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The reactions of chloromethylsilanes with amines, hexamethyldisilazane, and silylcarbamates were studied. The dependence of the composition and structure of the resulting products on the nature of the reagents used and reaction conditions was determined. A scheme for the synthesis of 4,9-diaza-2,7-dioxa-1,6-disilacyclodecane-3,8-dione derivatives was suggested.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1798–1801, October, 1994. 相似文献
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A. D. Kirilin L. O. Belova A. V. Gavrilova E. A. Korobova 《Russian Journal of General Chemistry》2009,79(10):2137-2141
Reaction of 3-aminopropyltriethoxysilane and N-[2-(aminoethyl)-N-3-(trimethoxysilyl)propyl]-amine and their derivatives with diethylcarbamic acid trimethylsilyl ether and trimetisilylisocyanate
proceeds through the stage of formation of intermediate products which under conditions of the synthesis undergo intramolecular
(in the case of formation O-silylcarbamates) and intermolecular (in the case of the formation of carbamide trimethylsilyl derivatives) desilylation leading
to the cyclic and linear products respectively. 相似文献
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A. D. Kirilin A. A. Dokuchayev N. B. Sokova E. A. Chernyshev 《Russian Chemical Bulletin》1999,48(1):169-172
Reactions of carbofunctional organosilicon compounds withN,N-dimethyl-N′-trimethylsilylhydrazine andN,N-dimethyl-N′,N′-bis(trimethylsilyl)hydrazine were studied. The composition and structure of the reaction products were found to be dependent
on the reagent nature and the reaction conditions. 1,4-Dimethylamino-2,2,5,5-tetramethyl-1,4-diaza-2,5-disilacyclohexane,
a first representative of a new type of 2,5-disilapiperazines, was synthesized. A scheme of its formation was proposed.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 169–173, January, 1999. 相似文献
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Kirilin A. D. Belova L. O. Zhvakina L. A. Chernyshev E. A. 《Russian Journal of General Chemistry》2003,73(10):1539-1542
The reaction of chloro(chlorodimethyl)dimethylsilane and hexamethyldisilazane with O-silylurethanes and nicotinic hydrazide gives rise to products whose structure is determined by the composition, structure, and basicity of intermediate compounds. The reaction allowed synthesis of previously unknown linear and heterocyclic compounds. 相似文献
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Alexey Kirilin Serap Sahin Päivi Mäki‐Arvela Johan Wärnå Tapio Salmi Dmitry Yu. Murzin 《国际化学动力学杂志》2010,42(10):629-639
The kinetics of the acylation of (R,S)‐1‐phenylethanol was investigated using lipase as a catalyst. The main parameters were temperature, reaction atmosphere, different acyl donors, and different amounts of acyl donor as well as the presence of some additives in the reaction mixture. The initial reaction rate increased with increasing temperature and with a decreasing amount of an acyl donor. The activated esters, such as isopropenyl‐ and vinyl acetate, exhibited very high acylation rates for R‐1‐phenylethanol, whereas low rates were obtained with ethyl acetate and 2‐methoxyethyl acetate. The addition of water and acetophenone decreased the acylation rate. A kinetic model was developed based on a sequential step mechanism, in which enzyme was reacting in the first step with an acyl donor followed by the reaction of a modified enzyme complex with the reactant, R‐1‐phenylethanol. Comparison with experimental data obtained at different temperatures allowed simplification of this model, leading to a kinetic equation with just one apparent parameter. The influence of the amount of acyl donor, ethyl acetate, could be quantitatively described by taking into account the competitive inhibition of the ethanol produced. The rate constants and apparent activation energy for experiments performed under different temperatures and the amounts of acylation agent were determined. The apparent activation energy was 24.5 kJ/mol. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 629–639, 2010 相似文献
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A. Kirilin S. Sahin A. Tokarev P. Mäki-Arvela K. Kordas A. -R. Leino A. Shchukarev J. -P. Mikkola L. M. Kustov T. Salmi D. Yu. Murzin 《Kinetics and Catalysis》2010,51(6):809-815
The kinetics and reaction network of the one-pot synthesis of R-1-phenylethyl acetate was investigated at 70°C in toluene over a combination of three different catalysts: PdZn/Al2O3 as a catalyst for acetophenone hydrogenation, lipase as an enzymatic catalyst for R-1-phenylethanol acylation with ethyl acetate and Ru/Al2O3 as a racemization catalyst for S-1-phenylethanol. In addition to the desired reactions, other reactions, namely hydrogenolysis and dehydration of (R, S)-1-phenylethanol and debenzylation of (R, S)-1-phenylethyl acetate also occurred. The kinetic results revealed that ethylbenzene formation was enhanced with higher amounts of PdZn/Al2O3, whereas lipase did not catalyze ethylbenzene formation. Furthermore, ethylbenzene was formed in the hydrogenolysis of (R, S)-phenylethanol and in the debenzylation of (R, S)-1-phenyl-ethylacetate over Pd/Al2O3 catalyst. The presence of Ru/Al2O3 catalyst, in which Ru was in the oxidation state of 3+, enhanced the formation of R-1-phenylethyl acetate, although no clear racemization of S-1-phenylethanol during the one-pot synthesis of R-1-phenylethyl acetate was observed. Dynamic kinetic resolution of (R, S)-1-phenylethanol in toluene, was, however, demonstrated over Ru/Al2O3 and lipase. 相似文献
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A. D. Kirilin L. O. Belova M. V. Pletneva V. M. Panfilova P. A. Storozhenko V. D. Sheludyakov 《Russian Journal of General Chemistry》2011,81(7):1493-1495
The N-siloxycarbonylation and transamination reactions were studied by an example of diazoles. We found that because of insufficient
nucleophilicity of the nitrogen atoms in the first case only the sililylation process occurs, in the second case the low-boiling
amine is replaced by the higher boiling one and the process is completed by the formation of O-silyluretans. 相似文献
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E. G. Gordeev A. Yu. Shkulipa A. D. Kirilin 《Russian Journal of General Chemistry》2014,84(7):1330-1338
Insertion of CCl2, SiCl2, and GeCl2 into the B-H and C-H bonds of the carborane(12) molecules as well as into the B-Hal, C-Hal bonds of some halogen-substituted ortho-carboranes are studied at the B3LYP/6-311+G(d,p) and M06-2X/6-311+G(d,p) levels of theory. Thermodynamic parameters of the reactions are calculated and their variation for the isomeric carboranes(12) and for a series of carbenoid species is shown. For several insertion reactions the energies of activation are calculated based on the model of three-center synchronous transition state. The energy barriers are regularly varied depending on the position of the B-H bond in the carborane molecule. 相似文献