- METHOD FOR PRODUCING TERTIARY ALKYLSILANE AND METHOD FOR PRODUCING TERTIARY ALKYLALKOXYSILANE
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PROBLEM TO BE SOLVED: To provide a method for producing a tertiary alkylsilane using more inexpensive tertiary alkyl Grignard reagent as compared with an organic lithium reagent and achieving the production of a tertiary alkylsilane with high production e
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Paragraph 0062-0064; 0066-0084
(2020/02/18)
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- METHOD FOR PRODUCING TERTIARY ALKYLSILANE AND TERTIARY ALKOXYSILANE
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PROBLEM TO BE SOLVED: To provide a method for efficiently producing a tertiary alkylsilane using an inexpensive material, and further to provide a method for producing a tertiary alkoxysilane using a tertiary alkylsilane having an Si-Cl bond thus produced. SOLUTION: There is effectively produced a tertiary alkylsilane by carrying out a reaction between a tertiary Grignard reagent and chlorosilane at a low temperature in the coexistence of a catalyst. Further, there is produced a tertiary alkoxysilane by reacting a tertiary alkyl silane having an Si-Cl bond thus produced with alcohol. SELECTED DRAWING: None COPYRIGHT: (C)2016,JPOandINPIT
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Paragraph 0044; 0045; 0046
(2018/09/08)
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- Stereoselective alcohol silylation by dehydrogenative Si-O coupling: Scope, limitations, and mechanism of the Cu-H-catalyzed non-enzymatic kinetic resolution with silicon-stereogenic silanes
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Ligand-stabilized copper(I)hydride catalyzes the dehydrogenative Si-O coupling of alcohols and silanes-a process that was found to proceed without racemization at the silicon atom if asymmetrically substituted. The present investigation starts from this pivotal observation since silicon-stereogenic silanes are thereby suitable for the reagent-controlled kinetic resolution of racemic alcohols, in which asymmetry at the silicon atom enables discrimination of enantiomeric alcohols. In this full account, we summarizeour efforts to systematically examine this unusual strategy of diastereoselective alcohol silylation. Ligand (sufficient reactivity with moderately electron-rich monophosphines), silane (reasonable diastereocontrol with cyclic silanes having a distinct substitution pattern) as well as substrate identification (chelating donor as a requirement) areintroductorily described. With these basic data at hand, the substrate scope was defined employing enantiomerically enriched tert-butyl-substituted 1-silatetraline and highly reactive 1-si-laindane. The synthetic part is complemented by the determination of the stereochemical course at the silicon atom in the Si-O coupling step followed by its quantum-chemical analysis thus providing a solid mechanistic picture of this remarkable transformation.
- Rendler, Sebastian,Plefka, Oliver,Karatas, Betuel,Auer, Gertrud,Froehlich, Roland,Mueck-Lichtenfeld, Christian,Grimme, Stefan,Oestreich, Martin
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supporting information; scheme or table
p. 11512 - 11528
(2009/12/07)
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- 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
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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.
- Okamoto, Masaki,Onodera, Satoshi,Yamamoto, Yuji,Suzuki, Eiichi,Ono, Yoshio
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- Photoinduced Direct Synthesis of Silylene-Bridged Dinuclear Iron Complexes5-C5H5)2Fe2(CO)2(μ-CO)(μ-SiHR)> from 5-C5H5)Fe(CO)2SiMe3> and RSiH3 (R=t-Bu, (CMe2)2H)
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Photolysis of (Cp=η5-C5H5) in the presence of RSiH3 (R=t-Bu, (CMe2)2H) afforded silylene-bridged dinuclear complexes .The structure of the complex was determined by X-ra
- Tobita, Hiromi,Kawano, Yasuro,Shimoi, Mamoru,Ogino, Hiroshi
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p. 2247 - 2250
(2007/10/02)
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- HEXAMETHYLSILIRANE. I. PREPARATION, CHARACTERIZATION AND THERMAL DECOMPOSITION
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Hexamethylsilirane has been prepared by the action of magnesium on dimethyl-bis(α-bromoisopropyl)silane in tetrahydrofuran (THF) solution.It was found to be highly reactive toward atmospheric oxygen and moisture and to decompose when heated in solution at 60-75 deg C.Its decomposition results in the extrusion of dimethylsilylene which may add to the tetramethylethylene produced in the decomposition to regenerate the silirane, insert into the reactive SiC2 ring of the silirane to give octamethyl-1,2-disilacyclobutane or oligomerize to give (Me2Si)n oils.Dimethyldiisopropyl-, tetraisopropyl- and tert-butyltriisopropylsilane were prepared by catalytic hydrogenation of the corresponding isopropenylsilanes.Bromination of dimethyldiisopropylsilane at 65 deg C resulted in exclusive formation of dimethyl-bis(α-bromoisopropyl)silane.
- Seyferth, Dietmar,Annarelli, Dennis C.,Vick, Steven C.,Duncan, Don P.
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p. 179 - 195
(2007/10/02)
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