авторефераты диссертаций БЕСПЛАТНАЯ БИБЛИОТЕКА РОССИИ



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Russia, Kazan, 420088, Arbuzov str., 8, A.E. Arbuzov Institute of Organic and Physical Chemistry The design of various molecular devices is a top of current interest during recent decades. The transition metal complexes are suitable building blocks for energy and electron transfer processes based N molecular devices such as logic gates, molecular sensors and mo N lecular wires. Such devices consist of three parts: donor, acceptor N n+ Me and bridging ligand as a spacer. Transition metal ions and com N plexes can be used as a donor and an acceptor. Organic com- N pounds with preorganized binding groups can serve as a matrix for N SO3 formation of these molecular devices. p-Sulfonatotiacalix[4]arene -O3S (STCA) is able to bind positivly charged transition metal com- -O3S SO3 plexes in the outer sphere complexation mode owing to the pres ence of cavity and charged groups on the upper rim. Moreover S phenolate groups on the lower rim are able to coordinate d- or f- S S S OH OH metal ions. So, STCA is a convenient matrix for polynuclear com- O O plex formation, and enable to develop conditions for metal-to- n+ Me metal energy and electron transfer. One of the metal centers of dinuclear complexes is included into the cavity of calixarene as charged metal complex and another one is bound through the in ner sphere coordination with the lower rim. The pH and concentration conditions of dinuclear com plex formation, where [Me(dipy)3]n+ are complexes of Co(III) and Ru(II) have been selected. Metal ions bound with the lower rim are d- or f- ions: Fe(III), Ru(III), Gd(III), Eu(III), Tb(III). The forma tion of such dinuclear complexes was confirmed by various techniques: absorbance spectroscopy, pH-metric titration, nuclear magnetic relaxation, NMR spectroscopy. The mutual effect of both metal centers fixed on the upper and lower rims of calixarene platform have been evaluated from the photophysical, photochemical and electrochemical behavior of these complexes with the use of various techniques.

We thank RFBR (grant N 07-03-00282) and BRHE (Y3-C-07-15) for financial support.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 POLYOXOMETALATE CLUSTER COMPLEXES – A NEW TYPE OF HYBRIDE SYSTEMS IN COORDINATION AND SUPRAMOLECULAR CHEMISTRY Sokolov M.N.a, Kalinina I.V.a, Cadot E.b, Fedin V.P.a a Nikolayev Institute of Inorganic Chemistry, Pr. Lavrentyeva 3, 630090 Novosibirsk, Russia b Versailles University, Institut Lavoisier, 45 av. Etats-Unis, 78035 Versailles, France Coordination of chalcogenide clusters to the polyoxometalate anions gives rise to a new type of co ordination compounds, with both cluster and polyoxometalate components in the same structure.

For example, the trivacant ion [AsW9O33]9- reacts with incomplete cuboidal clusters [M3S4(H2O)9]4+ (M = Mo, W) in 2:1 molar ratio, to give new hybrid complexes {[AsW9O33]2[M3S4(H2O)6]}14- which further dimerize through supramolecular S…S contacts and hydrogen bonds. They act as macrolygands towards Ag+ and Cu+, giving, for example, highly stable {Ag2[AsW9O33]2[M3S4(H2O)6]}226- By incorporation of Pd(0) and Ni(0) heterometal complexes {[AsW9O33]4[Mo3PdS4(H2O)5]2}28– and {[AsW9O33]4[Mo3Ni’0.5S4(H2O)5]2}28– were also prepared.

Under more drastic conditions {[AsW9O33]2[M3S4(H2O)6]}14- undergoes a unique rearrangement with the formation of a closed-Dawosn-type [AsW15Mo3O54S4(H2O))3]11-. This is the first example of direct incorporation of a cluster unit into a polyoxometalate framework, and the first example of a stable POM structure with as many as four chalcogen atoms substituting for oxygens. In a similar way, starting form [Mo3O2S2(H2O)9]4+, [AsW15Mo3O56S2(H2O))3]11-, was obtained. A vast family of mixed oxo/sulfido bridged Dawson-type complexes [EW15M3O59-xQx]n- (E = As, Sb…;

M = Mo, W;

Q = S, Se;

x = 1–4) with unique properties is anticipated.

Synthesis, structure and reactivity of theses compounds will be presented.

Fig. 1. Structure of [AsW15Mo3O54S4(H2O))3]11– This work was supported by Russian Foundation for Basic Research (grant 0603-32831a) and by Presidential Grant (MD-7072.2006.03).

2332 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SYNTHESIS AND BINDING PROPERTIES OF SOME LOWER RIM FUNCTIONALIZED THIACALIXARENES Solovieva S.E.a, Kleshnina S.R.a, Kluchnikov Ya.O.b, Gubaidullin A.T.a, Latipov Sh.K.a, Antipin I.S.ab, Konovalov A.I.a a A.E.Arbuzov Institute of Organic & Physical Chemistry,420088, Arbuzov str., 8, Kazan, RUSSIA b A.M.Butlerov Chemical Institute, Kazan State University, 420008, Kremlevskaya str., 18 Kazan, RUSSIA Thiacalixarenes are one of important macrocyclic molecules as hosts for binding neutral and charged molecules. Thiacalix[4]arene were found to bind metal ions without introduction of sup plementary ligating groups at the lower or upper rims owing to the coordination of the bridging sul fur atom with metal ions. In this report the results of the study liquid-liquid extraction of alkali and alkaline earth metal ions and lantanides picrate salts by some lower rim substituted calixarenes will be discussed in order to evaluate the influence of steric and electronic properties of peripheral sub stituents (R, R1). Some synthesized thiacalix[4]arenes and their alkali metal picrate complexes were investigated by X-ray and the differences of molecular packing and interatomic distances were dis covered.

R R R R R R R R R R1 R O O R 1O S S S S S S O O S S O R R1 O OR S S S S R O OO O 1R R R1 R R 1 R1 R R 1,3-alternate Cone Paco Acknowledgements – The work was supported by RFBR (grant N 07-03-00834), US DOE (RUC2-20010-MO-04).

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 PHYSICO-CHEMICAL AND BIOLOGICAL PROPERTIES OF SUPRAMOLECULAR SYSTEMS BASED ON N,N- DIMETHYL-N,N-DIALLYLAMMONIUM CHLORIDE WITH METHYLMETACRILATE AND METHACRYLIC ACID Staroverova I.N.a, Maksimov V.I.a, Zaitsev S.Yu.a, Kordonskay M.A.a, Korchikova A.V.a, Glagolev N.N.b, Os`kina O.Yu.b, Tcherkachyn M.I.b a FGOY VPO “Moscow state academy of veterinary medicine and biotechnology named by K.I.Skryabin”, Ak. Skriabin str.23, Moscow b N.N. Semenov Institute of Chemical Physics RAS, Moscow, Kosygin str., Polymers and copolymers of diallyl row are widely used as flockulators for the raw-water purifica tion, in cellulose-paper industry as antistatics by production of high quality papers and other field of industry. Special attention is devoted to the antistatic and antibacterial properties of polymers based on N,N-dimethyl-N,N-diallylammonium chloride. The properties of these polymers make them suitable for the application in the textile industry1. These properties are “activating” due to the su pramolecular organization and interactions of polymers and copolymers N,N-dimethyl-N,N diallylammonium chloride with proteins of viruses and bacteria, leading to the charge conversion of the cell membranes.

The aim of this work is the study of antistatic and thermal properties of the copolymers based on the N,N-dimethyl-N,N-diallylammonium chloride (DMDAAC) with methylmetacrilate (MMA) and methacrylic acid (MAA) monomers.

For the fulfillment of this task the copolymers with a different ratios of comonomers DMDAAC:MMA and DMDAAC:MAA (from 1:0,5 till 1:3) have been synthesized. The structure of the obtained copolymers has been studied by means of NMR-spectroscopy. All the obtained samples have been “destructed in a multistep manner” that has been shown by thermo-gravimetric method.

Thermal stability and thermo-oxidative stability have been higher for the copolymers with the monomer ratio DMDAAC: MMA in the range of 1:1 – 1:1,5. Comparison of antistatic properties of these copolymers have been resulted by the charge kinetics according to a method2. It has been proved that copolymers with higher molecular mass possess the best antistatic properties.

Thus the obtained copolymers possessing antistatic and antibacterial properties due to their su pramolecular organization and special interactions, are promising for application in the textile in dustry.

References 1. N.M.Boyarkina, V.V.Krutchkov, E.S.Parchamovitch, Plastic mass, 1987, 17-19, 8.

2. I.N. Staroverova, S.A. Krylova, D.S.Lychnikov, Electrization of woolen and half-woolen fabrics and natural fur: The Manual.-M.: Publ. Rus. Econ. Acad., 2006, 104.


SYNTHESIS AND STUDY OF COMPLEXATION ABILITIES Stoikov I.I.a, Zhukov A.Yu.a, Ushkova E.A.a, Ibragimova D.Sh.a, Antipin I.S.a, Konovalov A.I.a a Kazan State University, A.M.Butlerov Chemistry Institute, Russia, 420008, Kazan, Kremlevskaya, Design of “smart” molecules with functions of molecular recognition of important biological sub strates is necessary step in a study of programmed intellectual materials. Modification of macrocyc lic molecular platform is a frequently used way to construct receptor structures which allows attain ing needed orientation of the binding centers. Amide fragment is the most interesting for creation intellectual receptor structures based on thiacalix[4]arenes molecular platform, which combines in its structure the binding centers of various kinds.

In order to create stereoisomers of cone-, partial cone- and 1,3-alternate – p-tert butylcalix[4]arenes, which have amide and ester fragments in lower rim, interaction of those amines with tetraethers of thiacalix[4]arenes was investigated.

R R R H H H N N N R O O O O O O S S S S S S S S S S S S O O OO O O OO O O O O H O HN O O H O O N N N O NH HN HN H N R H N R R R H R R R R R The structure of synthesized calix[4]arenes were characterized by complex of physical methods:

H and 13C NMR, IR spectroscopy and ESI mass-spectrometry.

Stereoisomers of synthesized compounds containing carbomoyl group were studied as mole cules-receptors for cations of s-alkali, p- (Al3+, Pb2+) and d- (Ag+, Fe3+, Ni2+, Cu2+, Co3+, Hg2+, Cd2+) – metals. Constants of extraction and stoichiometry of thiacalix[4]arenes’ complexes with metals were calculated from data of extraction. Binding affinity and selectivity was shown to de pend on macrocycle configuration and the nature of binding centers.

The financial support from RFBR (06-03-32160), CRDF (RUC1-2825-KA-06), joint program of CRDF and Minis try of science and education of RF “Fundamental researches and higher education” (REC-007) is gratefully acknowl edged.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 VIBRATIONAL MODES IN DIHYDROGEH BONDED SUPRAMOLECULAR SYSTEMS Tsupreva V.N., Filippov O.A., Garbuzova I.A., Faershtein E.G., Epstein L.M., Shubina E.S.

A. N. Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences Vavilov str. 28, 119991 Moscow, Russia The direct evidence of dihydrogen bonded complexes formation in solution obtained based on the IR spectroscopy and quantum chemical calculations.

The spectral characteristics of dihydrogen bonded complexes (DHB) of EH4– hydrides (E=B, Al, Ga) with the various Bronsted acids were studied by DFT(B3LYP) method. Normal coordinate analysis and potential energy distribution for the vibration frequencies of DHB complexes reveals the specific mode corresponding to H-H vibrations in DHB and showed to be only H-H stretch im pact. The position of this band is 350-230 cm-1 and increases when increasing reactants strength.

The analysis of IR spectra of DHB’s of Bu4NBH4 with OH and NH proton donors (CFH2CH2OH, CF3CH2OH, (CF3)2CHOH, PhOH, indole) in CH2Cl2 and (CH2Cl)2 solutions allows to assign all bands of DHB complex. Changes in spectra of reactants – appearing of OH and BH bonded bands which are common indicator for DHB formation and changes in deformation vibra tions of partners were in agreement with calculated ones. Bands in low frequency range were in special attention and a new band related to H…H stretch in DHB was located. The low temperature study shows, that the intensities of the new H…H band increase when the temperature decreases.

This indicates shift for the H-bonding equilibrium to the DHB complexes upon cooling.

With the increase of the proton donating ability of XH-acid the H…H stretch vibration shifts to the high-frequency range. The isotopic effect on the new H-H stretch was studied.

This work was supported by RFBR (№07-03-00739), INTAS YSF (06-1000014-5809).

2336 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, COMPARATIVE STUDY OF THE LIPASE ACTIVITY IN SUPRAMOLECULAR POLYMER COMPLEXES Tulskaya E.V., Zaitsev S.Yu.

Moscow state academy of veterinary medicine and biotechnology, Ak. Skriabin str.23, Moscow A study of lipase activity in supramolecular systems based on polyelectrolytes in important both in fundamental and applied aspects, taking into account their broad application in medicine, biotech nology, food and textile industry. The main advantages of immobilizations are increasing enzyme stability by denaturative environmental conditions and other technological properties, such as mul tiple usage and simple purification from the reaction mixture.

The aim of this work is the study of enzyme activity of lipase from Hog pancrease and lipase from Mucor javanicus in the presence of polyelectrolytes PSS and PAMA.

Lipase activity was measured by potentiometric titration method in the presence of PSS and PAMA at ratios lipase: polymer from 1:1 till 1:100 at pH 7,0 and 25°C. The highest lipase H. p. ac tivity was shown by ratio lipase:PAMA=1:10 (94%). In the case of PSS the maximal lipase (H. p.) activity was found for ratios 1:10 and 1:100 (117% and 115% respectively).

The gradual increase in lipase (M. j.) activity (from 96% till 116% of was shown in the presence of PAMA by increasing relative polymer concentration (from 1:1 till 1:100). The highest lipase ac tivity (152%) was found in the complexes with PSS at ratio lipase:polymer=1:1.

This lipase from M. j. seems to be more promising for further application due to its higher activ ity in these supramolecular polyelectrolyte systems, as well as – higher stability to denaturation.

The obtained results are important for optimization of biotechnological and biochemical proc esses with application of immobilized enzymes;

their practical importance proved by applications for patents positive decision from № 2006111373 from 10.04.2006 and № 2006111374 from 13.02.2007.

This work was supported by RFBR and Rector of MSAVMB.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STUDY OF CROWN-ETHER ANNELATED STYRYL DYES AS LIGHT-UP PROBES FOR DOUBLE-STRANDED DNA Tulyakova E.V.a, Ihmels H.b, Li H.b, Fedorova O.A.a a Chemistry Department, M. V. Lomonosov Moscow State University, 119992, Moscow, Russia b Organische Chemie II, Universitt Siegen, Adolf-Reichwein-Str.2, 57068 Siegen, Germany The cyanine dyes, in particular the styryl dyes, are a well-investigated class of synthetic compounds which continues to be of significant interest from a viewpoint of supramolecular chemistry and ap plications in the life sciences. One particularly important application involves their propensity to bind to double-stranded DNA by intercalation and the resulting large fluorescence enhancement upon binding. The design of styryl dyes which may not only constitute light-up probes for biomac romolecules, but which also incorporate functional moiety for participation in chemical or catalyti cal reactions is a highly topical research area nowadays. Along these lines, we proposed that the introduction of crown ether moiety to a styryl dye would allow to increase the interaction with the DNA, because the crown ether may assist the counter-ion release from the DNA grooves by ion complexation. To further assess structure-property relationships in styryl dye–DNA recognition, the binding properties of selected styryl dyes with varying crown-ether fragment with calf thymus DNA were studied. Binding of the probes to the DNA was examined by viscosimetry, photometric and spectrometric titrations, and thermal denaturation studies. The results give evidence that the major binding mode for monostyryl dyes 1-4 is intercalation, whereas the binding mode for bis-styryl dyes 5-6 is minor-groove binding. The data clearly indicate that pyridinium derivative 1a stabilizes the DNA duplex to a marginal extent, whereas the addition of quinolinium, benzothiazolium, and acrid inium derivatives 2, 3, 4 leads to a significant stabilization of the DNA duplex. The resembling ef fect was observed for isomeric bis-styryl dyes 5a, 5b, 6a, and 6b. Notably, the binding of most of the dyes leads to a fluorescence enhancement by a factor of up to 78 upon binding to the biomac romolecules.

Acknowledgements. Generous financial support from the Deutscher Akademischer Austausch Dienst (A-05-56984), Russian Science Support Foundation, supporting grant for talented students, PhD students and young scientists 2006 of M.V. Lomonosov Moscow State University, RFBR (05-03-32268, 06-05-32899) is gratefully acknowledged.

2338 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, MONO-, DI- AND TETRA- MERCAPTODERIVATIVES OF THIACALIX[4]ARENES Tyuftin A.A.a, Solovieva S.E.a, Galiullina L.F.a, Lysenko K.A.b, Antipin M.U.b, Antipin I.S.a, Konovalov A.I.a a A.E. Arbuzov Institute of Organic and Physical Chemistry KazCS RAS, Russia 420088, Kazan, Arbuzov str. 8. E-mail:antyuf@iopc.knc.ru, svsol@iopc.knc.ru b A.N. Nesmeyanov Institute of Organoelement Compounds RAS 119991, Moscow, Vavilova str. 28, Russia Thiacalix[4]arenes (TCA) 1 are next member of calixarene family. Special interest has focused on using TCAs as suitable building blocs, multidentate preorganized macrocyclic type ligands, precur sors for creation of supramolecular architectures and much another applications in nanotechnology and chemistry. Free OH groups on TCA (2 – 6) can be modificated by different functional groups and are able to coordinate metal ions. Thiacalixarenes with narrow rim mercapto substituents (5, 8) are potential precursor molecules for metallocages, heavy metal ion sensors, nanodevices, new building blocks for nanonetworks and other applications.


R1=R2=R3=R4=H 7 X=S;

R1=R2=R3=R4=(CH2)nSC(O)CH 2 X=S;


R4=CH2CH2SC(O)CH3 8 X=S;

R1=R2=R3=R4=(CH2)nSH, n=2- 3 X=S;


R2=R4=CH2CH2SC(O)CH 9 X=S;

R1=R2=R3=R4=(CH2)3SC(NH2)2Br 4 X=S;



R4=CH2CH2Br 5 X=S;


R4=CH2CH2SH Synthesis and structure of new compounds are discussed. Elucidation of their structure was made by one and two dimensional NMR spectroscopy (1D NOE;

2D HSQC, HMBC, COSY, ROESY), MALDI-TOF MS, IR spectra and elemental analysis. Some molecules structure were assigned by X-ray analysis.

The work was supported by RFBR (grant N 07-03-000834).

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 STRUCTURE AND PROPERTIES OF THE SUPRAMOLECULAR DONOR-ACCEPTOR COMPLEXES INVOLVING BIS(18-CROWN-6)STILBENE Ushakov E.N.a, Vedernikov A.I.b, Kuz’mina L.G.c, Alfimov M.V.b, Gromov S.P.b a Institute of Problem of Chemical Physics, Chernogolovka 142432, Russia, eushakov@icp.ac.ru b Photochemistry Center, Novatorov str., 7A, Moscow 119421, Russia c Institute of General and Inorganic Chemistry, Leninskiy prosp., 31, Moscow 119991, Russia Bis(18-crown-6)stilbene S and bisammonium derivatives of -acceptor heterocyclic compounds V are able to form supramolecular charge-transfer (CT) complexes of the donor-acceptor and donor acceptor-donor composition in solution as well as in the solid state. The structures and properties of these complexes were comprehensively studied by absorption and fluorescence spectroscopy, NMR spectroscopy, and X-ray diffraction analysis.

O O O O O O O O O O O O R S + N + R N + N+ R R N (CH 2) + N R V3 N+ V V R + + R N N R + N+ R R N + R N + N R V V4 V R = (CH2) nNH3 + (n = 2,3) It was shown that the bimolecular complexes S · V have a pseudocyclic structure resulting from two-center host-guest interactions. In non-aqueous medium these complexes show a very high thermodynamic stability (the log K values in MeCN are between 8 and 10) and can act as selective fluorescent indicators for alkaline-earth metal cations.

The termolecular complexes S · V · S have a sandwich-type three-layered structure in which the acceptor molecule is located between two molecules of stilbene S. The main driving forces of the reaction leading to the donor-acceptor triads S · V · S were determined from the analysis of struc ture-property relationships.

Ultrafast excited state dynamics of the supramolecular CT complexes S · V1 and S · V1 · S (n = 3) was studied using transient pump-supercontinuum probe spectroscopy. The back electron-transfer reaction in S · V1 · S was found to occur twice slower in comparison with the bimolecular complex (1.08 ps vs 540 fs, MeCN).

This work was supported by the Russian Foundation for Basic Research, and the Division of Chemistry and Mate rial Sciences of the Russian Academy of Sciences.

2340 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SENSING OF ATP IN AQUEOUS SOLUTIONS AND MITOCHONDRIA BY A FLUORESCENT FLAVONOL PROBE Vadzyuk O.B.a, Yushchenko D.A.bc, Kosterin S.O.a, Duportail G.c, Mly Y.c, Pivovarenko V.G.b a O.V. Palladin Institute of Biochemistry, Kyiv 01030 (Ukraine) b Organic Chemistry Department, Chemistry Faculty, National Taras Shevchenko University of Kyiv, 01033 Kyiv (Ukraine) E-mail: pvg@mail.univ.kiev.ua c Photophysique des Interactions Biomolculaires, UMR 7175-LC1 du CNRS, Institut Gilbert Laustriat, Facult de Pharmacie, Universit Louis Pasteur, 67401 Illkirch (France) Despite the key role of adenosine-5’-triphosphate (ATP), no accurate method of determination of its local concentration in living cells is actually available. The determination of local ATP concentra tion and its changes with time in live cells is a complex problem not only due to the restricted space and/or time scale limitations, but also due to the selectivity required in the determination of this pe culiar anion. In this respect multi-channel 3-hydroxyflavone fluorescent probes might be effective tools for resolving the problem.

We demonstrate the formation of complexes between the tetra-anion ATP and 3-hydroxy-4’ (dimethyl-amino)flavone (FME). Two kinds of complexes are evidenced. The higher affinity 1: complex corresponds to a stacked configuration between the aromatic moieties of the two mole cules and leads to a strong hypochromicity of the absorption spectrum of the dye. The lower affinity (ATP)2-FME complex results in a strong increase of the fluorescence intensity (~ 20-fold), mainly due to the appearance of the anionic form of FME, as shown by the important red-shift (60 nm) of both excitation and emission spectra. The collected data indicates that this anionic form results from the deprotonation induced by the phosphate groups of the second ATP molecule1,2. In the presence of 250 mM sucrose, the interaction with the second ATP molecule appears to weaken the spectral effect, which nevertheless remains appreciable. This red shift of excitation spectrum together with a strong enhancement of fluorescence intensity due to the formation of the 2:1 complex should enable the quantitative evaluation of the ATP concentration in both physiological conditions and physio logical range. A first set of experiments appears promising to monitor the succinate-induced pro duction of endogeneous ATP in mitochondria.

[ATP], mM:

a 0 CH H3C Fluorescence Intensity N 0. 0. 0. 0. 0. 1. O O 2. H 4. O 350 400 450 500 Wavelength (nm) FME Figure. Fluorescence excitation spectra (a) of FME probe in 15 mM TRIS buffer pH 7.4. Emission wavelength is 555 nm. (b) Structure of the FME and (ATP)2-FME complex obtained by quantum chemical simulation.

References 1. V.G. Pivovarenko, O.B. Vadzyuk, S.O. Kosterin. J. Fluorescence, 2006, 16, 9.

2. V.V. Shynkar, A.S. Klymchenko et. al. J. Phys. Chem. B, 2004 108, 18750.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SYNTHESIS OF DIHYDROAZOLOPYRIMIDINE-CONTAINING CROWN-ETHERS Valova M.S., Ovchinnikova I.G., Fedorova O.V., Koryakova O.V., Slepukhin P.A., Rusinov G.L.

I.Ya. Postovsky Institute of Organic Synthesis of RAS, 620041 Ekaterinburg, GSP-147, Akademicheskaya Str., 22, Russian Federation. E-mail: fedorova@ios.uran.ru The approach to synthesis of dihydroazolopyrimidine-containing crown-ethers is developed. It was shown that depending on a ratio of chalcono-podand 1 and 3-amino-1,2,4-triazole various products were obtained. Heating in DMF chalcono-podand 1 (0.1 mol) and surplus 3-amino-1,2,4-triazole (0.3 mol) results in the formation of dihydroazolopyrimidine podand 2. Use equimolar ratio of re agents leads to an unusual crown-ether 3 bearing the dihydroazolopyrimidine fragment.

O O O 1 HN N HN N 2 H2N N Ph O Ph O H2N N DMF DMF O O O O O O O NN NN NN Ph N N N N Ph N Ph N 2 Work is executed with financial support of the Russian Foundation for Basic Research (grants № 06-03-33172, 06 03-08144, 07-03-96113) and the Presidium of the Russian Academy of Science (the project «Design of new su pramolecular structures containing heterocyclic fragments»).

2342 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, FUNCTIONAL DONOR TECTONS IN COORDINATION POLYMER CONSTRACTION Vatsadze S.Z., Manaenkova M.A., Semashko V.S., Medved’ko A.V., Schetinina O.M., Zyk N.V.

Chemistry Department, M.V.Lomonosov Moscow State University, Moscow, Russia, szv@org.chem.msu.ru The most exciting and promising way of design of new donor molecules is conjugation in one struc ture the central functional core and the peripheral donating units. Number and spatial arrangement of such donating units could be varied according to wish of ivestigator. Central core carries the functional property required for functional material, such as ability to absorb/emit light, magnetic properties, spin density, redox properties. In particular, are interesting those tectons which consist of endo-exo-dentating ligand and central metal(s) part. The chelating part of a ligand (endo) serves as clue to arrange an internal metal and a ligand, whereas exo-oriented donor groups are available for complexation to external metals. On application of such metalloligands to the synthesis su pramolecular architectures we suggest to call them “METALLOTECTONS”.



DONOR GROUPS In this report we will discuss examples of tectons known from literature as well as our own ef forts in design and synthesis of such molecules. Particularly, our attention will be drawn to tectons based on pyridine-containing formazanes, beta-diketones, cross-conjugated dienones, carboxyferro cenes, 3,7,-diazabicycl[3.3.1]nonanes, cupper helicates.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 INCLUSION COMPLEXES OF CUCURBIT[N]URILS WITH VIOLOGEN ANALOGUES AND STYRYL DYES: SYNTHESIS, STRUCTURE, STABILITY, AND PHOTOREACTIONS Vedernikov A.I.a, Sazonov S.K.a, Lobova N.A.a, Botsmanova A.A.a, Kuz‘mina L.G.b, Strelenko Yu.A.c, Howard J.A.K.d, Alfimov M.V.a, Gromov S.P.a a Photochemistry Center of the RAS, 7a Novatorov str., Moscow 119421, Russia;

e-mail: artem@photonics.ru b Institute of General and Inorganic Chemistry of the RAS, 31 Leninskiy pr., Moscow 119991, Russia c Institute of Organic Chemistry of the RAS, 47 Leninskiy pr., Moscow 119991, Russia d Chemistry Department, Durham University, South Road, Durham DH1 3LE, UK A series of new cationic unsaturated compounds – viologen analogues 1 and styryl dyes 2 having different N-substituents were synthesized and their complex formation with cucurbit[n]urils (CB[n], n = 7, 8) was studied in water and solid state using X-ray diffraction, NMR and electronic spectro scopies.

_ 2 ClO R h R CB[n] N+ +N + + (A = CH=CH) N R A N R + + H2O N N R R A 1: A =, 4,4'-CH=CH, 3,3'-CH=CH, 4,4'-CH2CH2, CB[n] · R = Et, (CH2)mNH3+ClO4-, (CH2)mSO3-, m = 2- OMe + OMe CB[8] + R OMe h OMe + N R N OMe RN + _ MeO OMe MeO N H2O N R R ClO + MeO MeO 2: R = Et, (CH2)3NH3+ClO4-, (CH2)3SO3 CB[8] · {2} Cucurbit[n]urils and compounds 1, 2 form stable inclusion complexes CB[n]·1(2) having pseu dorotaxane structures (lgK = 3.4–5.3). In the case of N-ammonioalkyl compounds, it was found the formation of hydrogen bonding between the NH3+ groups and the oxygen atoms of CB[n] portals increasing stability of the supramolecular complexes. Due to the larger cavity, CB[8] is able to form also stable termolecular complexes CB[8]·{1(2)}2, in which two guest molecules are arranged one under another. Compounds 1, 2, having the central C=C bond and being complexed with CB[n], undergo efficient photoinduced transformations such as reversible E–Z isomerisation in the case of viologen analogues, or [2+2]-photocycloaddition reaction (for n = 8) – in the case of styryl dyes.

These properties of the CB[n] complexes presume a possibility for the creation of optical systems for information storage and molecular machines operated by light.

This work was financially supported by the Russian Foundation for Basic Research, the Russian Academy of Sci ences, and the Royal Society of Chemistry (UK).


Kazan state technological university 420015 Kazan, K.Marksa It is known, that at the presence of basic nitriles isocyanates are capable to form the structures of the triisocyanurate character. During trimerization of isocyanates of a various structure by us the oppor tunity of formation supramolecular complexes trichlorophenylisocyanurate and heterogeneous ring compounds containing carboxylic atom of carbon (ethylencarbonate, e caprolactone) was found.

Synthesized compounds had crystalline structure, stability under normal conditions, at temperatures above melting points decaid on triisocyanurate and the relevant heterogeneous ring compound. At the same time, expansion of some composite ether rings, capable to form similar compound insert will allow to determine quantity of the triisocyanurate meshes, and probably to receive the crystals described by more an ordered structure.

In the submitted operation synthesis supramolecular complexes trichlorophenylisocyanurate and the composite ether rings distinguished by quantity of a cycle and hydrocarbonaceous radicals (в-butyrolactone, г-valerolactone, г-caprolactone) has been carried out. Influence of composition of an initial reaction mixture on structure of received molecular complexes is investigated. It is shown, depending on the content 3-chlorophenylisocyanate in an initial reaction mixture crystalline com pounds of a various structure are formed. So, in the case of the molecular complex of в hydroxyolactone and triisocyanurate compounds insert in which structure on one molecule tri chlorophenylisocyanurate it is necessary three molecules of the composite ether ring have been re ceived. Synthesis supramolecular complexes have been explored by methods of the X-ray diffrac tion, element analysis, differential scanning calorimetry. Character of melting of synthesized yields was explored, depending on composition of an initial reaction mixture. The melting temperature of the molecular complex triisocyanurate and, for example г-valerolactone at the equal a relation of reagents it has made 385 K. It was shown, that quantity composite ether a cycle influences, on structure of the supramolecular complex.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 INFLUENCE OF THE EXOGENOUS SUPRAMOLECULAR ADDITIVE «RIBAV»


FGOY VPO “Moscow state academy of veterinary medicine and biotechnology named by K. I. Skriabin”, Akad. Skriabin Str. 23, Moscow One of the modern biologically active preparations is «Ribav» which can be considered as «exoge nous» biological supramolacular system because it represents spirituous extract from roots of a gin seng and the mushrooms, containing a plenty of biologically active substances (amino acids, en zymes, vitamins, etc.). The given preparation is already widely and successfully used in animal in dustries as a highly effective growth factor and immunomodulator. However, its action on an organ ism of egg chickens is investigated only fragmentary, that especially concerns an influence of «Ri bav» on metabolic processes in an organism of a bird.

The aim of this work was to study influence of «Ribav» (as «exogenous» biological supramola cular system) on "protein" parameters of chicken blood (as «endogenous» biological supramolacu lar system).

This aim was realized by conducting of the special experiments with research of the biological materials (eggs, daily chickens of cross-country «Haiseks white », as well as blood received from these chickens). At realization of this study the experimental and control sets of eggs from one pa rental herd (215 days) stole up at observance of analogousness of parameters of eggs (into each group entered on 300 pieces). This work carried out in conditions of the farm "Kuchinsky". Before a bookmark to an incubator and at 19-th day we spent the aerosol processing an experimental batch of eggs from a spray solutions of a preparation which optimum concentration, have been certain in a number of the previous experiments. By results of biochemical researches, after «Ribav» action, in blood serum of daily chickens the contents of the general protein has increased on 10.5% in com parison with the control, and the level of activity of enzymes has increased: ALT – in 1.27-1. times, ACT – in 1.69-2.15 times;

-amilase – in 1.15-1.54 times, alkaline phosphatase – in 1.56 times.

The authentic tendency to increase in the contents in blood serum of these chickens of some impor tant proteins, such as albumins: preALB – on 23.6%, ALB – on 2.1%, postALB – on 13.6%, as well as globulins: TF – on 10.2%;

2 – on 17.7%, S2 – on 45.5%, 1 – on 9.1% (in comparison with control group of chickens). Development of bodies and tissues of daily chickens after «Ribav» ac tion in all experimental groups surpass the control. Zootechnical and economic parameters have also considerably improved in this case.

Thus, the obtained results of biochemical researches proved a positive «Ribav» influence (as «exogenous» biological supramolacular system) on "protein" parameters of chickens blood serum (as «endogenous» biological supramolacular system), as well as an optimization at young growth of the protein metabolism at a level of bodies and tissues. However, biochemical mechanisms of the specified processes still demand an explanation on the molecular and supramolacular levels.


Moscow State Technical N.E.Bauman University, Moscow, 2-ya Baumanskaya, 5, Russia Polinuclear copper(II) chelate complexes are known to exhibit high catalytic activity for oxidation of organic compounds with molecular oxygen, hydrogen peroxide and other oxidants. They poorly dissolve in organic solvents and usually are used as heterogeneous catalysts. In most cases polinu clear chelates are supported on solids to provide higher surface area. Anyway, supported samples show many times lower efficiency than the corresponding homogeneous catalysts. Super lattice of the photonic crystals provides an ambiguously opportunity for placing of supramolecular species such as polinuclear metal chelates. Interspheric voids within photonic crystallites are used in this work as microreactors to synthesize catalytically active copper chelate macromolecules based on phenyl hydrozoneimines of enamino ketones. The monomeric copper(II) chelates adsorbed within photonic crystallites undergo interspheric condensation with benzidine to yield polinuclear copper oligomeric molecules. The product of the topochemical synthesis was studied by FTIR spectros copy. The polinuclear copper(II) chelates are retained topologicaly inside the voids of the photonic crystals and extracted with no organic solvents. The samples obtained are catalytically active in adamantanon-2 oxidation with hydrogen peroxide. Liquid-phase oxidation of adamantanon-2 by (H)2(O)2 was studied in ethanol and acetone solutions at 40-60°C. The reaction kinetics were monitored chromatographically and spectrophotometrically (UV). The reaction was shown to be the two-step transformation. Lactone was the main product on the first stage of the oxidation. The con version of adamantanon-2 was about 90% after 1 h at 60°C. A small amount of a by-product (2-5%) also was formed. The nature of the solvent was found to play important role for the selectivity of the oxidation of adamantanon-2. The first step of the reaction seemed to be solvent independent.

Lactone forming on the first step in the presence of both acetone and ethanol is transformed by the following break of the C-O bond of seven-membered cycle to give carbonyl compound in the pres ence of acetone and the mixture of ester and carbonyl compound in the presence of ethanol.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 DESIGN OF SUPRAMOLECULAR CATALYTIC SYSTEMS FOR THE REACTION OF NUCLEOPHILIC SUBSTITUTION Zakharova L.Ya., Mirgorodskaya A.B., Zhiltsova E.P., Kudryavtseva L.A., Semenov V.E., Reznik V.S., Konovalov A.I.

A.E.Arbuzov Institute of Organic and Physical Chemistry, Kazan Research Center of the Russian Academy of Sciences, 8 Acad. Arbuzova Str., 420088 Kazan, Russian Federation, e-mail: lucia@iopc.knc.ru An approach for the design of supramolecular catalytic systems based on amphiphilic and poly meric amines showing the complex mechanism of the catalytic action similar to the enzyme cataly sis has been worked out. As a model reaction, nucleophilic substitution in carbon and phosphorus acid esters is studied. In these processes, amines can be involved as nucleophiles or homogeneous catalysts, thus taking part in the formation of the functional nanoaggregates. In this study, long chain aliphatic amines, branched polyethyleneimines (PEI) with different molecular mass (from to 50000), modified PEIs including hydrophobized ones, Polymin SK, and also polypropyleneimine dendrimer of the third generation were used. They are capable of multicentered binding the sub strates and participating in co-aggregation with other amphiphiles. As additional building blocks, surfactants (solubilization mechanism of the binding) and cyclophanes (inclusion mechanism) are explored. A diversity of nonionic, anionic, cationic including gemini surfactants and also their bi nary systems are studied. As macrocycles, cyclodextrins, calixarenes functionalized at the upper and lower rims, amphiphilic pyrimidinophanes with different cavity size are investigated. The for mation of catalytic systems in aqueous and nonaqueous (chloroform, ethylene glycol, mixed solvent water-DMFA) media are carried out by methods of the directed self-assembly and parallel control of the processes of self-organization and catalysis with the help of a number of techniques including NMR-, IR-, UV-vis-spectroscopy, dynamic light scattering, atomic force and polarization micros copy, conductometry, tensiometry, etc. A correction of the catalytic activity was fulfilled by means of the optimization of the composition of supramolecular systems, temperature and concentration conditions and so on. High efficiency of the catalysis is found to be due to synergetic effect caused by mutual influence of the components of the systems in the processes of the self-organization and catalysis. Based on this approach, effective supramolecular systems for nucleophilic substitution at carbon and phosphorus atoms are formed, which demonstrate polyfunctional mechanism of cataly sis, high efficiency (a more than 104-fold acceleration), substrate specificity at low concentration (0.00001-0.001 M) in mild conditions.

This work was supported by the Russian Foundation for Basic Researches, grants no. 07-0300392a.

Секция II Российско-индийский симпозиум по органической химии Руководители – академик О.М.Нефедов, профессор С.Чандрасекаран (S.Сhandrasekaran) Устные доклады 2350 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, RATIONAL DESIGN OF ENEDIYNES AND RELATED SYSTEMS Basak A., Kar M.

Department of chemistry, Indian Institute of Technology, Kharagpur, India Email: absk@chem.iitkgp.ernet.in Natural product chemistry has seen a rebirth in recent years. This revival is primarily because of the discovery in late eighties of molecules like enediynes with intricate structural features and fascinat ing mode of biological action. Some interesting features of these molecules include their complex architecture and thermal instability. It is this instability factor that has translated into a constant tus sle between the inherent decomposition processes and the synthesis of model compounds with suf ficient stability. This has imposed a great challenge to contemporary organic synthesis and the re searcher at the bench. Right from the time when the mechanism of biological action of enediynes was unravelled, methods to generate carbon-centred radicals under ambient conditions have become an active area of research. Bergman and Myers-Saito cyclization still remain at the centre stage while the rearrangement of bis-allenic sulphones to the thiophene oxide radical (Garratt-Braverman) has largely been overlooked. This lecture will highlight some of our recent results obtained with both enediynes and bis-propargyl sulphones.

H R R R X H Bergman Cyclization R R R H X H R R R X H Myers-Saito. R R R Cyclization H X.

. O Garratt O O B S S S O.

O O.

Braverman References 1. Kar, M.;

Basak A. Chem. Commun. 2006, 3818;

Roy, S.;

Basak. A. Chem. Commun. 2006, 1646;

Basak, A.;

Roy S.


Mandal, S. Angew. Chem. Int. Ed. Engl. 2005, 44, 132.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 ORGANIC MOLECULAR MAGNETS FROM HIGH-SPIN NITRENES Chapyshev S.V.

Institute of Problems of Chemical Physics, Russian Academy of Sciences, 142432 Chernogolovka, Moscow Region, Russia. E-mail: chap@icp.ac.ru Aromatic polyazides are of considerable interest as anti-cancer and anti-HIV compounds and as precursors of nitrogen-rich carbon nanomaterials and high-spin organic molecules. This report is devoted to the synthesis and photochemical transformations of new aromatic polyazides 1-6 into organic molecular magnets 7-11.

R N3 N3 N Cl Cl Cl Cl R N N N N3 N N3 N3 N R N3 N3 N3 N 1 N3 N N N3 N3 N N N N3 N R N R1 R2 N N N N N3 N N3 N3 N3 N N3 N 3 N3 N3 N N N3 N N 3 N3 N CN R N 3 h N R N N R N N Cl Cl Cl Cl R1 R2 N N N N N N N N N R N N N N N N N N 7 R N N N N N N N R The work was supported by the Russian Foundation for Basic Research (Project RFBR 05-03-32410).

2352 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SYNTHETIC STUDIES WITH CYCLCOPROPANE CARBOXYLATED SUGAR DERIVATIVES Haveli S.D., Ramu Sridhar P., Suguna P., Chandrasekaran S.

Department of Organic Chemistry Indian Institute of Science, Bangalore-560012, India A wide range of linear-fused perhydrofuro[2,3-b]pyran or furan ring systems are encountered in a number of biologically active natural product structures. A few approaches are available for the construction of this kind of fused motif;

these involve radical cyclization of substituted furans or pyrans, cycloadditions, intramolecular dehydration reactions, acid catalyzed cyclization of hy droxyacetals, and spontaneous intramolecular ketalisation of acyclic dihydroxyaldehydes. However, these strategies suffer from harsh reaction conditions, multi step reactions and low overall yield. We recently reported an efficient methodology for the synthesis of 2-C-branched glyco-amino-acids by ring opening of 1,2-cyclopropanecarboxylated sugar derivatives(1). Logically, a similar strategy can be utilized for the construction of fused perhydrofuro[2,3-b]pyran/furan ring systems by trapping the intermediate oxonium ion in an intramolecular fashion.

In this lecture an efficient method for the stereoselective construction of linear-fused perhydro furo[2,3-b]pyran motifs using NIS mediated ring opening and cyclization of 1,2-cyclopropanated sugar derivatives will be discussed (2). Studies related to a general method for the synthesis of fused perhydrofuro[2,3-b]pyrano--butyrolactone systems under similar reaction conditions using sugar derived 1,2-cyclopropanecarboxylic acids will also be presented.

References 1. P.Ramu Sridhar, K.Chinna Ashalu and S.Chandrasekaran, Organic Lett., 2004,6 1777-1779.

2. S.D.Haveli, P.Ramu Sridhar, P.Suguna and S.Chandrasekaran, Organic Lett., 2007,9,1331- ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 NOVEL MATERIALS FROM BILE ACIDS Maitra U.

Department of Organic Chemistry, Indian Institute of Science Bangalore 560 012, India (maitra@orgchem.iisc.ernet.in) Bile salts play important roles in a number of physiological functions, including cholesterol solubi lization and fat metabolism. My group has been working on the chemistry of a variety of bile acid analogues for over a decade. In this lecture a brief overview of our research on bile acid-derived molecular gels, dendrimers and novel materials will be presented.

A polymer bound fluorescent sensor A cholaphane with A gel-nanoparticle (left: no K+/right: with K+) two bound F– hybrid References 1. N. Vijayalakshmi and Uday Maitra, Macromolecules, 2006, 39, 7931.

2. S. Bhat and Uday Maitra, Chem. Mater., 2006, 18, 4224.

3. S. Nath and Uday Maitra, Organic Lett., 2006, 8, 3239.

4. S. Ghosh and Uday Maitra, Organic Lett., 2006, 8, 399.

5. P. Babu, D. Chopra, T.N. Guru Row and Uday Maitra, Org. Biomol. Chem., 2005, 3, 3695.

6. N.M. Sangeetha and Uday Maitra, Chem. Soc. Rev., 2005, 34, 821.

2354 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, TOTAL SYNTHESIS OF STRUCTRALLY NOVEL AND BIOLOGICALLY ACTIVE NATURAL PRODUCTS (Пленарный доклад на ХVIII Менделеевском съезде) Mehta G.

Department of Organic Chemistry, Indian Institute of Science, Bangalore 560012, India E-mail: gm@orgchem.iisc.ernet.in Nature, the master craftsman of molecules, creates almost an inexhaustible array of molecular enti ties, replete with myriad combination of rings, functionalities and stereochemical diversity. These natural products embody evolutionary experience in complex biological environment and invariably exhibit unique bioactivity profile. Consequently, natural products can serve as lead platforms for exploring a range of interactions in biological systems and to build diversity around their structures.

We have been interested in the synthesis of a variety of natural products that combine structural novelty and complexity with potential utility for human wellbeing. This lecture will highlight some of our recent accomplishments in the area of total synthesis that focus on simple, economical and diversity oriented approaches to natural products.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 ASYMMETRIC DESYMMETRIZATION:


Division of Organic Chemistry (Synthesis) National Chemical Laboratory, Pune 411 008, INDIA gp.pandey@ncl.res.in Asymmetric synthesis via enantiotopic differentiation of meso compound employing chiral reagents / catalysts is an attractive strategy for the synthesis of enantiomerically pure compounds. In the con text of our earlier interest in the synthesis of epibatidine (1);

a powerful analgesic (non-opioid, 200– 500 times more potent than morphine), we developed a strategy to obtain optically pure 7-azabi cyclo[2.2.1]heptan-2-one skeleton (2) via asymmetric desymmetrization of meso-5 using chiral alkoxide (4) as enantiotopic differentiating reagent. However, further development of 1 veined due to the detection of pronounced toxicity.

Cl H H N N O N 1 NaO Ph Ph Boc Boc NaO Ph N N O SO2Ph Ph O SO2Ph SO2Ph Scheme- Nevertheless, having developed a conceptually new and short strategy for the synthesis of 3, also endowed with attractive structural framework, we explored its synthetic potential for the synthesis of several important natural products and other useful compounds as shown in Scheme- Me NH N OH (-)-trans-aminocyclohexanol (+)-Ferruginine O NH2 NH HO OH OH [3] H2N OH OH OH OH (+)- Streptamine Conduramin A NH OH OH Ph C9H19 N H2N OH CH OH (+)-Prussin 2-deoxystreptamine Scheme- Concept and details of the synthetic endeavors will be presented.


Bioorganic Laboratory, Department of Chemistry, University of Delhi, Delhi – 110 00, India E-mail: virparmar@gmail.com Carbohydrates and nucleosides are among the most important biomolecules because of their crucial role in storage and transfer of metabolic energy and genetic information.

During he synthesis of tar geted nucleosides and their derivatives, selective manipulation of different hydroxyl groups in sugar moiety is always required. It is at this juncture that the nature’s catalyst “ENZYMES” come into the picture, the use of enzymes in synthetic sequences provides unique advantage of efficiency, regiose lectivity, stereoselectivity and environment friendliness. We have synthesized quite a few novel ribo- arabino-, pyrazolyl and triazolylnucleosides under a research program on synthesis of modi fied nucleosides as potential antiviral agents and have studied selective manipulation of their differ ent hydroxyl groups in the presence of lipases.

In addition, we have synthesized quite a few C- nucleosides containing bulky aromatic aryl groups instead of natural nucleobases. Further, we have synthesized small DNA fragments involv ing these C- nucleosides and have demonstrated that the nucleosides with biphenyl as a base cause local disruption of DNA-base stacking.

Detailed results of selective enzymatic acylation reactions, and synthesis and DNA-base stacking experiments will be discussed during the presentation.

The financial support from Nucleic Acid Research Center, University of Southern Denmark and Department of Bio technology (DBT, New Delhi, India) is gratefully acknowledged.

References 1. A.K. Prasad, M.D. Sorensen, V.S. Parmar, J. Wengel.Tet. Lett. 1995, 36, 2. S.K. Sharma, S. Roy, R. Kumar, V.S. Parmar. Tet. Lett. 1999, 40, 3. A.K. Prasad, Himanshu, A. Bhattacharya, C.E. Olsen, V.S. Parmar. Bioorg. Med. Chem. 2002, 10, 4. I. Singh, W. Hecker, A.K. Prasad, V.S. Parmar, O. Seitz. Chem. Commun. 2002, 5. C. Beuck, I. Singh, A. Bhattacharya, W. Hecker, V.S. Parmar, O. Seitz, E. Weinhold. Angew. Chem. Int. Ed. 2003, 42, 6. A.K. Prasad, S. Roy, R. Kumar, N. Kalra, J. Wengel, C.E. Olsen, A.L. Cholli, L.A. Samuelson, J. Kumar, A.C.

Watterson, R.A. Gross, V.S. Parmar. Tetrahedron 2003, 59, 7. A. Bhattachary, A.K. Prasad, J. Maity, Himanshu, Poonam, C.E. Olsen, R.A. Gross, V.S. Parmar. Tetrahedron 2003, 59, 8. N. Kalra, M.C. Parlato, V.S. Parmar, J. Wengel. Bioorg. Med. Chem. Lett. 2006, 16, 9. V. Kumar, V.S. Parmar, S.V. Malhotra. Tet. Lett. 2007, 48, 10. A.K. Prasad, N. Kalra, Y. Yadav, R. Kumar, S.K. Sharma, S. Patkar, L. Lange, J. Wengel, V.S. Parmar. Chem.

Commun. 2007, (Advance Article) DOI: 10. 1039/b618426l ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 SYNTHETIC APPROACHES TOWARDS GLYCOSIDASE INHIBITORS Ramana D.V., Rawal G.K., Vankar Y.D.

Department of Chemistry, Indian Institute of Technology Kanpur 208016, India Synthetic approaches towards the following pyrrolidine and piperidne based glycosidase inhibitors will be discussed. Newer synthons, reagents, reagent systems have been developed en route to these biologically important molecules. These will also be discussed during the presentation.


Department of Chemistry, Indian Institute of Technology Kanpur-208016 India Enantioselective reactions catalyzed by organic molecules (asymmetric organocatalysis) is an emerging area in asymmetric synthesis. In this process, a organic reaction is catalyzed by sub stoichiometric amount of chiral organic compounds which do not contain a metal atom. Thus, one can avoid toxicity of metals, making the process environment friendly. These reactions seldom suf fer from the requirement for inert conditions frequently needed in metal chemistry. Although the initial reports appeared in the literature several years ago, the area of asymmetric organocatalysis became a main focus of research only recently. In this lecture, I will summarize some of our work on enantioselective C-C bond formation reaction using small chiral organic molecules. I will stress upon mainly two reactions;

enantioseletrive aldol1,2 and enantioselective 1,4-addition. O R Ph N Ph OH O H N O O OH H + R H R 99% ee The work was supported by grants from Department of Science & Technology, Government of India.

References 1. M. Raj, V. Maya, S.K. Ginotra, and V.K. Singh, Org. Lett. 2006, 8, 4097.

2. V. Maya, M. Raj, and V.K. Singh, Org. Lett. 2007, 9, 0000.

3. V. Maya and V.K. Singh, Org. Lett. 2007, 9, 1117.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 RECENT TRENDS IN MODERN INDUSTRIAL SYNTHESIS (Пленарный доклад на ХVIII Менделеевском съезде) Yadav J.S.

Indian Institute of Chemical Technology, E-mail: yadav@iict.res.in Over the past two decades, the concerns over environmental issues have been at the helm of affairs.

The global warming has been attributed to indiscriminate use of natural resources. The chemical community has taken the responsibility of bringing down their contribution to this ‘unusual warning phenomenon’ by diverting the resources to development of a new theme called “Green chemistry”.

The whole objective has been to cleanup the waste, material balance, use of non conventional but easily recoverable solvents, microwavesynthesis, avoiding unnecessary derivatizations and protec tive groups, development of new multifunctional synthons and catalysis besides several other ef forts. Our research group also has played its role in designing ‘novel green protocols’, development of APIs in non-conventional solvent media, microwave and ionic liquid chemistry, multicomponent reactions and catalytic asymmetric synthesis of biologically relevant compounds. The present lec ture will cover these aspects of these areas of research.

References 1. Yadav, J.S., Reddy, B.V.S., Baishya, G. J. Org. Chem. 2003, 68, 7098-7100.

2. Yadav J.S., B.V.S. Reddy, K.V.Rao, K.S. Raj, A.R.Prasad, S. K. Kumar, A. C. Kunwar, P. Jayaprakash, B. Angew.

Chem. Int. Engl. 2003, 42, 5198.

3. Yadav, J.S., Reddy, B.V.S., Srinivas, C., Rajasekhar, R.K. J. Org. Chem. 2003, 68, 2525-2527.

4. Yadav, J.S., Reddy, B.V.S., Bhaishya, G. Green Chemistry 2003, 5, 264-266.

5. Yadav, J.S., Reddy, B.V.S., Basak, A.K., Narsaiah, A.V. Green Chemistry 2003, 5, 60-63.

6. Yadav, J.S., Reddy, B.V.S., Basak, A.K., Venkat Narsaiah, A. Tetrahedron Lett. 2003, 44, 1047-1050.

7. Yadav, J.S., Reddy, B.V.S. Tetrahedron Lett. 2002, 43, 1905-1907.

8. Yadav, J.S., Reddy, B.V.S., Shubashree, S., Sadashiv, K., Naidu, J.J. Synthesis (14), pp. 2376-2380, 2004.

9. Yadav, J.S., Subba Reddy, B.V., Sridhar, P., Reddy, J.S.S., Nagaiah, K., Lingaiah, N., Saiprasad, P.S. European Journal of Organic Chemistry (3), pp. 552-557, 2004.

10. Yadav, J.S., Reddy, B.V.S., Saritha Raj, K., Prasad, A.R. Tetrahedron 59 (10), pp. 1805-1809,2003.

2360 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, SYNTHESIS OF NEW BIOLOGICALLY ACTIVE COMPOUNDS ON THE BASIS OF TERPENOIDS Yunusov M.S., Flekhter O.B.

Institute of Organic Chemistry Ufa Research Center of the Russian Academy of Sciences, 71, prosp. Oktyabrya, 450054 Ufa, Russian Federation. Fax: +7 3472 356066. E-mail: obf@anrb.ru Terpenoids are the largest and most widespread class of secondary metabolites, mainly in plants and lower invertebrates. A few of them have been used for therapeutic purposes for centuries. The wide variety of biological activities shown by terpenoids, our knowledge of which is being continually augments as new molecules are investigated, underlines their practical importance as a source of pharmacologically interesting agents.

As a result of our investigation the structure of 100 new diterpene alkaloids from Aconitum and Delphinium was established. We have developed new methods of structure elucidation and deter mination of different functional groups in the skeletal of C19-diterpene alkaloids. The “structure – antiarrhythmic activity” relationship was studied. The drug “allapinin” is introduced to the medici nal practice. The complex of lappaconitine and glycyrrhizic acid has some advantages in the com parison with allapinin.

OCH CH3O OCH H OH N H CH2OH OH H O COOH HO CO H levopimaric acid NHCOCH3 betulin lappaconitine Synthetic transformations of natural occurring terpenoids levopimaric acid and betulin included the following modifications: – reactions of O-glycosylation and N- and O-acylation;

– selective oxidation with dimethyldioxirane, ozone, sodium hypochlorite, Swern reagent;

– realization of new skeletal modifications;

– methods of heterocyclization of di- and triterpenoids;

dichlorocyclopro panation of triterpenoids;

– study of pharmacological activity for 150 semisynthetic terpenoids. We have discovered that triterpenoids are active against influenza and enterovirus ECHO6. The pa rameters for betulinic acid against ECHO6 virus are higher than those of pleconaril. Some new triterpene derivatives with strong activity against herpes simplex and HIV-1 were found. Combina tion of antiviral activity with hepatoprotective, anti-inflammatory, antiulcer, antioxidant, immuno modulating, radioprotective effects of synthetic oleanane and lupane triterpenoids was also shown.

As a result five terpenoids (betulin dinicotinate and bishemiphthalate, betulinic and 3-oximino betulonic, dihydroquinopimaric acids) could be recommended for preclinical study.

The work was supported by RFBR Grant 05-03-32832 and Scientific School Grant 4434.2006.3.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 ФТОРАЛКИЛИРОВАННЫЕ 1,3-ДИКАРБОНИЛЬНЫЕ СОЕДИНЕНИЯ В СИНТЕЗЕ ПИРИМИДИНОВ Бургарт Я.В., Худина О.Г., Прядеина М.В., Салоутин В.И., Чупахин О.Н.

Институт органического синтеза им. И.Я. Постовского УрО РАН, 620041, г. Екатеринбург, ул. С. Ковалевской/Академическая, д. 22/20, e-mail: saloutin@ios.uran.ru Пиримидиновый структурный фрагмент входит в состав ряда природных соединений, в син тетические лекарственные средства и химиотерапевтические препараты. Биологическая важ ность производных пиримидина обуславливает значительный интерес к их синтезу.

В докладе рассматриваются методы создания производных пиримидина на основе фторалки лированных 1,3-дикарбонильных соединений (3-оксоэфиров и 1,3-дикетонов). Показано, что эффективным методом построения функционализированных пиримидинов является исполь зование 2-замещенных 1,3-дикарбонильных соединений. Обсуждаются вопросы строения и возможные пути применения синтезированных пиримидинов.

X Ar O OH OH Rf R Rf CF Ar R O N OAlk N N AlkO2 C NN HN NH HN N Ph R1 Rf N HO XH X N Y R Rf R H N N NH NH O Ar EtO2C NH AlkO 2C f R OEt HO X N X N N HO Rf H N O O O HO Rf H Rf H R Rf N N N Rf H N R O O N EtO2C N HN Ar EtO C + R AlkO NH N Rf AlkO2C H 2N N NN Rf O N O N X EtO2C HO NN N Rf + N S N Rf H N H Br NH2 N N Rf H HO O R Rf Rf N HO EtO2C NN EtO2C EtO2C NN Rf NN EtO2C NN AlkO X N N N Rf N N N H H H R R f HO R Ar Ar Ar Ar O EtO2C N CO2Et EtO2C EtO2 C N N NH N OR N Rf Rf H Rf N N NH2 CO2Et N Rf N H Работа выполнена при финансовой поддержке гранта Президента Российской Федерации (программа для государственной поддержки ведущих научных школ Российской федерации НШ-9178.2006.3.).

2362 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, СТЕРЕОХИМИЯ СОМЕТАТЕЗИСА ЦИКЛООЛЕФИНОВ В СИНТЕЗАХ ПОЛОВЫХ ФЕРОМОНОВ НАСЕКОМЫХ Быков В.И., Финкельштейн Е.Ш.

Институт нефтехимического синтеза им. А.В. Топчиева РАН, 119991, Москва, Ленинский просп., 29.E-mail: bykov@ips.ac.ru Половые феромоны (ПФ) вырабатывают самки насекомых для привлечения самцов к спари ванию и, таким образом, определяют уровень размножения. Использование синтетических препаратов, идентичных по строению и составу природным ПФ, позволяет регулировать численность популяции насекомых. При этом не происходит привыкания насекомых к при меняемым препаратам, а эффективность действия достигается при очень малом расходе.

ПФ, как правило, представляют собой ненасыщенные длинно-цепные (С10-С16) ацетаты, спирты, альдегиды, с двойной связью в положениях 5-11. Большинство экономически зна чимых феромонов содержат преимущественно или только Z-изомеры. В настоящее время для их получения используют Z-стереоселективные варианты реакции Виттига или методы превращения тройной связи в Z-двойную. Они весьма трудоемки, что сдерживает их широ комасштабное использование.

Принципиально новая стратегия синтеза компонентов ПФ, лишенная недостатков тради ционных методов тонкой органической химии, была предложена в лаборатории химии кар боциклических соединений ИНХС РАН.1– Основной смысл разработанной стратегии сводится к следующему:

В сометатезис вовлекаются, с одной стороны циклоолефины (ЦО) С5-С10, а с другой -олефины С4–С8 (нефтехимическое сырье). Целевыми продуктами такого взаимодействия являются 1,-диены (- показывает положение внутренней двойной связи). Подбирая нуж ные сочетания пар ЦО – -олефин, можно варьировать длину углеводородной цепочки и по ложение внутренней двойной связи в 1,-диене. На второй стадии полученные 1,-диены подвергаются региоселективной реакции гидроборирования-окисления концевой двойной связи.

Без фундаментальных исследований по стереохимии новую стратегию невозможно реали зовать в практике. Мы впервые изучили стереохимию сометатезиса ЦО с –олефинами. Ус тановлено, что стереосостав целевых 1,-диенов зависит от размера кольца ЦО, его конвер сии, условий проведения реакции и не зависит от длины углеводородной цепочки -олефина. При невысоких конверсиях ЦО (циклопентен, циклогептен циклооктен и цикло нонен в продуктах реакции преобладают 1,Z--диены, а для циклодецена преобладает Е-стереоизомер. Предложен механизм объясняющий стереоспецифические особенности со метатезиса циклоолефинов с -олефинами.

Работа выполнена при поддержке программ фундаментальных исследований Президиума РАН: «Тео ретическое и экспериментальное изучение природы химической связи и механизмов важнейших химических реакций и процессов» и «Разработка методов получения химических веществ и создание новых мате риалов». Координаторы программ академики Нефедов О.М. и Тартаковский В. А.

Литература 1. Bykov V. I., Finkelshtein E.Sh. // J.Mol.Catal., 1998, v. 133, p 17.

2. Bykov V. I., Butenko T. A., Petrova E.B., E.Sh. Finkelshtein E.Sh. // Tetrahedron, 1999, v. 55, p. 8249.

3. Bykov V. I., Butenko T. A., Henderson P.T., Finkelshtein E.Sh. // J. Mol. Catal., 1994, v.90, p.111.

ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 НОВЫЕ ЭФФЕКТИВНЫЕ МЕТОДЫ СИНТЕЗА ТИАЗОЛО[3,4-а]ХИНОКСАЛИНОВ И РОДСТВЕННЫХ ГЕТЕРОЦИКЛИЧЕСКИХ СИСТЕМ Мамедов В.А.а, Жукова Н.А.а, Котовская С.К.b, Левин Я.А.а, Чарушин В.Н.b a Институт органической и физической химии имени А.Е. Арбузова Казанского научного центра Российской академии наук, 420088 Казань, ул. Арбузова, 8;

Факс: (843)2732253. E-mail: mamedov@iopc.kcn.ru б Институт органического синтеза им. И.Я. Постовского Уральского отделения Российской академии наук, Российская Федерация, 620219, г. Екатеринбург, ул. С. Ковалевской, 20. Факс: (343)2740458. E-mail: charushin@prm.ustu.ru Ранее нами было обнаружено, что при взаимодействии стабильного интермедиата реакции Ганча – 4-гидрокси-3,5-дифенил-4-метоксикарбонил-2-фенилимино-тиазолидина (1a) с 1,2-фенилендиамином (2a) в кипящей уксусной кислоте легко происходит конденсация с элиминированием воды, метанола, ацетанилида с образованием 4,5-дигидро-3-фенил 1-фенилиминотиазоло[3,4-a]хиноксалин-4-она (3).

PhN S O NH OH Ph N Ph MeO AcOH, N + NH2 -MeOH, -PhNHAc, -H2O, N N Ph O S H Ph 1a 2a Использование тиазолидинов, селеназолидинов (1а-e) и 1,2-фенилендиаминов (2а-d) и (4) в этой новой реакции позволило найти простые и эффективные пути синтеза не только 1, 3, и 8-замещенных тиазоло[3,4-a]- и селеназоло[3,4-a] хиноксалинов (5, 6), но также и их азаа налогов (7, 8).

O R1 NH NH OH Ar MeO N R2 N NH NH R N X 2a-d Ar 1a-e (Ar1)ArN (Ar1)ArN (Ar1)ArN (Ar1)ArN X S S X (R2)R N N N N N R R R R N N N N (R1)R2 O O O O N H H H H 6 7 X = S, Se В докладе рассматриваются структурные особенности и спектральные характеристики тиазолидинов, селеназолидинов и трициклов и обсуждаются возможные пути их образова ния.

Работа выполнена при финансовой поддержке Российского фонда фундаментальных исследований (грант № 07-03-00613-а).

2364 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, РЕАКЦИЯ Р,Р,Р-ТРИГАЛОГЕНБЕНЗО[d]-1,3,2-ДИОКСАФОСФОЛОВ С МОНОЗАМЕЩЕННЫМИ АЦЕТИЛЕНАМИ – УДОБНЫЙ ПОДХОД К СИНТЕЗУ ПРОИЗВОДНЫХ БЕНЗО[e]-1,2-ОКСАФОСФОРИНИНОВ – Р-АНАЛОГОВ КУМАРИНОВ Миронов В.Ф., Вараксина Е.Н., Богданов А.В., Немтарев А.В., Татаринов Д.А., Баронова Т.А., Коновалов А.И.

Институт органической и физической химии им. А.Е.Арбузова КазНЦ РАН, 420088, Казань, ул. Арбузова, В докладе обобщены результаты исследования реакции замещенных в ароматическом кольце 2,2,2-тригалогенбензо[d]-1,3-диоксафосфолов с монозамещенными, а также некоторыми ди замещенными ацетиленами (йодфенилацетилен). Рассмотрены родственные процессы, про текающие в трехкомпонентной системе орто-хинон – арилацетилен – тригалогенид фосфо ра. В результате реакций получены с высокими и средними выходами производные аннели рованных Р-гетероциклов – бензо[e]-1,2-оксафосфоринины,1 1,2-оксафосфатрифенилены – Р-аналоги природного гетероцикла кумарина2. Установлена региохимия ипсо-замещения ки слорода и галогенирования ариленового фрагмента в зависимости от природы заместителей в производном Р(V) и ацетилене. В целом региоселективность хлорирования и бромирования ариленового фрагмента при использовании пропаргилхлорида ниже, чем в случае арилаце тиленов. В реакциях с этоксиацетиленом наряду с образованием бензофосфоринов происхо дит классическое присоединение по кратной связи ацетилена. Процессы замещения йода на водород обнаружены в реакции йодфенилацетилена с 2,2,2-трихлорбензо[d]-1,3-ди оксафосфолом. Побочный процесс замещения брома на хлор в образующемся бензофосфо рине обнаружен в реакции пропаргилбромида с фосфораном 1. Показано также, что в реак цию способны вступать и производные гексакоординированного фосфора – ат-комплексы фосфолов 1 с пиридином и хлоридом триэтилбензиламмония.

Y O O O R C C ZO RCCZ P Y X PX3 Y PX O Z O X 1 2R X = Cl, Br;

Y = 3-Me, 4-Me, 4-Cl, 4-Br, 4-t -Bu, 4,5-Br2 (1);

Y2 = 2,6-(t -Bu)2, 2,4-(t -Bu)2, 2,3,4,5-Cl4;

R, Z = OEt, H;

Ph, I;

ClCH2, H;

BrCH2, H;

Ar, H;

Alkyl, H.

Структура выделенных соединений 2 доказана методами ЯМР 1Н, 31Р, 13С, а также ИКС и РСА. В докладе также обсуждаются возможные пути образования продуктов реакций 2 ис ходя из хинонов 3, тригалогенида фосфора и ацетиленов.

Работа выполнена при поддержке РФФИ (грант № 07-03-00180).

Литература 1. В.Ф.Миронов, А.И.Коновалов, И.А.Литвинов и др. // ЖОХ, 1998, 68, 1482.

2. В.Ф.Миронов, Т.А.Баронова, А.Т.Губайдуллин, и др. // Докл. АН, 2002, 385, 196.


Институт органической химии им. Н. Д. Зелинского РАН 119991, Москва, Ленинский просп., 47. E-mail: volchkov@ioc.ac.ru Традиционные методы синтеза фторированных ароматических соединений основаны на ре акциях прямого замещения фтором водорода или функциональных групп в ароматическом ядре под действием различных фторирующих реагентов. Нами разработана альтернативная стратегия получения фтораренов, заключающаяся в синтетической сборке фторированных бензоидных структур или их предшественников через реакции циклообразования с участием фторгалогенметанов (как источников фторгалогенкарбенов) или полифторолефинов, способ ных выступать одновременно в качестве структурообразующих блоков и переносчиков свя занного с C-атомом фтора.

Одним из эффективных путей реализации этой методологии является карбенный метод синтеза фтораренов, включающий циклоприсоединение фторгалогенкарбенов к циклопента диеновым структурам и последующую селективную перегруппировку промежуточно обра зующихся дигалогенбицикло[3.1.0]гексеновых аддуктов, протекающую с расширением цик ла и дегидрогалогенированием F F 550-700°C CX2YF flow X - HX X = Cl, F Y = H, Cl, F :CFX R F F KOHaq, R X CHCl 2F X = Cl, F - HX -5 – +5 °C F R 550-700°C F Метод позволяет осуществлять синтез фторбензола и его производных, дифторбензолов, моно- и дифторнафталинов, вовлекая в подобные превращения различные диеновые суб страты и некоторые алкениларены и используя простые методы генерирования фторгалокар бенов из коммерчески доступных фторгалогенметанов (CHClF2, CHCl2F, CFCI3, CF2Br2, CF2CI2).

Другой разработанный метод синтетической блоковой сборки фтораренов основан на термических реакциях [2+2]-циклоприсоединения фторолефинов к 1,3-диенам и последую щей ароматизации образующихся винилциклобутанов через термическую винилциклобутан циклогексеновую перегруппировку и дегидрогалогенирование.

X F Y Y X F Y X X + -HY + F F -HF F CF 2 CXY F F X = F, Cl, CF3, C4F9;

Y = F, Cl В докладе обсуждаются перспективы практического применения предлагаемой методоло гии для получения моно-, ди- и полифторированных ароматических соединений и синтеза на их основе фторхинолонов и других биологически активных соединений.

2366 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, УДАЛЕННОЕ СОДЕЙСТВИЕ КАК ЭФФЕКТИВНЫЙ ИНСТРУМЕНТ СТЕРЕОКОНТРОЛЯ В СИНТЕЗЕ ОЛИГОСАХАРИДОВ Устюжанина Н.Е., Комарова Б.С., Крылов В.Б., Злотина Н.С., Каськова З.М., Гербст А.Г., Цветков Ю.Е., Нифантьев Н.Э.

Лаборатория химии гликоконъюгатов, Институт органической химии им. Н. Д. Зелинского, Российская академия наук, Ленинский проспект 47, 119991 Москва, Россия В ходе исследования внутримолекулярных взаимодействий, определяющих стереоизбира тельность -L-фукозилирования, нами впервые обнаружено удаленное стереоконтролирую щее соучастие ацильных заместителей при О-3 в фукозилдонорах1 с образованием стабили зированных катионных интермедиатов I. Найденный эффект был также продемонстрирован на примере ряда других гликозилирующих агентов, полученных и из глюкуроновой кислоты, глюкозы и ксилозы. LG Me O OBn O O BnO O HO R MeO O O R BnO O BnO LG O O O R O G -гликозид BnO OBn BnO O BnO O I BnO LG O R O BnO O O BnO LG O HO R R = Me or Ph, LG = Br, SEt, OC(NH)CCl3, OC(NPh)CF 3, G= H, CO 2Me, CH 2OBn, Me Для выяснения механизма содействия ацильных заместителей при О-3 были проведены компьютерные расчеты энергий стабилизации катионов I и показано, что значения энергий стабилизации коррелируют с эффективностью -стереоизбирательности гликозилирования.

С помощью компьютерного моделирования были предсказаны оптимальные соучаствующие ацильные группы и места введения дополнительных содействующих групп с тем, чтобы обеспечить максимальную -стереоизбирательность реакций. Исследованные методы стереоконтроля были успешно использованы в синтезе сложных гетероолигосахаридов – линейных и разветвленных гомофукозных4 и гетеросахаридных фрагментов фукоиданов, три-5 и пентасахаридных фрагментов кора липополисахарида Pseudomonas aeruginosa, -ксилозил-содержащих олигосахаридов, входящих в состав факто ров свертываемости крови VII и IX.

Работа выполнена при финансовой поддержке программы 10 Отделения химии и наук о материалах и Рос сийскиго фонда фундаментальных исследований (грант 06-03-33080).

Литература 1. A. Gerbst, N. Ustuzhanina, A. Grachev, E. Khatuntseva, D. Tsvetkov, D. Whitfield, A. Berces, N. Nifantiev, J. Car bohydr. Chem. 2001, 20, 2. N. Ustuzhanina, B. Komarova, N. Zlotina, V. Krylov, A. Gerbst, Y. Tsvetkov, N. Nifantiev, Synlett 2006, 6, 921.

3. A. Gerbst, N. Ustuzhanina, A. Grachev, D. Tsvetkov, E. Khatuntseva, N. Nifantiev, Mendeleev Commun. 1999, 4. N. Ustuzhanina, V. Krylov, A. Grachev, A. Gerbst, N. Nifantiev, Synthesis, 2006, 5. B. Komarova, Y. Tsvetkov, Y, Knirel, U. Zringer, G. Pier, N. Nifantiev, Tetrahedron Lett., 2006, 47, ХVIII Менделеевский съезд по общей и прикладной химии, Москва, 2007 СТЕРЕОХИМИЧЕСКИ НЕЖЕСТКИЕ МЕТАЛЛАКАРБОРАНОВЫЕ КЛАСТЕРЫ НА ОСНОВЕ ДИ- И МОНОУГЛЕРОДНЫХ КАРБОРАНОВ Чижевский И.Т.

Институт элементоорганических соединений имени А. Н. Несмеянова Российской академии наук, 119991 Москва, ул. Вавилова Направленно синтезированы ди- и моноуглеродные металлакарборановые комплексы плати новой группы металлов (Rh, Ir, Ru, Os) с лигандами различного типа (фосфины, терминаль ные и мостиковые гидриды, циклические -диен/диенильные углеводороды), проявляющие динамические свойства в растворе и/или обладающие склонностью к внутримолекулярным перегруппировкам. С помощью современных физических методов (низкотемпературный РСА, динамический ЯМР на разных ядрах с использованием методов двумерной спектро скопии) изучено строение стереохимически нежестких комплексов в твердом состоянии и растворах, и исследованы процессы, связанные с их внутримолекулярной динамикой, в част ности: а) процессы миграции металлсодержащих группировок по карборановому остову в комплексах с 2-э, 3-ц связями В-Н...М (миграция экзо-RuCl(PPh3)2 группы по тругольным граням моноуглеродного карборанового лиганда1, экзо-нидо клозо перегруппировка и H/H обмен терминальных OsН2 и мостиковых {В-Н}2...Os атомов водорода в экзо-нидо дигидридоосмакарборанах, производных {нидо-7,9-RС2В9}-карборанов2);

б) процессы ми грации агостического водорода по системе металл-карбоциклический лиганд в комплексах с агостической C-Н...М связью3;

в) процессы структурной перегруппировки карбоциклических лигандов с участием агостического C-Н...М взаимодействия4 и г) низкотемпературные поли эдрические перегруппировки, происходящие в металлакарборанах с изменением положения остовных углеродных атомов и заместителей в карборане относительно друг друга5.

Работа выполнена при поддержке Программы ОХНМ (ОХ-1 2006-2007 гг.) и частично гранта РФФИ (грант 06-03-32172).

Литература 1. I. V. Pisareva, V. E. Konoplev, P. V. Petrovskii, E. V. Vorontsov, F. M. Dolgushin, A. I. Yanovsky, I. T.

Chizhevsky, Inorg. Chem., 2004, 43, 6228.

2. E. V. Balagurova, D. N. Cheredilin, G. D. Kolomnikova, O. L. Tok, F. M. Dolgushin, A. I. Yanovsky, I. T. Chiz hevsky, J. Am. Chem. Soc., 2007, 129, 3745.

3. A. V. Safronov, T. V. Zinevich, F. M. Dolgushin, O. L. Tok., E. V. Vorontsov, I. T. Chizhevsky, Organometallics, 2004, 23, 4970.

4. A. В. Сафронов, М. Н. Соколова, Е. В. Воронцов, П. В. Петровский, И. Г. Бараковская, И. Т. Чижевский, Изв.

АН, Сер. хим., 2004, 1875.

5. A. V. Safronov, F. M. Dolgushin, P. V. Petrovskii, I. T. Chizhevsky, Organometallics, 2005, 24, 2964.


Chemistry Department, Islamic Azad University-Zanjan Branch, P O Box 49195-467, Zanjan, Iran E-mail: alirezakazemizadeh@yahoo.com Phosphorus ylides are reactive systems, which take part in many valuable reactions in organic syn thesis.1-2 In recent years we have established a convenient, one-pot method for preparing stabilized phosphorus ylides utilizing in situ generation of the phosphonium salts.3-4 In this paper, we wish to describe the preparation of phosphorus ylides from malononitrile in solvent-free conditions in fairly high yields. Protonation of the highly reactive 1:1 intermediates, produced in the reaction be tween triphenylphosphine (1) and dialkyl acetylenedicarboxylates (2), by malononitrile (4) under microwave irradiation, thermal conditions and also at room temperature in solvent-free conditions leads to vinyltriphenylphosphonium salts, which undergo Michael addition reaction with conjugate base to produce dialkyl 2-(dicyanomethyl)-3-(triphenyl-5-phosphoranylidene)succinates (6) in fairly good yields. The structures of these compounds were confirmed by IR, 1H, 31P and 13C NMR spectroscopy.

+ Microwave or thermal Ph3P CO 2R conditions or at room _ + RO2C CO2R Ph3P temperature in solvent- RO2C free conditions (1) (2) (3) _ CN + + Ph3 P C CH CO2R CN CN CN CO2R (4) (5) NC + CN Ph3P _ 6a : R= Me H 6b : R= Et CO2R CO2R (6) References 1. R. Engel, Synthesis of Carbon-Phosphorus Bonds (CRC Press, Boca Raton, FL, 1988).

2. L. D. Quin, A Guide to Organophosphorus Chemistry (Wiley- Interscience, New York, 2000).

3. A. Ramazani, A. R. Kazemizadeh, and F. Marandi, Phosphorus, Sulfur, and Silicon, 180, 1537 (2005).

.4 A. Ramazani, A. R. Kazemizadeh, E. Ahmadi, K. Slepokura, and T. Lis, Z. Naturforsch. 61b, 1128 (2006).

2370 ХVIII Менделеевский съезд по общей и прикладной химии, Москва, ОКИСЛЕНИЕ СЕЛЕНАЦИКЛОГЕКСАНОВ ДО СОЛЕЙ СЕЛЕНОПИРИЛИЯ Алмаева А.Ф., Древко Б.И., Исаев И.Н., Мандыч В.Г., Баранчикова Г.А.

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