1627-98-1Relevant articles and documents
THERMAL AND PHOTOCHEMICAL BEHAVIOR OF 2-SILA- AND GERMA-CYCLOPENTANONE
Hassner, Alfred,Soderquist, John A.
, p. 429 - 432 (1980)
Pyrolysis and photolysis of the first examples of five-membered ring sila and germa ketones 2 is reported.The photolysis of 2a leading to a cyclic acetal via a siloxycarbene is contrasted to the behavior of the germa analog 2b wich gives ring cleavage via a ketene intermediate.
Kinetics of Addition of 2-Methyl-2-silapropene to Hydrogen Chloride, Hydrogen Bromide, and Oxygen
Davidson, Iain M. T.,Dean, Christopher E.,Lawrence, F. Timothy
, p. 52 - 53 (1981)
2-Methyl-2-silapropene adds rapidly to hydrogen chloride and hydrogen bromide in the gas phase to form the corresponding trimethylsilyl halide, and to molecular oxygen to form dimethylsilanone; Arrhenius parameters for these reactions have been measured.
An Electron Diffraction Study of 1,1-Dimethylsilaethylene
Mahaffy, Peter G.,Gutowsky, Robb,Montgomery, Lawrence K.
, p. 2854 - 2856 (1980)
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L'electrosynthese, une alternative pour la synthese de polycarbosilanes
Bordeau, M.,Biran, C.,Pons, P.,Leger, M.-P.,Dunogues, J.
, p. C21 - C24 (2007/10/02)
The electrochemical reduction of chloromethyldimethylchlorosilane affords polycarbosilanes in high yields and this route constitutes a competitive route to 1,1,3,3-tetramethyl-1,3-disilacyclobutane formed in 34percent crude yield.The solvent mixture was varied to yield its precursor, Cl(CH2SiMe2)2Cl, in 43percent yield after distillation, while electrosynthesis in the presence of dimethyldichlorosilane provided bis(dimethyl-chlorosilyl)methane, another polycarbosilane precursor, in 60percent yield after distillation.
SILYL AND SILYLMETHYL RADICALS, SILYLENES, SILA-ALKENES, AND SMALL RING SILACYCLES IN REACTIONS OF ORGANOCHLOROSILANES WITH ALKALI METAL VAPOURS
Gusel'nikov, L. E.,Polyakov, Yu. P.,Volnina, E. A.,Nametkin, N. S.
, p. 189 - 204 (2007/10/02)
Dehalogenation of the organochlorosilanes Me3SiCl (I), Me2PrSiCl (II), Me3SiSiMe2Cl (III), Me3SiCH2SiMe2Cl (IV), ClCH2SiMe3 (V), ClCH2SiMe2SiMe3 (VI), ClCH2Me2SiSiMe2CH2Cl (VII), Me2SiCl2 (VIII), MePrSiCl2 (IX), Me3SiCH2SiMeCl2 (X), Me3SiCH2CH2SiMeCl2 (XI), Me3SiCH2CH2CH2SiMeCl2 (XII), ClCH2Si(H)MeCl (XIII), ClCH2SiMe2Cl (XIV), ClMe2SiSiMe2Cl (XV), ClCH2CH2CH2Si(H)MeCl (XVI), ClCH2CH2CH2SiMe2Cl (XVII), ClCH2CH2OSiMe2Cl (XVIII), ClMe2SiCH2SiMe2Cl (XIX), ClMe2SiCH2CH2SiMe2Cl (XX), and ClMe2SiCH2CH2CH2SiMe2Cl (XXI) with K/Na alloy vapours at 0.1-1 Torr and 300-320 deg C yields products derived from the reactions of short-lived intermediates, such as silyl and silylmethyl radicals, silylenes, and sila-alkenes.In addition, small-ring silacycles of low stability are formed as the intermediates in some of the dehalogenation reactions.Combination and H-atom abstraction are the main reactions of silyl and silyl-methyl radicals.These radicals are not prone to decomposition reactions when C-H, C-C, or Si-C bonds are at the β(Si-Si) bond with the formation of Me2Si=CH2 and the trimethylsilyl radical.The generation of alkylmethylsilylenes is accompanied by their decomposition processes, which involves intramolecular β(C-H) insertion of alkylmethylsilylenes and 2+1>-thermocyclodecomposition of intermediate silacyclopropanes.The contribution of δ(C-H) and ε(C-H) insertion reactions is much less pronounced, and in the formation of five- or six-membered silacycles.We did not succeed in obtaining monosilacyclobutanes, as the intramolecular γ(C-H) insertion is not typical for silylenes with alkyl substituents.Dehalogenation of chloromethylchlorosilanes with alkali metal vapours yields sila-alkenes, and that of 1,2-dichlorodisilanes gives disilenes. 1-Methyl-1-silaethylene, obtained by this method, does not rearrange into dimethylsilene, but dimerizes to give 1,3-dimethyl-1,3-disilacyclobutane.The formation of 1,3,5-trisilacyclohexanes takes place due to subsequent radical addition at the silicon-carbon double bond and cyclization of 1,6-biradicals.Dehalogenation of organochlorosilanes XVI, XVII, and XX opens up possibilities for the gas-phase synthesis of small organosilicon heterocycles: monosilecyclobutanes and 1,2-disilacyclobutanes.A new, low-stability heterocycle, i.e. 1,1,2,2-tetramethyl-1,2-disilacyclobutane, has been obtained, which enables a new, high polymer, polyethylenetetramethyldisilene, to be obtained.In the case of organochlorosilanes XVIII and XIX, cyclization is accompanied by secondary reactions of silacycles, rearrangements, dimerization, or decomposition.
