- SELECTIVE PREPARATION OF VINYL- AND ETHYL-FUNCTIONALIZED CHLOROSILANES
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A method of preparing an organosilicon compound via selective silylation of ethylene is disclosed. The method comprises reacting via silylation (A) a hydridochlorosilane compound and (B) ethylene in the presence of (C) a catalyst, thereby preparing the organosilicon compound. The silylation may be selectively conducted as a dehydrogenative coupling to prepare the organosilicon compound as a vinylchlorosilane compound, or as a hydrosilylation to prepare the organosilicon compound as an ethylchlorosilane compound. The catalyst (C) comprises a Ru(0) complex, and may be recycled for use in subsequent silylation reactions without purification. The organosilicon compound prepared according to the method is also disclosed.
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Paragraph 0097-00107; 00108-00110
(2021/06/26)
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- Reactions of Trichlorogermane and Trimethylgermane Etherates with 1,3-Divinyl-1,1,3,3-tetramethyldisiloxane
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Abstract: The effect of the reactant ratio in the reaction of tetramethyldisiloxane with germanium tetrachloride and diethyl ether on the structure and reactivity of the resulting trichlorogermane–diethyl ether complexes was studied, and the products were
- Blagushina, A. I.,Efimenko, D. A.,Gritskova, I. A.,Komalenkova, N. G.,Lakhtin, V. G.,Semyashkina, I. A.,Sokol?skaya, I. B.,Storozhenko, P. A.,Ushakov, N. V.
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p. 968 - 976
(2020/07/27)
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- Preparation method of unsaturated organosilazane
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The invention provides a preparation method of unsaturated organosilazane, and the method comprises the following steps: mixing an organic silicide, an organic solvent and a metal halide, dropwisely adding an acylation reagent at 50-100 DEG C under stirring conditions, and refluxing for 3-8 hours to obtain R1R2R3SiX; X is selected from Cl, Br or I; the organic silicide is selected from R1R2R3SiO4or R1R2R3SiOSiR1R2R3; R1 is selected from alkyl containing a double-bond functional group; R2 and R3 are selected from alkyl containing a double-bond functional group, C1-C4 alkyl or phenyl; R4 is selected from a C1-C4 alkyl group; and by introducing ammonia gas into the R1R2R3SiX to carry out a reaction, unsaturated organosilazane R1R2R3SiNHSiR1R2R3 is obtained. The method is simple, mild in condition, free of pollution and high in yield. The yield of the R1R2R3SiNHSiR1R2R3 is 95-96%.
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Paragraph 0041-0043; 0046-0050
(2020/09/16)
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- Synthesis method for dimethylvinylchlorosilane
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The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method for dimethylvinylchlorosilane. Antimony butter SbCl3 is taken as a catalyst, dimethyldichlorosilance Me2SiCl2 is taken as a raw material, and the antimony butter SbCl3 and the dimethyldichlorosilance Me2SiCl2 react with vinylmagnesium bromide or vinylmagnesium chloride to undergo Grignard reaction; the antimony butter SbCl3 which performs a key function as the catalyst is added to enable the yield of the dimethyldichlorosilance Me2ViSiCl to be greatly improved to be 80% or more (91% is highest) from the yield which does not exceed 15% according to the report in an original literature; when the comparison reaction of the catalyst antimony butter SbCl3 is not used, the yield of the dimethylvinylchlorosilane Me2ViSiCl is only 32.8%.
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Paragraph 0039; 0040
(2019/02/19)
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- A dimethyl vinylchloride silane preparation method
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The invention discloses a preparation method of dimethylvinylchlorosilane, and the method is as follows: in the presence of a catalyst, reacting chloroacetyl chloride with dimethyl vinyl ethyoxyl silane for esterification, to obtain the dimethylvinylchlorosilane. The preparation method is not only cheap in raw materials, mild in reaction condition, and easy in purification of product, and the product yield and purity are high.
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Paragraph 0025-0040
(2019/02/02)
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- Silyl and σ-silane ruthenium complexes: Chloride substituent effects on the catalysed silylation of ethylene
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Silylation of ethylene by the chlorosilanes HSiMe2Cl and HSiMeCl2 was catalysed by the bis(dihydrogen) complex RuH 2(η2-H2)2(PCy3) 2 (1). Dehydrogenative silylation leading to the formation of the corresponding vinylsilanes was in competition with hydrosilylation. The rate and selectivity of the reactions were influenced by the number of chloro substituents and the ethylene pressure. A comparative mechanistic study was performed in toluene-d8 with the two chlorosilanes. Reaction of 1 with an excess of HSiMe2Cl (10 equiv.) produced the σ-silane complexes RuH2(η2-H2)(η2- HSiMe2Cl)(PCy3)2 (2Me2Cl), RuH 2(η2-HSiMe2Cl)2(PCy 3)2 (3Me2Cl) and the silyl complex RuCl(SiMe2Cl)(η2-H2)(PCy3) 2 (4Me2Cl), all characterised by multinuclear NMR spectroscopy. Complexes 2Me2Cl and 3Me2Cl adopt a cis configuration for the two bulky phosphine ligands as a result of stabilising SISHA (Secondary Interactions between Silicon and Hydrogen Atoms) interactions. Complex 4Me2Cl resulted from the stoichiometric reaction of HSiMe2Cl with 1 producing RuHCl(η2-H 2)(PCy3)2in situ which further reacted with evolution of H2 and formation of 4Me2Cl. When reacting 1 with 10 equiv. of HSiMeCl2, the corresponding complexes 3MeCl 2 and 4MeCl2 were detected as well as traces of 2MeCl 2. The reactivity toward ethylene was then examined. Under catalytic conditions (excess silane in toluene-d8, ethylene atmosphere) only two compounds could be characterised: free PCy3 and the new (η6-aryl)(disilyl) complexes of the general formula Ru(η6-C6D5CD3)(SiMe 3-nCln)2(PCy3) (6Me 3-nCln-d8, n = 1,2). The X-ray structure of 6MeCl2 was obtained on a single-crystal at 160 K. When only 2 equiv. of HSiMe2Cl were added, the ethylene(silyl) complex RuH(SiMe 2Cl)(C2H4)(PCy3)2 (7Me2Cl) was obtained in addition to the organic products resulting from catalytic hydrogenation, hydrosilylation and dehydrogenative silylation, i.e. C2H6 (major one), C2H3SiMe 2Cl and C2H5SiMe2Cl. In the case of 2 equiv. of HSiMeCl2, upon ethylene addition, 7MeCl2 was formed in minority compared to a new disilyl complex Ru(SiMeCl2) 2(PCy3)2 (8MeCl2) characterised by NMR spectroscopy and X-ray diffraction on a single crystal at 160 K. In 8MeCl2, a formal 14-electron species, stabilisation through two agostic C-H bonds of the cyclohexyl groups was ascertained by DFT calculations.
- Lachaize, Sebastien,Vendier, Laure,Sabo-Etienne, Sylviane
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experimental part
p. 8492 - 8500
(2011/01/08)
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- Hydrosilylation process for gaseous unsaturated hydrocarbons
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Organosilicon compounds are prepared by the addition reaction of a gaseous unsaturated hydrocarbon with a silane or siloxane containing at least one silicon-bonded hydrogen atom in the presence of a hydrosilylation catalyst in a liquid reaction medium. In this process the unsaturated hydrocarbon and optionally the silane or siloxane is dispersed into the liquid reaction medium by a jet eductor (also known as a venturi pump) device and the resultant gas-in-liquid dispersion is introduced into a bubble reactor.
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Page/Page column 5
(2010/02/16)
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- Mechanistic studies on ethylene silylation with chlorosilanes catalysed by ruthenium complexes
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Silylation of ethylene by chlorosilanes is catalysed by ruthenium complexes. Mechanistic investigations reveal the presence of a complicated network of reactions leading to new σ-silane, ethylene and silyl complexes.
- Lachaize, Sebastien,Sabo-Etienne, Sylviane,Donnadieu, Bruno,Chaudret, Bruno
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p. 214 - 215
(2007/10/03)
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- Transition Metal Complexes of Troeger's Base and their Catalytic Activity for the Hydrosilylation of Alkynes
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Rhodium(III) and iridium(III) complexes of Troeger's base (TB), of structural type TB*2MCl3 (M=Rh, Ir), were prepared by treatment of TB with MCl3.The rhodium complex readily catalyzed the hydrosilylation of alkynes with high regio- and stereoselectively observed in some cases.
- Goldberg, Yuri,Alper, Howard
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p. 369 - 372
(2007/10/02)
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- Method for preparing monohalogenosilanes
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This invention relates to a method for preparing a monohalogenosilane, R1R2R3SiX which comprises the step of subjecting, to a rearrangement reaction, an organodisiloxane, (R1R2R3Si)2O and a polyhalogenosilane, R4nSiX4-nin the presence of active carbon or an ammonium salt, R5R6R7R8NY as a catalyst (wherein R1, R2, R3 and R8 each represents a hydrogen atoms or a monovalent hydrocarbon group; R4, R5, R6 and R7 each represents a monovalent hydrocarbon group, a part or whole of the hydrogen atoms in each hydrocarbon group may be substituted with other atoms or groups; X represents a halogen atom; Y represents a monovalent anion; n is 0, 1 or 2). The method permits the easy preparation of monohalogenosilanes, in a high yield, which are useful as starting materials for use in making silylating agents as well as a variety of organosilicon compounds without using any harmful hexaalkylphosphoric acid triamide type catalyst.
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- REACTIONS OF (Me3Si)3CSiMe2R COMPOUNDS (R = CH=CH2, CH2CH=CH2, CCPh, Ph, AND CH2Ph) WITH ELECTROPHILES
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No products of addition to the multiple bond are formed in reactions of TsiSiMe2R species (Tsi=(Me3Si)3C; R=CH=CH2, CH2CH=CH2, or (CCPh) with halogens or hydrogen halides.TsiSiMe2CH=CH2 gave (a) TsiSiMe2Cl on treatment with ICl in CCl4; (b) TsiSiMe2Br on treatment with Br2 in CCl4;.(c) TsiSiMe2I (slowly) on treatment with I2 in CCl4; and (d) TsiSiMe2OCOCF3 on treatment with neat CF3CO2H.TsiSiMe2CH2CH=CH2 gave: (a) TsiSiMe2Cl and TsiSiMe2I on treatment with ICl in CCl4; (b) TsiSiMe2Br on treatment with Br2 in CCl4; (c) TsiSiMe2I on treatment with I2 in CCl4; and (d) TsiSiMe2OCOCF3 rapidly on treatment with neat CF3CO2H.TsiSiMe2Ph gave TsiSiMe2Br on treatment with Br2 in CCl4 or CH3CO2H, and (b) TsiSiMe2Cl on treatment with HCl in Et2O.Reaction of TsiSiMe2Ph with nitric acid in (CH3CO)2O gave two mono-nitration products, probably the m- and p-isomers.Reaction of TsiSiMe2CH2Ph with Br2 gave exclusively TsiSiMe2Br, whereas reaction with nitric acid in (CH3CO)2O gave o- and p-nitro derivatives in 65/35 ratio.This last result casts serious doubt on previously proposed explanations of the predominance of ortho-nitration in the case of Me3SiCH2Ph.
- Damja, Ramadan I.,Eaborn, Colin,Sham, Wing-Cheong
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- Studies of silyl and germyl Group VI species. Part VII. The substituent effects of the vinyl group in 1,3-divinyltetramethyldisilyl chalcogenides
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Symmetrically substituted 1,3-divinyltetramethyldisilyl chalcogenides (CH2=CHSiMe2)2E, where E = O, S, Se, and Te have been prepared and characterized by their ir, Raman, (1)H and (13)C nmr spectra.Reactions of the sulfide and selenide with anhydrous H2S and H2Se, respectively, are discussed.
- Drake, John E.,Vahradian, Ankin,Glavincevski, Boris M.
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p. 2712 - 2715
(2007/10/02)
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- Process for the preparation of halogenosilanes
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Halogenosilanes are prepared from an organohalogenosilane and an organopolysiloxane as the starting materials by subjecting them to an intermolecular redistribution reaction in the presence of a monohydrochloride of a hexaalkylphosphotriamide. The thus prepared halogenosilanes, which are different from the starting halogenosilane reactant, are very useful in the silicone industry.
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