18236-82-3Relevant articles and documents
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.
Effect of the substituents at the silicon of (ω-chloroalkyl)silanes on the alkylation to benzene
Yoo, Bok Ryul,Hyun Kim, Jeong,Lee, Ho-Jin,Lee, Kang-Bong,Nam Jung, Il
, p. 239 - 245 (2007/10/03)
(ω-Chloroalkyl)silanes [Cl3-mMemSi(CH2)n-Cl: m=0-3, n=1-3] underwent Friedel-Crafts alkylation with benzene in the presence of aluminum chloride to give alkylated products. Such alkylation reactions took place at temperatures ranging from room temperature (m=0-1, n=2, 3; m=3, n=1) to 80 (m=1, 2; n=1) and 200°C (m=0; n=1), depending on the substituent(s) of the silicon and the alkylene-chain spacer between the silicon and C-Cl bond of (ω-chloroalkyl)silanes. In the alkylation to benzene, the reactivities of (ω-chloroalkyl)silanes increase as the number (m) of methyl-group(s) at the silicon and the alkylene length between the silicon and C-Cl bond increases. While decomposition of alkylation products was observed at two more methyl groups substituted at silicon in the cases of (chloromethyl)silanes such as (chloromethyl)dimethylchlorosilane and (chloromethyl)trimethylsilane. The reaction with (chloromethyl)trimethylsilane occurred at room temperature to give trimethylchlorosilane, toluene and xylene via a decomposition reaction of the products. No (trimethylsilylmethyl)benzene was formed. In the alkylation to benzene, the reactivity of (ω-chloroalkyl)silanes decreases in the following order: m=3>2>1>0; n=3>2?1. The results are consistent with the stability of the carbocation generated by the complexation of (ω-chloroalkyl)silanes with aluminum chloride.
CONVERSION OF DISILANES TO FUNCTIONAL MONOSILANES. XII. THE PALLADIUM(0)-CATALYZED DECHLORINATIVE SILYLATION OF BENZYLIC CHLORIDES WITH METHYLCHLORODISILANES. A FACILE ROUTE TO BENZYLMETHYLCHLOROSILANES
Matsumoto, Hideyuki,Kasahara, Miyuki,Matsubara, Ikuya,Takahashi, Masatoshi,Arai, Takeshi,et al.
, p. 99 - 108 (2007/10/02)
This paper describes the facile dechlorinative silylation of benzylic chlorides of types XC6H4CH2Cl (X = H, Me and Cl) and ClCH2C6H4CH2Cl (o-, m- and p-isomers) with methylchlorodisilanes ClMe2SiSiMe2Cl, ClMe2SiSiMeCl2 and Cl2MeSiSiMeCl2 in the presence of Pd(PPh3)4 to give the corresponding benzylmethylchlorosilanes in good to high yields.
