1719-04-6Relevant articles and documents
DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl
Gonzalez, Paulina E.,Sharma, Hemant K.,Pannell, Keith H.
, p. 376 - 381 (2017/06/30)
The room temperature reactions between R3SiH (R3?=?Et3, PhMe2, Ph2Me) and R′3SiCl (R′3?=?Me3, PhMe2, Ph2Me), with an excess of dimethylformamide (DMF) in the presence of (Me3N)Mo(CO)5 as a catalyst, result in the initial formation of R3SiCl, R′3SiOSiR′3 and Me3N as detected by 29Si, 13C, 1H NMR spectroscopy and GC/MS. As the reaction proceeds, the more so if the reaction temperature is raised, mixed disiloxanes R3SiOSiR′3 and ultimately lesser amounts of R3SiOSiR3 may be detected. A mechanism involving the activation of chlorosilanes by the nucleophilic DMF is proposed to produce transient imminium siloxy ion pairs, [Me2N[dbnd]CHCl]+[R′3SiO]? ? [Me2N[dbnd]CH(OSiR′3)]+Cl? which react with R3SiH to form Me2NCH2OSiR′3 and R3SiCl. A secondary reaction of Me2NCH2OSiR′3 with R′3SiCl produces the symmetrical disiloxane R′3SiOSiR′3 and ClCH2NMe2. The final stage of the reaction is the reduction of ClCH2NMe2 by R3SiH, a reaction which is reported for the first time. The newly created chlorosilane R3SiCl can become involved in the initial DMF activation chemistry thereby forming the other disiloxanes observed as the reaction proceeds.
Method for producing polyimidesiloxane
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Paragraph 0043, (2018/10/16)
PROBLEM TO BE SOLVED: To provide a method for synthesizing siloxanes at will in good yield while maintaining high structural controllability, which can be applied to substrates having various substituents.SOLUTION: The method comprises reacting benzyloxysilanes and silicon halides in the absence of hydrogen using a catalyst comprising a transition metal or a compound thereof, preferably a metal of group 9 or group 10 of the periodic table or a compound thereof. Thereby, corresponding siloxanes can be produced safely and simply in high yield under a mild reaction condition accompanied by elimination of a benzyl halide. Especially, by using an active carbon-supported catalyst as a heterogeneous catalyst, the target siloxanes can be separated easily.
Salt-free preparation of trimethylsilyl ethers by B(C6F 5)3-catalyzed transfer silylation by using a Me 3SiH surrogate
Simonneau, Antoine,Friebel, Jonas,Oestreich, Martin
supporting information, p. 2077 - 2083 (2014/04/17)
An unprecedented transfer silylation of alcohols catalyzed by the strong Lewis acid B(C6F5)3 is described. Gaseous Me3SiH is released in situ by B(C6F5) 3-catalyzed decomposition of 3-trimethylsilylcyclohexa-1,4-diene and subsequently reacts with an alcohol in a dehydrogenative Si-O coupling promoted by the same boron catalyst. Benzene and dihydrogen are formed during the reaction, but no salt waste is. This expedient protocol is applicable to several silicon groups, and the preparation of trimethylsilyl ethers presented here is potentially useful for alcohol derivatization prior to GLC analysis. Copyright
Pd/C-catalyzed cross-coupling reaction of benzyloxysilanes with halosilanes for selective synthesis of unsymmetrical siloxanes
Igarashi, Masayasu,Kubo, Keiko,Matsumoto, Tomohiro,Sato, Kazuhiko,Ando, Wataru,Shimada, Shigeru
, p. 19099 - 19102 (2014/05/20)
A new protocol for the nonhydrolytic synthesis of unsymmetrical siloxanes has been developed. The cross-coupling reaction of benzyloxysilanes with halosilanes catalyzed by Pd/C afforded various unsymmetrical siloxanes with co-production of benzyl halides. the Partner Organisations 2014.
