546-56-5Relevant articles and documents
Divergent reactivity of divinylsilanes toward sulfonamides in different oxidative systems
Astakhova, Vera V.,Moskalik, Mikhail Yu.,Shainyan, Bagrat A.
, p. 40514 - 40528 (2020)
Oxidative sulfonamidation of divinylsilanes with various sulfonamides in different solvents is reported. With t-BuOI as an oxidant, halogenation is the main process, whereas aziridines are the minor products. With NBS in CH2Cl2 the products of bromination or bromosulfonamidation were obtained, whereas in MeCN or THF the Ritter-type solvent interception products are formed. The obtained bromosulfonamidation products undergo base-induced cyclization to various heterocycles, including imidazolines, 1,4-oxazocanes, or Si,N-containing heterocycles of a new type, 1,3,5-diazasilinanes, in up to quantitative yield.
Harber et al.
, p. 255,258 (1972)
A simple synthesis of octaphenylcyclotetra(siloxane)
Luo, Mei,Yan, Bing
, p. 5208 - 5209 (2009)
An essential industrial monomer octaphenylcyclotetra(siloxane) or (Ph2SiO)4 was obtained by very simple procedures, The product was confirmed by NMR, IR, MS, elemental analysis, and X-ray crystallography.
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Burkhard,Decker,Harker
, p. 2174 ()
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Reactions of silicon hydrides catalyzed by rhodium(III) sulfoxide complexes
Eliseeva,Prudnikova,Panikorovskii,Skvortsov
, p. 1884 - 1886 (2017)
Dehydrocondensation reactions of silicon hydrides catalyzed by the rhodium(III) complex [RhCl3(Me2SO)3] in the absence of the second substrate were studied. It was found that the complex [RhCl3(Me2SO)3] catalyzed the dehydrocondensation reaction with the formation of compounds containing siloxane bonds. Analysis of NMR spectra has shown that the reaction of [RhCl3(Me2SO)3] with silicon hydride includes sequential desoxygenation of sulfoxide ligands to sulfide ligands with the complex [RhCl3(Me2S)3] formation.
Cobalt-Catalyzed Selective Synthesis of Disiloxanes and Hydrodisiloxanes
Pattanaik, Sandip,Gunanathan, Chidambaram
, p. 5552 - 5561 (2019/06/05)
Selective syntheses of symmetrical siloxanes and cyclotetrasiloxanes are attained from reactions of silanes and dihydrosilanes, respectively, with water, and the reactions are catalyzed by a NNNHtBu cobalt(II) pincer complex. Interestingly, when phenylsilane was subjected to catalysis with water, a siloxane cage consisting 12 silicon and 18 oxygen centers was obtained and remarkably the reaction proceeded with liberation of 3 equiv of molecular hydrogen (36 H2) under mild experimental conditions. Upon reaction of silane with different silanols, highly selective and controlled syntheses of higher order monohydrosiloxanes and disiloxymonohydrosilanes were achieved by cobalt catalysis. The liberated molecular hydrogen is the only byproduct observed in all of these transformations. Mechanistic studies indicated that the reactions occur via a homogeneous pathway. Kinetic and independent experiments confirmed the catalytic oxidation of silane to silanol, and further dehydrocoupling processes are involved in syntheses of symmetrical siloxanes, cyclotetrasiloxanes, and siloxane cage compounds, whereas the unsymmetrical monohydrosiloxane syntheses from silanes and silanols proceeded via dehydrogenative coupling reactions. Overall these cobalt-catalyzed oxidative coupling reactions are based on the Si-H, Si-OH, and O-H bond activation of silane, silanol, and water, respectively. Catalytic cycles consisting of Co(II) intermediates are suggested to be operative.
Controlled synthesis of cyclosiloxanes by NHC-catalyzed hydrolytic oxidation of dihydrosilanes
Qing, Guoping,Cui, Chunming
, p. 8746 - 8750 (2017/07/22)
Hydrolytic oxidation of various hydrosilanes in acetonitrile and in the absence of organic solvents catalyzed by an N-heterocyclic carbene organocatalysis is described. The NHC organocatalyst exhibited a very high activity with only 0.1 mol% loading of the catalyst in acetonitrile for aryl-substituted dihydrosilanes to produce hydrogen gas and cyclosiloxanes almost quantitatively in several minutes. The calculated TOF (15 000 h-1) of this organocatalyst is comparable to those of precious metal-based heterogeneous catalysts and much superior to those of the existing homogeneous metal catalysts. The catalytic reaction selectively yielded cyclosiloxanes in high yield without the contamination of silanols. Furthermore, the catalytic reaction can also be furnished under solvent-free conditions at elevated temperatures with 2.5 mol% loading of the NHC in 5-12 hours.
