libraries
Herein we report the synthesis of the enantiopure unnatural L-alanine derived trans-
octahydrocyclohepta[b]pyrroles 5a and 5b via the aza-Cope-Mannich reaction (Scheme 1) Epoxide
2 (the source of chirality) was prepared according to the literature procedures from commercially
available alcohol 1 applying Shi epoxidation protocol1 The LiClO4-meditated epoxide ring-opening
of 2 with L-alanine ethyl ester gave the diastereomeric mixture of amino ethanols 3a and 3b After
the chromatographic separation the compounds 3a and 3b were obtained as single isomers with
high enantiomeric purity (ee = 99 and 86 respectively chiral HPLC) The hydrogenation of 3a
and 3b on the Lindlar catalyst gave desired alkenes 4a and 4b and unexpected side products (S)ndash
and (R)ndashethyl 2ndash(4567ndashtetrahydrondash1Hndashindolndash1ndashyl)propanoates Finally carrying out the aza-
Cope-Mannich reaction under previously optimized conditions2 gave the target enantiopure
products 5a and 5b without epimerization
Scheme 1 Synthesis of target compounds 5a and 5b
As a result two diastereomeric unnatural L-alanine analogues 5a and 5b were synthesized in 5
steps from commercially available materials The study showed that conditions of the aza-Cope-
Mannich reaction are mild enough to be applied in the complex settings for example to the
synthesis of molecules with several stereocenters which are prone to racemization3
This study was supported by the Russian Foundation for Basic Research (RFBR) Russia (Projects
No 14-03-31685 14-03-31709 14-03-01114)
References
1 Wang Z-X Cao G-A Shi Y J Org Chem 1999 64 7646ndash7650
2 Belov D S Lukyanenko E R Kurkin A V Yurovskaya M A J Org Chem 2012 77
10125ndash10134
3 Ratmanova N K Belov D C Andreev I A Kurkin A V Tetrahedron Asymmetry 2014
25 468ndash472
245
P134
MECHANISTIC STUDIES OF PALLADIUM-MEDIATED ALKYNE
INSERTION REACTION USING ELECTROSPRAY IONIZATION TANDEM
MASS SPECTROMETRY
KS Rodygin1 LL Khemchyan
2 VP Ananikov
2
1 - Saint Petersburg State University Institute of Chemistry Stary Petergof Russia
2 - N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Rapid development of transition metal catalysis allows rational design of a new methodology to
carry out three-component coupling To achieve this aim challenging question concerning
mechanistic features of insertion reaction should be resolved[1]
Oxidative addition of an aryl halide to Pd in Pd(PPh3)4 (a common source of Pd in cross-coupling
reactions) is the first step in the catalytic cycle Addition of an alkyne to the mixture containing
Pd(PPh3)2ArX results in the formation of another intermediate Pd(Ar)(PPh3)2(alkyne)X The
intermediate containing the alkyne-unit has three possibilities to evolve π-complex acetylide or
vinyl complex (insertion product)
For development of the present project it was important to reveal the nature of transition metal
intermediates and their role in the catalytic cycle in order to improve selectivity and scope of
three-component coupling reaction The questions of key importance in this regard (see Scheme)
how facile is the insertion reaction And what types of complexes ndash π-complex acetylide or vinyl
complex ndash are formed
Few important features of the studied system deserve a note Oxidative addition proceeds with
formation of Pd complex the corresponded ion was detected as [Pd(PPh3)2Ph]+ The elimination of
PPh3-containing species is typical and expected under these conditions More interesting series of
alkyne insertions into Pd-C bond starting from initial complex lead to the formation of
Pd-containing vinyl complexes Reductive elimination results in formation of corresponded
substituted alkenes dienes triene and tetraene Note formation of these Pd-free olefinic species
provides an evidence for the fact of alkyne insertion into Pd-C bonds
On the next stage ESI-(+MSMS) experiment via collision-induced dissociation (CID) was
performed The detected fragment ions serve as an additional evidence for the investigated alkyne
insertion step In the present study we were able to distinguish π-complex and insertion intermediate
using ESI-(MSMS) experiment
KR gratefully acknowledges Saint Petersburg State University for a postdoctoral fellowship (
125015602013)
References
[1] Hydrofunctionalization VPAnanikov MTanaka (Eds) Springer 2013 Heidelberg ISBN
978-3-642-33734-5
246
P135
FACILE AND EFFICIENT SYNTHESIS 2-AMINO-4H-CHROMENES VIA
SOLVENT-FREE CASCADE ASSEMBLING OF SALICYLALDEHYDES
AND CYANOACETATES
FV Ryzhkov RF Nasybullin MN Elinson
N D Zelinsky Institute of Organic Chemistry Russian Academy of Sciences 119991 Moscow
Russian Federation
2-Amino-4H-chromenes (or 2-amino-4H-benzo[b]pyranes) are of particular interest as they belong
to privileged medicinal scaffolds serving for generation of small-molecule ligands with highly
pronounced spasmolitic- diuretic- anticoagulant- and antianaphylactic activities [1] The current
interest in 2-amino-4H-chromenes bearing nitrile functionality arises from their potential
application in the treatment of human inflammatory TNFα-mediated diseases such as rheumatoid
and psoriatic arthritis and in cancer therapy [2]
The development of solvent-free organic synthesis has become an important research area This is
not only due to the need for the more efficient and less labour-intense methodologies for the
synthesis of organic compounds but also because of the increasing importance of the
environmental considerations in chemistry The elimination of volatile organic solvents in organic
synthesis is also the most important goal in lsquogreen chemistryrsquo
We were prompted to use a convenient and facile solvent-free cascade methodology for the
synthesis of 2-amino-4H-chromene scaffold from salicylaldehydes and cyanoacetates We have
found that potassium fluoride as catalyst can produce under solvent-free mild conditions a fast and
selective cascade trasformation of salicylaldehydes and cyanoacatates into substituted at ambient
temperature 2-amino-4H-chromenes chromenes in 88ndash98 yields
The catalytic procedure utilizes simple equipment it is easily carried out and is valuable from the
viewpoint of environmentally benign diversity-oriented large-scale processes This efficient
potassium fluoride catalyzed solvent-free approach to substituted 2-amino-4H-chromenes represents
a new synthetic concept for cascade reactions and allows for the combination of the synthetic
virtues of conventional cascade processes with ecological benefits and convenience of solvent-free
procedure 1 H Aryapour M Mahdavi SR Mohebbi Frch Pharm Res 2012 35 9 1573-1582
2 J Skommer D Wlodkowic M Matto MEray J Pelkonen Leukemia Res 2006 30 322-333
247
P136
A NEW 3D CHEMICAL FORMULAS FOR ANALYZING OF
GEOMETRICAL STRUCTURES OF ACTIVE BIOMOLECULES IN
laquoSTRUCTURE-ACTIVITYraquo PROBLEM
EA Smolenskii AN Ryzhov PO Guskov IV Chuvaeva
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
We suggest a new way (ldquothe method of trianglesrdquo) to describe 3D molecule structures and solid surfaces with
account their spatial geometry making the difference between stereo and conformational isomers The new
formulas allow using well-known procedures of the ldquostructure-propertyrdquo and ldquostructure-activityrdquo problems for
large molecules Furthermore the method clears the novel ways of circumscribing solid surfaces and in
ldquostructure-catalytic activityrdquo problems The approach is based on taking into account every of the spatial-
orientated atom triples i j k designating triangle Let us to consider vertex i of the triangle and vectors
jiijVVV
kiik
VVV
being the entries of the i-row of the Matrix of Geometrical Distances (MGD) And
now we proceed to description in terms of the triangles matrix
jkij
jkij
ijkjkijijkijkijkjkijijkkji
ijk
VV
VVnVVnVV
sin
2
1
2
1
Since a vectors product determines the triangle it automatically means an orientation of the triangle surface in
space There are 3 sets of indexes with the same direction of normal vectors i jk
n and 3 ones in opposite One can
selects internal or external triangles from the triangle matrix by following rule triangle ijk
is external if
m i j k and i j k 0ijk m
n V for triples of atoms placed on one line i jk
n is determined as vector
that is perpendicular to and finished on this line and started from the mass center of molecule
Changing internal triangles in the matrix ijk
by zeros we get the external triangles matrix
ex
ijk
This matrix
contains the same external triangle i j k three times Thus we define geometrical structure of a molecule
Usually a biomolecule activity is defined by small site being complimentary to its natural substrates The site (ldquok-
complexrdquo) is consisted of k inter-oriented triangles Vector m
F of entry numberslm
a for every type of the k-
complex triangles in molecule with number m may be called as ldquo3D chemical formulardquo of this molecule One can
selects the triangles of k-complex considering the matrix (
M
m
k
N m
CM
1
dimension) of entry numbers lm
a for
every type of the k-complex triangles in each compound of the set m
P ( (1 )m M ) of active and non-active
substances Here lm
a ( 1m M 1
(1 )m
M
k
N
m
l C ) is the entry number of k-complex with number l in m -
compound taking into account conformational isomerism M ndash the number of compounds m
N - the number of
triangles in m-compound
M
m
mNN
1
- the general number of triangles in all substances This matrix is based on
3D chemical formulas Here we must using rule any triangle being among type of triangles contained in inactive
substances cannot be contained in k-complex Remaining triangles (approximately they are contained in k-
complex their number as show on example of set of castanospermines tested by anti-HIV activity [GWJ Fleet
et al FEBS Letters 1988 V 237 1-2 P 128-132] as a rule less than number of active compounds) is used
for making of additive scheme for calculating of biological activity
So 3D chemical formulas can be used for describing genes catalyst surfaces proteins and other biomolecules
248
P137
A PROBLEM OF DEFINITION OF CHEMICAL EQUILIBRIUM IN
CONTEMPORARY CHEMISTRY
AN Ryzhov EA Smolenskii PO Guskov MS Molchanova
ND Zelinsky Institute of Organic Chemistry Russian Academy of Sciences Moscow Russia
Unfortunately a many definitions of chemical equilibrium of systems exist and are used now In
process of our investigation we find that principle of detailed equilibrium is sufficient but not
necessary condition of chemical equilibrium from the viewpoint of formal kinetics We propose a
new definitions
1 Steady-state chemical system is called chemical system with constant temperature pressure
volume and activities of compounds
2 Equilibrium chemical system is called steady-state and adiabatically isolated system
3 System with detailed equilibrium is called equilibrium system with equilibrium in all
elementary reactions
4 Quasiequilibrium chemical system is open system with time of parameter stabilization been
more less than time of changing of external conditions
Necessary and sufficient condition of chemical equilibrium is equality between sum of velocities of
elementary reactions with getting of some compound and sum of velocities of elementary reactions
with expenses of this compound for all compounds of system
For system with three compounds
A
B C
in the case of detailed equilibrium
(S=[A]+[B]+[C]) A C C B B A A B B C C Ak k k k k k
B A C A
B A C A A B C A B A A CA
Sk k
k k k k k k
A B C B
A B C B BA C B A B BCB
Sk k
k k k k k k
B C A C
B C A C C B A C B C C AC
Sk k
k k k k k k
For this system in the common case of equilibrium
vBA vAB vCA
vAC
vBC
vCB
249
P138
SYNTHESIS STRUCTURE AND THERMAL PROPERTIES OF
PROPYLENE OXIDE CARBON DIOXIDE AND L-LACTIDE
TERPOLYMERS
ZN Nysenko1 EE Said-Galiev
1 YaE Belevtsev
2 SI Daineko
2 MI Buzin
3 GG Nikiforova
4
AM Sakharov1
1 - NDZelinsky Institute of Organic Chemistry of the Russian Academy of Sciences Moscow
Russia
2 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Physical Chemistry Moscow Russia
3 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Academy of sciences Polymer Physics Moscow Russia
4 - ANNesmeyanov Institute of Organoelement Compounds of Rusian Academy of Sciences
Polymer Physics Moscow Russia
Poly(propylene carbonate) (PPC) is a sustainable polymer that undergoes complete ash-free
incineration accompanied by the formation of CO2 and H2O PPC is prepared by copolymerization
of propylene oxide (PO) with CO2 and it exhibits attractive physical and mechanical properties
responsible for its potential practical applications It is known that ester units introduction into a
polymer chain promotes increasing its biodegradability
Copolymers with different L-lactide concentrations were synthesized in the presence of zinc adipate
The combination of 1Н
13С and 2D
1Н-
13СHMBC NMR DSC FT-IR spectroscopy and GPC
study results allows one to assume that copolymerization of СО2 PO and L-lactide yields to
partially crystalline terpolymers composed of propylene carbonate blocks combined with L-lactic
acid blocks and may be depicted by segment II of structure represented onto Scheme
The synthesis of the terpolymers is not aggravated by side reactions No inversion of the
configuration of L-lactide occurs during its addition to the polymer chain and the copolymer
possesses optic activity that depends on the L-lactide concentration in its chain All possible types
of the PO addition (head-to-head head-to-tail and tail-to-tail) where head-to-tail addition
predominates are found in the propylene carbonate blocks L-Lactic acid content increase was
shown to be accompanied with elevation of terpolymers onset degradation temperature values
The research was supported by the Russian Ministry of Education and Science (Contract No
14513110139)
250
P139
SIMPLE PRECURSORS FOR THE REGIOSELECTIVE SYNTHESIS OF
METHYLENE-EXPANDED ANALOGUES OF C-NUCLEOSIDES
VK Brel1 AV Samet
2 LD Konyushkin
2 VV Semenov
2
1 - AN Nesmeyanov Institute of Organoelement Compounds
2 - N D Zelinsky Institute of Organic Chemistry
Nucleosides with heterocyclic base linked to sugar through CndashC bond instead of CndashN attachment in
natural nucleosides attract much attention because of their chemical and enzymatic stability
Compounds with methylene group inserted between the ring oxygen and the carbon atom linked to
the base moiety are considered as ring-expanded (six-membered ring) analogues of nucleosides
(Figure 1 A) Several of these molecules showed potent antiviral and antitumor activity
We have developed the synthesis of C2 chiral derivatives of
dihydrolevoglucosenone 1a 2a and 3ndash7 as simple precursors for
preparation of methylene-expanded C-nucleosides (A) using pyrolysis of
cellulose as a key step followed by hydrogenation of LG and
introduction of vinyl and ethynyl fragments to 2-position
The opening of 16-anhydrohexitols acetal ring could be used for transformation of derivatives 3ndash7
into methylene-expanded C-nucleosides (Figure 1 A)
O
O
O
O
O
OH
CH
O
O OH
CH
O
O
OH
CH2
O
O OH
CH2
O
O OH
O
N R
O
O OH
N
N
N
CH2Ph
++
LG
Cellulose
7 2b
2a
1b
1a
DLG
stainless steel
autoclave
2 PdC (Sibunit)
EtOAc 40o
20 bar 8 h
6
23
15
4
O
O
O
THF 40o 2 h
CH CMgBr CH2 CMgBr
63
48
85
Et2O rt 2 h
38
42
Et2O
-40o 3 h54-75
84
H2O rt 1 h
Cu(OAc)2
PhCH2N3
RC N+
O-
R
3 Ph
4 p-Me-Ph
5 p-F-Ph
6 Ac
O
OH
C
12
34
5
6
H e t
A
F ig u re 1
251
P140
SYNTHESIS AND BIOLOGICAL EVALUATION OF
FURANOALLOCOLCHICINOIDS
ES Schegravina1 YuV Voitovich
1 NS Sitnikov
1 VI Faerman
1 VV Fokin
1 H-G Schmalz
2
S Combes3 D Allegro
4 P Barbier
4 IP Beletskaya
5 EV Svirshchevskaya
6 AYu Fedorov
1
1 - Department of Organic Chemistry Nizhny Novgorod State University Gagarina av 23 Nizhny
Novgorod 603950 Russian Federation
2 - University of Cologne Department of Chemistry Koln Germany
3 - Institut Paoli-Calmettes Aix-Marseille Universite Laboratory of Integrative Structural and
Chemical Biology Marseille France
4 - Aix-Marseille Universit INSERM UMR_S 911 CRO2 F-13005 Marseille France
5 - MVLomonosov Moscow State University Department of Chemistry Moscow Russian
Federation
6 - Shemyakin-Ovchinnikov Institute of Bioorganic Chemistry RAS Moscow Russian Federation
A series of conformationally flexible furan-derived allocolchicinoids was prepared from
commercially available colchicine in good to excellent yields using a three-step reaction sequence1
Compounds containing a hydroxyl group in the pseudo-benzylic position of the furan side chain
exhibited high cytotoxicity toward epithelial and lymphoid cell lines (AsPC-1 HEK293 and Jurkat)
in the nanomolar concentration range
In vivo studies also demonstrated significant activity of compounds bearing a hydroxymethyl
fragment in the α-position of the furan ring against the tumor growth without symptoms of neuro-
toxicity
Acknowledgment
We thank the Russian Foundation for Basic Research (projects 14-03-91342 and 12-03-00214-a)
The Ministry of Education and Science of The Russian Federation (project 46192014K) The
research is partly supported by the grant 02В49210003 of The Ministry of Education and
Science of the Russian Federation to Lobachevsky State University of Nizhni Novgorod
References
1 Voitovich YuV Sсhegravina ES Sitnikov NS Faerman VI Fokin VV Schmalz H-G
Comes S Allegro D Barbier P Beletskaya IP Svirshchevskaya EV Fedorov AYu
Synthesis and biological evaluation of furanoallocolchicinoids J Med Chem 2014 (submitted)