4170-46-1Relevant articles and documents
PRODUCTION METHOD FOR LINEAR AND CYCLIC TRISILAALKANE
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Page/Page column 6, (2011/04/19)
The present invention relates to a preparation method for a linear or cyclic trisilaalkane which is a substance useful in the preparation of polycarbosilane and silicon carbide precursors. Linear or cyclic trisilaalkane and organic trichlorosilane derivatives can be synthesized simultaneously and in high yield by reacting bis(chlorosily)methane having a Si—H bond, either alone or together with an organic chloride, using a quaternary organic phosphonium salt compound as a catalyst. Further, since the catalyst can be recovered after use, the present invention is very economical and is thus effective for mass-producing precursors for organic/inorganic hybrid substances.
Enantio- and diastereotopos differentiation in the palladium(II)-catalyzed hydrosilylation of bicyclo[2.2.1]alkene scaffolds with silicon-stereogenic silanes
Rendler, Sebastian,Froehlich, Roland,Keller, Manfred,Oestreich, Martin
supporting information; experimental part, p. 2582 - 2591 (2009/04/05)
The palladium(II)-catalyzed hydrosilylation of meso-configured bicyclo[2.2.1]alkene scaffolds proved to be an invaluable model reaction for the development of reagent-controlled asymmetric transformations based on silicon-stereogenic silanes as stereoinducers. In the present investigation, the subtle structural requirements of the silane substitution pattern in enantiotopos-differentiating single hydrosilylations of a norbornene-type substrate are disclosed. Extension of this chemistry to a double hydrosilylation of norbornadiene entails a significant increase in stereochemical complexity. Although differentiation of enantiotopic positions by the chiral reagent is demanded in the first hydrosilylation, the same reagent must then differentiate diastereotopic positions in the second. Remarkably high stereocontrol was found in this double hydrosilylation with several silanes first used in the hydrosilylations of the norbornene-type system. Depending on the enantiomeric purity of the silane, C2- and Cs-symmetric adducts, respectively, were obtained. The identity of the key quaternary silanes was revealed by crystallographic analysis. By this method, the relative and absolute configurations were also assigned, which, in turn, imply that all enantiospecific substitutions at silicon proceed with stereoretention. On the basis of these solid-state structures, we also discuss the structural implications of silane substitution for the diastereoselectivity-determining step of this palladium(II)-catalyzed hydrosilylation reaction. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.
PROCESS FOR PREPARING ORGANOCHLOROSILANES BY DEHYDROHALOGENATIVE COUPLING REACTION OF ALKYL HALIDES WITH CHLOROSILANES
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, (2008/06/13)
The present invention relates to a process for preparing organochlorosilanes and more particularly, to the process for preparing organochlorosilanes of formula I by a dehydrohalogenative coupling of hydrochlorosilanes of formula II with organic halides of formula III in the presence of quaternary phosphonium salt as a catalyst to provide better economical matter and yield compared with conventional methods, because only catalytic amount of phosphonium chloride is required and the catalyst can be separated from the reaction mixture and recycled easily, wherein R1 represents hydrogen, chloro, or methyl; X represents chloro or bromo; R2 is selected from the group consisting of C1-17 alkyl, C1-10 fluorinated alkyl with partial or full fluorination, C2-5 alkenyl, silyl containing alkyl group represented by (CH2)nSiMe3-mClm wherein n is an integer of 0 to 2 and m is an integer of 0 to 3, aromatic group represented by Ar(R′)q wherein Ar is C6-14 aromatic hydrocarbon, R′ is C1-4 alkyl, halogen, alkoxy, or vinyl, and q is an integer of 0 to 5, haloalkyl group represented by (CH2)pX wherein p is an integer of 1 to 9 and X is chloro or bromo, and aromatic hydrocarbon represented by ArCH2X wherein Ar is C6-14 aromatic hydrocarbons and X is a chloro or bromo; R3 is hydrogen, C1-6 alkyl, aromatic group represented by Ar(R′)q wherein Ar is C6-14 aromatic hydrocarbon, R′ is C1-4 alkyl, halogen, alkoxy, or vinyl, and q is an integer of 0 to 5; and R4 in formula I is the same as R2 in formula III and further, R4 can also be (CH2)pSiR1Cl2 or ArCH2SiR1Cl2, when R2 in formula III is (CH2)pX or ArCH2X, which is formed from the coupling reaction of X—(CH2)p+1—X or XCH2ArCH2X with the compounds of formula II; or when R2 and R3 are covalently bonded to each other to form a cyclic compounds of cyclopentyl or cyclohexyl group, R3 and R4 are also covalently bonded to each other in the same fashion.
Process for preparing organochlorosilanes by dehydrohalogenative coupling reaction of alkyl halides with chlorosilanes
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, (2008/06/13)
The present invention relates to a process for preparing organochlorosilanes and more particularly, to the process for preparing organochlorosilanes of R4R3CHSiR1Cl2(I) by a dehydrohalogenative coupling of hydrochlorosilanes of HSiR1Cl2(II) with organic halides of R2R3CHX (III) in the presence of quaternary phosphonium salt as a catalyst to provide better economical matter and yield compared with conventional methods, because only a catalytic amount of phosphonium chloride is required and the catalyst can be separated from the reaction mixture and recycled easily.
Direct synthesis of organodichlorosilanes by the reaction of metallic silicon, hydrogen chloride and alkene/alkyne and by the reaction of metallic silicon and alkyl chloride
Okamoto, Masaki,Onodera, Satoshi,Yamamoto, Yuji,Suzuki, Eiichi,Ono, Yoshio
, p. 71 - 78 (2007/10/03)
Dichloroethylsilane was synthesized by the reaction of metallic silicon, hydrogen chloride and ethylene using copper(I) chloride as the catalyst, the silicon conversion and the selectivity for dichloroethylsilane being 36 and 47%, respectively. At a lower reaction temperature or at a higher ratio of ethylene: hydrogen chloride a higher selectivity was obtained, however the silicon conversion was lower. The silicon-carbon bond formation is caused by the reaction of a surface silylene intermediate with ethylene. The reaction with propylene in place of ethylene gave dichloroisopropylsilane (22% selectivity) and dichloro-n-propyl-silane (8% selectivity) together with chlorosilanes. A part of the dichloroisopropylsilane is formed by the reaction of silicon, hydrogen chloride and isopropyl chloride formed by hydrochlorination of propylene. Use of acetylene instead of alkenes resulted in dichlorovinylsilane formation with a 34% selectivity. Alkyldichlorosilanes were also produced directly from silicon with alkyl chlorides, propyl and butyl chlorides. During the reaction the alkyl chloride is dehydrochlorinated over the surface of copper originating from the catalyst to afford hydrogen chloride and alkene. The hydrogen chloride formed participates in the formation of the silicon-hydrogen bond in alkyldichlorosilane, and the reaction of silicon, hydrogen chloride and alkene also causes alkyldichlorosilane formation. The reaction with isopropyl chloride gave a very high selectivity (85%) for dichloroisopropylsilane, the silicon conversion being 86%. The Royal Society of Chemistry 2001.
Reaction of Hydrogen Peroxide with Organosilanes under Chemical Vapour Deposition Conditions
Moore, Darren L.,Taylor, Mark P.,Timms, Peter L.
, p. 2673 - 2678 (2007/10/03)
When a stream of vapour at low pressure which contained a mixture of H2O2 with an organosilane, RSiH3 (R = alkyl or alkenyl), impinged on a silicon wafer, deposition of oxide films of nominal composition RxSiO(2-0.5x), where x 3 or higher alkenyl groups. or higher alkenylgroups. Possible mechanism for the Si-C bond cleavage reaction are discussed, with energetic rearrangement of radical intermediates of type Si(H)(R)(OOH)' being favoured.
