cas 1066-35-9, Chlorodimethylsilane | Articles data

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Dual Role of Doubly Reduced Arylboranes as Dihydrogen- and Hydride-Transfer Catalysts
Doubly reduced 9,10-dihydro-9,10-diboraanthracenes (DBAs) are introduced as catalysts for hydrogenation as well as hydride-transfer reactions. The required alkali metal salts M2[DBA] are readily accessible from the respective neutral DBAs and Li metal, Na metal, or KC8. In the first step, the ambiphilic M2[DBA] activate H2 in a concerted, metal-like fashion. The rates of H2 activation strongly depend on the B-bonded substituents and the counter cations. Smaller substituents (e.g., H, Me) are superior to bulkier groups (e.g., Et, pTol), and a Mes substituent is even prohibitively large. Li+ ions, which form persistent contact ion pairs with [DBA]2-, slow the H2-addition rate to a higher extent than more weakly coordinating Na+/K+ ions. For the hydrogenation of unsaturated compounds, we identified Li2[4] (Me substituents at boron) as the best performing catalyst; its substrate scope encompasses Ph(H)CNtBu, Ph2CCH2, and anthracene. The conversion of E-Cl to E-H bonds (E = C, Si, Ge, P) was best achieved by using Na2[4]. The latter protocol provides facile access also to Me2Si(H)Cl, a most important silicone building block. Whereas the H2-transfer reaction regenerates the dianion [4]2- and is thus immediately catalytic, the H--transfer process releases the neutral 4, which has to be recharged by Na metal before it can enter the cycle again. To avoid Wurtz-type coupling of the substrate, the reduction of 4 must be performed in the absence of the element halide, which demands an alternating process management (similar to the industrial anthraquinone process).
Von Grotthuss, Esther,Prey, Sven E.,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
(2019)
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Controllably oxidized copper flakes as multicomponent copper-based catalysts for the Rochow reaction
The metallic Cu flakes prepared by milling metallic Cu powder were controllably oxidized in air at different temperatures to obtain the Cu-based catalysts containing multicomponents of Cu, Cu2O, and CuO. These catalysts are explored in the Rochow reaction using silicon powder and methyl chloride (MeCl) as reactants to produce dimethyldichlorosilane (M2), which is the most important organosilane monomer in the industry. The samples were characterized by X-ray diffraction, temperature-programmed reduction, thermogravimetric analysis, oxidimetry analysis, particle size analysis, transmission electron microscopy, and scanning electron microscopy. Compared to the metallic Cu powder and Cu flakes, the controllably oxidized Cu flakes containing Cu, Cu2O, and CuO species show much higher M2 selectivity and silicon conversion in the Rochow reaction. The enhanced catalytic performance may stem from the larger interfacial contact among the gas MeCl, solid Si particles, and solid Cu-based catalyst flakes, as well as the synergistic effect among the different Cu species. The work would be helpful to the development of novel Cu-based catalysts for organosilane synthesis.
Liu, Shaomian,Wang, Yingli,Zhu, Yongxia,Wang, Guangna,Zhang, Zailei,Che, Hongwei,Jia, Lihua,Su, Fabing
p. 7826 - 7833
(2014)
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Kinetics of Insertion Reactions of Dimethylsilylene
Dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, inserts into the silicon-hydrogen bond in trimethylsilane and pentamethyldisilane with approximately zero activation energy, while insertion into hydrogen chloride requires an activation energy of 28 kJ mol-1; the results for silicon-hydrogen insertion shed some light on the mechanism of the thermolysis of pentamethyldisilane.
Davidson, Iain M. T.,Lawrence, F. Timothy,Ostah, Naaman A.
p. 859 - 860
(1980)
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Unlocking the Catalytic Hydrogenolysis of Chlorosilanes into Hydrosilanes with Superbases
The efficient synthesis of hydrosilanes by catalytic hydrogenolysis of chlorosilanes is described using an iridium (III) pincer catalyst. A careful selection of a nitrogen base (including sterically hindered guanidines and phosphazenes) can unlock the preparation of Me3SiH, Et3SiH, and Me2SiHCl in high yield (up to 98%) directly from their corresponding chlorosilanes.
Durin, Gabriel,Berthet, Jean-Claude,Nicolas, Emmanuel,Cantat, Thibault
p. 10855 - 10861
(2021)
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Suryanarayanan,B. et al.
p. 65 - 71
(1973)
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Partial reduction of MeSiCl3 and Me2SiCl2 using CaH2 or (TiH2)n at high temperature (300°C) leads to MeSiHCl2 and Me2SiHCl, respectively, in good yields but in low proportion. In the presence of AlCl3 as catalyst the reaction affords Me2SiCl2 and Me3SiCl, in yields higher than those previously observed in the absence of a reducing agent. These redistribution reactions involve MeSiHCl2 and Me2SiHCl as intermediates. Consequently Me2SiHCl with or without Me2SiCl2 and Alcl3 deposited on carbon black as catalyst can undergo disproportionation to give Me3SiCl.
Simon, Gerard,Lefort, Marcel,Birot, Marc,Dunogues, Jacques,Duffaut, Norbert,Calas, Raymond
p. 279 - 286
(1981)
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Kriegsmann,Engelhardt
p. 100,108
(1961)
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Hydrosilane synthesis via catalytic hydrogenolysis of halosilanes using a metal-ligand bifunctional iridium catalyst
Hydrogenolysis of various halosilanes was catalysed by iridium amido complexes to produce hydrosilanes. Selective monohydrogenolysis of di- and trichlorosilanes similarly proceeded, resulting in the formation of chlorohydrosilanes (R2SiHCl or RSiHCl2) as synthetically important building blocks for various organosilicon compounds. A mechanistic study supported the in-situ formation of an iridium hydride species as a key intermediate, which could transfer the hydride to the silicon atom through a metal–ligand bifunctional mechanism. One-pot hydrotrimethylsilylation of olefins was achieved via successive hydrogenolysis and hydrosilylation reactions starting from Me3SiCl.
Beppu, Teruo,Sakamoto, Kei,Nakajima, Yumiko,Matsumoto, Kazuhiro,Sato, Kazuhiko,Shimada, Shigeru
p. 75 - 80
(2018)
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GAS-PHASE PHOTOCHEMICAL REACTIONS OF DODECAMETHYLCYCLOHEXASILANE WITH SILICON COMPOUNDS. KINETICS OF SOME INSERTION REACTIONS OF DIMETHYLSILYLENE
Attempts to measure the kinetics of gas-phase insertion reactions of dimethylsilylene, generated by photolysis of dodecamethylcyclohexasilane, are described.Insertion of dimethylsilylene into silicon-hydrogen bonds was the main reaction with trimethylsilane, pentamethyldisilane, and sym-tetramethyldisilane; in all cases the activation energy for insertion was zero, and the rate constants were in the ratio of 1:3.1:4.3.Dimethylsilylene also inserted cleanly into hydrogen chloride with an activation energy of 28 kJ mol-1.Photochemical reactions with methylchlorosilanes were much more complex, involving little or no silylene chemistry; such reactions as did occur appeared to proceed almost entirely by radical mechanisms.
Davidson, Iain M.T.,Ostah, Naaman A.
p. 149 - 158
(1981)
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Calas et al.
p. 371
(1974)
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Chlorine Abstraction from Silicon-Chlorine Bonds by Trimethylsilyl Radicals
Attempts to measure the kinetics of the unusual abstraction reaction, Me3Si. + Me2SiCl2 -> Me3SiCl + Me2Si.Cl using thermal radical sources were unsuccessful.Kinetic data were obtained by using a photochemical radical source, yielding unconvetional Arrhenius parameters, the significance of which is discussed.
Davidson, Iain M. T.,Matthews, J. Ioan
p. 2277 - 2280
(1981)
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Emeleus,Onyszchuk
p. 604,606
(1958)
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Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
The Müller–Rochow direct process (DP) for the large-scale production of methylchlorosilanes MenSiCl4?n (n=1–3) generates a disilane residue (MenSi2Cl6?n, n=1–6, DPR) in thousands of tons annually. This report is on methylchlorodisilane cleavage reactions with use of phosphonium chlorides as the cleavage catalysts and reaction partners to preferably obtain bifunctional monosilanes MexSiHyClz (x=2, y=z=1; x,y=1, z=2; x=z=1, y=2). Product formation is controlled by the reaction temperature, the amount of phosphonium chloride employed, the choice of substituents at the phosphorus atom, and optionally by the presence of hydrogen chloride, dissolved in ethers, in the reaction mixture. Replacement of chloro by hydrido substituents at the disilane backbone strongly increases the overall efficiency of disilane cleavage, which allows nearly quantitative silane monomer formation under comparably moderate conditions. This efficient workup of the DPR thus not only increases the economic value of the DP, but also minimizes environmental pollution.
Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
p. 3809 - 3815
(2019)
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Direct Formation of (CH3)2HSiCl from Silicon and CH3Cl
A Cu-catalyzed reaction procedure was found for the selective formation of dimethylchlorosilane from the direct reaction of CH3Cl with solid Si.The new procedure is a two-step process.A Cu/Si sample is prepared by evaporating Cu onto clean polycrystalline Si under ultrahigh vacuum, and the Cu/Si surface is first activated by exposure to 10percent HSiCl3/CH3Cl at 598 K.After the HSiCl3/CH3Cl mixture is evacuated from the reactor, the activated Cu/Si surface is reacted in fresh CH3Cl.For low surface concentrations of Cu, the partially hydrogenated silane, (CH3)2HSiCl, is selectively produced.Trichlorosilane was also found to activate polycrystalline Si (in the absence of Cu) for production of highly chlorinated methylchlorosilanes at a much higher rate than on the Cu/Si surface but with poor selectivity to (CH3)2HSiCl.All reactions are carried out at atmospheric pressure in a reactor that is attached to an ultrahigh-vacuum chamber.This allows surface analysis by Auger electron spectroscopy, which detected SiClx on reacted surfaces.These SiClx sites, which appear necessary for methylchlorosilane formation, are apparently formed during activation by HSiCl3.
Magrini, Kimberly A.,Falconer, John L.,Koel, Bruce E.
p. 5563 - 5568
(1989)
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Moedritzer,van Wazer
p. 69,70, 74
(1968)
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PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS
The invention relates to a process for the stepwise synthesis of silahydrocarbons bearing up to four different organyl substituents at the silicon atom, wherein the process includes at least one step a) of producing a bifunctional hydridochlorosilane by a redistribution reaction, selective chlorination of hydridosilanes with an ether/HCI reagent, or by selective chlorination of hydridosilanes with SiCI4, at least one step b) of submitting a bifunctional hydridochloromonosilane to a hydrosilylation reaction, at least one step c) of hydrogenation of a chloromonosilane, and a step d) in which a silahydrocarbon compound is obtained in a hydrosilylation reaction.
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Page/Page column 54; 58

(2021/12/08)

Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
The industry-scale production of methylchloromonosilanes in the Müller–Rochow Direct Process is accompanied by the formation of a residue, the direct process residue (DPR), comprised of disilanes MenSi2Cl6-n (n=1–6). Great research efforts have been devoted to the recycling of these disilanes into monosilanes to allow reintroduction into the siloxane production chain. In this work, disilane cleavage by using alkali and alkaline earth metal salts is reported. The reaction with metal hydrides, in particular lithium hydride (LiH), leads to efficient reduction of chlorine containing disilanes but also induces disproportionation into mono- and oligosilanes. Alkali and alkaline earth chlorides, formed in the course of the reduction, specifically induce disproportionation of highly chlorinated disilanes, whereas highly methylated disilanes (n>3) remain unreacted. Nearly quantitative DPR conversion into monosilanes was achieved by using concentrated HCl/ether solutions in the presence of lithium chloride.
Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
supporting information
p. 13202 - 13207
(2019/10/22)

Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
The industrial production of monosilanes MenSiCl4?n (n=1–3) through the Müller–Rochow Direct Process generates disilanes MenSi2Cl6?n (n=2–6) as unwanted byproducts (“Direct Process Residue”, DPR) by the thousands of tons annually, large quantities of which are usually disposed of by incineration. Herein we report a surprisingly facile and highly effective protocol for conversion of the DPR: hydrogenation with complex metal hydrides followed by Si?Si bond cleavage with HCl/ether solutions gives (mostly bifunctional) monosilanes in excellent yields. Competing side reactions are efficiently suppressed by the appropriate choice of reaction conditions.
Sturm, Alexander G.,Santowski, Tobias,Schweizer, Julia I.,Meyer, Lioba,Lewis, Kenrick M.,Felder, Thorsten,Auner, Norbert,Holthausen, Max C.
supporting information
p. 8499 - 8502
(2019/06/13)

DISILANE-, CARBODISILANE-AND OLIGOSILANE CLEAVAGE WITH CLEAVAGE COMPOUND ACTING AS CATALYST AND HYDROGENATION SOURCE
The invention relates to a process for the manufacture of monosilanes of formula (I): MexSiHyClz (I), comprising: the step of subjecting a silane substrate (methyldisilanes, methyloligosilanes, or carbodisilanes) to a cleavage reaction of the silicon-silicon bond(s) or the silicon- carbon bonds in silane substrates the reaction involving a cleavage compound selected from a quaternary Group 15 onium compound R4 QX, a heterocyclic amine, a heterocyclic ammonium halide, or a mixture of R3P and RX. The starting material disilanes to be cleaved has the formula (II): MemSi2HnClo (II) The starting material oligosilanes to be cleaved have the general formula (III): MepSiqHrCIs (II I), The starting material carbodisilanes to be cleaved have the general formula (IV): (MeaSiHbCle)-CH2-(MecSiHdClf) (IV)
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Page/Page column 52

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
The invention relates to a process for the manufacture of organomonosilanes bearing both hydrogen and chlorine substituents at the silicon atom by subjecting a silane substrate comprising one or more silanes selected from organomonosilanes, organodisilanes and organocarbodisilanes, with the proviso that at least one of these silanes has at least one chlorine substituent at the silicon atom, to a redistribution reaction in the presence of a phosphane or amine acting as a redistribution catalyst.
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Page/Page column 29; 36; 39

(2019/04/16)

SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
The invention relates to a process for the production of chlorosilanes by subjecting one or more hydndosilanes to the reaction with hydrogen chloride in the presence of at least one ether compound, and a process for the production of such hydndosilanes serving as starting materials.
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Page/Page column 36; 37

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
The invention relates to a process for the manufacture of organomonosilanes, in particular, bearing both hydrogen and chlorine substituents at the silicon atom by subjecting a silane substrate comprising one or more organomonosilanes, with the proviso that at least one of these silanes has at least one chlorine substituent at the silicon atom, to the reaction with one or more metal hydrides selected from the group of an alkali metal hydride and an alkaline earth metal hydride in the presence of one or more compounds (C) acting as a redistribution catalyst.
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Page/Page column 37; 38

(2019/04/16)

CLEAVAGE OF METHYLDISILANES TO METHYLMONOSILANES
The invention relates to a process for the manufacture of methylmonosilanes comprising the step of subjecting one or more methyldisilanes to the cleavage reaction of the silicon-silicon bond, and optionally a step of separating the resulting methylmonosilanes.
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Page/Page column 28; 29

(2019/04/16)

PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES FROM HYDRIDOSILANES
The invention relates to a process for the manufacture of organomonosilanes bearing both hydrogen and chlorine substituents at the silicon atom by subjecting one or more organomonosilanes to the reaction with one or more di- or carbodisilanes in the presence of one or more compounds (C) acting as a redistribution catalyst, wherein at least one of the silanes has only hydrogen and organic residues at the silicon atoms.
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Page/Page column 44; 45

(2019/04/16)

INTEGRATED PROCESS FOR THE MANUFACTURE OF METHYLCHLOROHYDRIDOMONOSILANES
The present invention relates to an integrated process for the manufacture of methylchlorohydridomonosilanes in particular, from products of the Müller-Rochow Direct Process.
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Page/Page column 41; 42

(2019/04/16)

Dual Role of Doubly Reduced Arylboranes as Dihydrogen- and Hydride-Transfer Catalysts
Doubly reduced 9,10-dihydro-9,10-diboraanthracenes (DBAs) are introduced as catalysts for hydrogenation as well as hydride-transfer reactions. The required alkali metal salts M2[DBA] are readily accessible from the respective neutral DBAs and Li metal, Na metal, or KC8. In the first step, the ambiphilic M2[DBA] activate H2 in a concerted, metal-like fashion. The rates of H2 activation strongly depend on the B-bonded substituents and the counter cations. Smaller substituents (e.g., H, Me) are superior to bulkier groups (e.g., Et, pTol), and a Mes substituent is even prohibitively large. Li+ ions, which form persistent contact ion pairs with [DBA]2-, slow the H2-addition rate to a higher extent than more weakly coordinating Na+/K+ ions. For the hydrogenation of unsaturated compounds, we identified Li2[4] (Me substituents at boron) as the best performing catalyst; its substrate scope encompasses Ph(H)C=NtBu, Ph2C=CH2, and anthracene. The conversion of E-Cl to E-H bonds (E = C, Si, Ge, P) was best achieved by using Na2[4]. The latter protocol provides facile access also to Me2Si(H)Cl, a most important silicone building block. Whereas the H2-transfer reaction regenerates the dianion [4]2- and is thus immediately catalytic, the H--transfer process releases the neutral 4, which has to be recharged by Na metal before it can enter the cycle again. To avoid Wurtz-type coupling of the substrate, the reduction of 4 must be performed in the absence of the element halide, which demands an alternating process management (similar to the industrial anthraquinone process).
Von Grotthuss, Esther,Prey, Sven E.,Bolte, Michael,Lerner, Hans-Wolfram,Wagner, Matthias
supporting information
p. 6082 - 6091
(2019/04/17)

Preparation method of dimethyl hydrogen chlorosilane
The invention discloses a preparation method of dimethyl hydrogen chlorosilane. The method comprises the following steps of introducing dimethyldichlorosilance, a catalyst A and hydrogen gas into a fluidized bed reactor to perform first reaction; performing cyclone separation on a intermediate product to remove the catalyst A; then, introducing the materials into a fixed bed reactor filled with a catalyst B to perform secondary reaction; performing post-treatment on reaction products to obtain the dimethyl hydrogen chlorosilane, wherein the catalyst A and the catalyst B are bimetallic loaded catalysts using active carbon as carriers; the active ingredients of the bimetallic loaded catalysts are at least two materials from Pd, Pt and Ni; the average particle diameter of the catalyst A is 30 to 50 mum; the average particle diameter of the catalyst B is 3 to 5mm. The preparation method of the dimethyl hydrogen chlorosilane provided by the invention can realize high raw material conversion rate and target product selectivity.
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Paragraph 0045-0046

(2017/08/29)

PROCESS FOR SELECTIVE PRODUCTION OF HALOSILANES FROM SILICON-CONTAINING TERNARY INTERMETALLIC COMPOUNDS
A process includes contacting an organohalide with a ternary intermetallic compound at a temperature of 300 °C to 700 °C to form a reaction product including a halosilane. The ternary intermetallic compound includes three metals. The first metal is Cu or Mg; the second metal is Au, Ni, or Pd; and the third metal is Si.
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Paragraph 0044

(2014/08/06)

METHOD FOR PREPARING AN ORGANO-FUNCTIONAL SILANE
A process includes reacting an organometallic cuprate and a silicon precursor in the presence of a solvent. The process produces a reaction product including an organo-functional silane.
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Paragraph 0027

(2014/05/24)

PROCESS FOR THE PRODUCTION OF SILANE PRODUCTS FROM CALCIUM SILICIDE
A process for preparing a reaction product including a silane product includes step (i), (ii), and (iii). Step (i) is contacting an organohalide with a calcium silicide at a temperature from 300 °C to 700 °C to form the reaction product including a spent reactant and the silane product. The silane product has formula RmHnSiX(4-m-n), where each R is independently a monovalent organic group, each X is independently a halogen atom; subscript m is 0 to 4; subscript n is 0 to 2; and a quantity (m + n) is 0 to 4. Step (ii) is contacting, at a temperature from 200 °C to 1400 °C, the spent reactant with a silane of formula HaRbSiX(4-a-b), where subscript a is 0 to 4, subscript b is 0 or 1, a quantity (a + b) ≤ 4. The silane of formula HaRbSiX(4-a-b) is distinct from the silane product of formula RmHnSiX(4-m-n). When the quantity (a + b) 2; thereby forming a reactant. Step (iii) is contacting the reactant formed in step (ii) with an additional organohalide at a temperature from 300 °C to 700 °C to form an additional silane product of formula RmHnSiX(4-m-n). Steps (ii) and (iii) are performed separately and consecutively after step (i).
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Paragraph 0052

(2014/11/11)

SYNTHESIS OF ORGANOHALOSILANE MONOMERS FROM CONVENTIONALLY UNCLEAVABLE DIRECT PROCESS RESIDUE
Disclosed herein is a catalytic process for the synthesis of organohalosilane monomers from tetraorganodihalodisilanes and other compounds that are not cleaved during the conventional hydrochlorination of Direct Process Residue. The process is characterized by the use of a catalyst containing (1) one or more heterocyclic amines and/or one or more heterocyclic ammonium halides, and (2) one or more quaternary Group 15 onium compounds.
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Paragraph 0092; 0095

(2013/07/19)

Phenyl(fluoro)dichlorosilane: A new synthon for the preparation of compounds containing chiral silicon atom
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Basenko,Voronkov,Zelenkov,Albanov
body text
p. 219 - 222
(2012/06/30)

PROCESS FOR PRODUCING ORGANOHALOHYDROSILANES
The invention pertains to a method of producing organohalohydrosilanes by treating a silicon metal with a halogen-containing compound, wherein the halogen-containing compound has a formula selected from RdSiX4-d (II) and RX (III), combining a catalyst and a promoter with the treated silicon metal, and contacting the combination with hydrogen gas and an organohalide. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a combination of silicon metal, a catalyst, a promoter and a hydrogen- storage material. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a combination of a silicon metal, a catalyst, a promoter and a hydrogenation catalyst. The invention also pertains to a method of producing organohalohydrosilanes by contacting an organohalide and hydrogen gas with a reaction mass residue and optionally a hydrogenation catalyst.
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Page/Page column 22-23

(2010/07/09)

Process For Preparing Methylchlorosilanes
The invention relates to a process for the direct synthesis of methylchlorosilanes by reaction of chloromethane with a contact composition comprising silicon and copper catalyst, wherein the concentration of oxygen in the chloromethane used is reduced by mixing a) chloromethane which contains oxygen, and b) chloromethane which contains a gaseous boron compound.
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Page/Page column 3

(2008/06/13)

Process For Preparing Si-H-Containing Silanes
Silanes of the general formula (1) [in-line-formulae]RaSiHbX4-b-a ??(1)[/in-line-formulae] are prepared by disproportionating at least one more highly chlorinated silane in the presence of a homogeneous catalyst in an apparatus with at least one reactive distillation column and at least one additional reactor selected from among prereactors and side reactors, where R is an alkyl, aryl, alkaryl or haloalkyl radical, X is a halogen atom, a is 0 or 1, and b is 2, 3 or 4.
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Page/Page column 4-5

(2009/01/24)

METHOD FOR MAKING ALKYHALOSILANES
A method for making alkylhalosilanes is provided comprising reacting an alkyl halide and silicon in the presence of a copper catalyst comprising copper powder, particulate copper, copper flake, or combinations thereof and at least one co-catalyst.
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Page/Page column 6-8

(2008/06/13)

Process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorsilanes
The invention provides a continuous process for preparing alkylchlorosilanes from the residues of direct synthesis of alkylchlorosilanes which comprise liquid constituents with a boiling point of at least 70° C. at 1013 hPa and may also contain solids, with hydrogen chloride, by passing the residues at a temperature not above 200° C. and hydrogen chloride at a temperature higher than the latter into a reactor so that the resultant reaction temperature is from 400° C. to 800° C.
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Page/Page column 2

(2008/06/13)

PREPARATION OF TITANIUM(II) OR ZIRCONIUM(II) COMPLEXES
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(2008/06/13)

A novel route to chlorodimethylsilane
A new efficient laboratory method of preparation of chlorodimethylsilane (Cl(CH3)2SiH) has been elaborated, which is a modification of the Eaborn et al. method (34) and is based on a transsilylation reaction of substituted (amino)dimethylhydrosilanes, R2NSiMe2H (R2 = Me2, Et2, (CH2)n, etc.) with dimethyldichlorosilane (Me2SiCl2). The reaction proceeds at reflux, at 70°C, preferably with an excess of Me2SiCl2. The most important feature of this novel method is a recovery of intermediate (amino)chlorodimethylsilanes (R2NSiMe2Cl), which can be again reduced to R2NSiMe2H. The transsilylation mechanism has been proven by reaction of (diethylamino)methylphenylsilane with Me2SiCl2. The products of this latter reaction are HMePhSiCl and R2NSiMe2Cl, thus a disproportionation mechanism has been excluded. New substituted bis(amino)dimethylsilanes ((R2N)2SiMe2), (amino)dimethylchlorosilanes (R2NSiMe2Cl), and (amino)dimethylhydrosilanes (R2NSiMe2H) have been synthesized and characterized by NMR and IR.
Chrusciel
p. 1405 - 1411
(2007/10/03)

Substituted indenyl containing metal complexes and olefin polymerization process
PCT No. PCT/US96/16012 Sec. 371 Date Feb. 19, 1998 Sec. 102(e) Date Feb. 19, 1998 PCT Filed Oct. 3, 1996 PCT Pub. No. WO97/15583 PCT Pub. Date May 1, 1997Group 4 metal complexes comprising an indenyl group substituted in the 2 or 3 position with at least one group selected from hydrocarbyl, fluoro-substituted hydrocarbyl, hydrocarbyloxy-substituted hydrocarbyl, dialkylamino-substituted hydroacrbyl, silyl, germyl and mixtures thereof, said indenyl group further being covalently bonded to the metal by means of a divalent ligand group, catalytic derivatives thereof and their use as olefin polymerization catalysts are disclosed.
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(2008/06/13)

Preparation of titanium(II) or zirconium(II) complexes
Titanium and zirconium complexes comprising one or more, cyclic, delocalized pi -bonded ligand groups wherein the metal of said complexes is in the +2 formal oxidation state are prepared in high yield and purity by reaction of the corresponding titanium or zirconium halides in the +3 or +4 oxidation state with a di(C1-20 alkyl) magnesium reagent. The complexes are used as catalyst components for olefin polymerization catalysts.
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(2008/06/13)

Intermediacy of surface silylene in the direct synthesis of methylchlorosilanes
The reaction of silicon with methyl chloride was carried out in the presence of butadiene. The products consisted of 1,1-dichlorosila-cyclopent-3-ene, 1-methyl-1-chlorosilacyclopent-3-ene and 1-chlorosilacyclopent-3-ene besides methylchlorosilanes. Silacyclopent-3-enes accounted for 25% of the whole products. The high selectivity for silacyclopent-3-enes indicates that surface silylene is the intermediate in the reaction of silicon with methyl chloride.
Okamoto, Masaki,Onodera, Satoshi,Okano, Tomoki,Suzuki, Eiichi,Ono, Yoshio
p. 67 - 71
(2007/10/03)

Process for preparing alkylhydrogenchlorosilanes
Alkylhydrogenchlorosilanes of formula I: wherein R are identical or different alkyl radicals, x is 1 or 2 and y is 1 or 2 and the sum of x and y is equal to 3, are prepared by comproportionating alkylchlorosilanes of formula II: wherein R denotes identical or different alkyl radicals, a is 1 or 2 and n is 2 or 3 and the sum of a and n is equal to 4 with hydrogenchlorosilanes of formula III: wherein R denotes identical or different alkyl radicals, b is 0, 1, 2 or 3 and c is 1, 2, 3 or 4 and the sum of b and c is equal to or smaller than 4, in the presence of a catalyst saturated with a hydrogen halide.
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(2008/06/13)

Preparation of a vinylsiloxane-benzocylobutene from a hydrolyzable vinylsilane-benzocylobutene
This invention relates to a novel process for preparing vinylsiloxane-BCBs (vinylsiloxane-benzocyclobutenes) comprising reacting a hydrolyzable hydrosilating reagent with an acetylene-BCB in the presence of a catalyst, then hydrolyzing the hydrolyzable vinylsilane-BCB to form a vinylsiloxane-BCB.
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(2008/06/13)

Concurrent preparation of dimethylchlorosilane and triorganochlorosilane
Dimethylchlorosilane and a triorganochlorosilane of the formula: R1 R2 R3 SiCl wherein R1, R2, and R3 are independently selected from monovalent hydrocarbon groups are concurrently prepared by reacting dimethyldichlorosilane with a SiH bond-containing silane compound of the formula: R1 R2 R3 SiH in the presence of a Lewis acid catalyst. The method is especially effective for concomitant preparation of dimethylchlorosilane and trimethylchlorosilane or t-butyldimethylchlorosilane in an inexpensive, simple, safe manner and in high yields.
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(2008/06/13)

Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
Disclosed is a process for preparing a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, comprising reacting (i) a lithium, sodium or potassium salt of a cyclopentadiene derivative with (ii) a silicon halide compound or a germanium halide compound in the presence of a cyanide or a thiocyanate. The cyanide or the thiocyanate is preferably a copper salt. According to the process of the invention, a cyclopentadienyl group-containing silicon compound or a cyclopentadienyl group-containing germanium compound, which is very useful for the preparation of a metallocene complex catalyst component, can be prepared in a high yield for a short period of time.
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(2008/06/13)

REACTIONS OF ORGANYLHALOSILANES WITH 1,1,3,3-TETRA- AND HEXAMETHYLDISILAZANE
Organylchlorosilanes, and also SiCl4, decompose 1,1,3,3-tetra- and hexamethyldisilazanes with formation of hitherto unknown organylchlorosilazanes of general formulas R4-nSiCln-1NHSiH(CH3)2 and R4-nSiCln-1NHSi(CH3)3 (n = 2-4) in yields of 54-98percent.The IR and mass spectra of the prepared compounds were studied.
Basenko, S. V.,Gebel', I. A.,Toryashinova, D. D.,Vitkovskii, V. Yu.,Mirskov, R. G.,Voronkov, M. G.
p. 1039 - 1042
(2007/10/02)

Method for preparing monohalogenosilanes
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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(2008/06/13)

Process for reducing silicon, germanium and tin halides
A process for reducing halogen-containing compounds of silicon, germanium or tin with lithium hydride in the presence of tetrahydrofuran wherein the lithium hydride is first heated in the tetrahydrofuran and then the halogen-containing compound is added.
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(2008/06/13)

Process for the preparation of diorganohalogenosilanes
A process for preparing diorganohalogenosilanes wherein diorganodihalogenosilanes are reacted with at least one organosilicon compound having at least one Si--H bond in the molecule and selected from polysilanes, polycarbosilanes and polysilphenylenes is described. This reaction proceeds in the presence of a Lewis acid.
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(2008/06/13)

EFFECT OF HCl ON THE HYDROLYSIS OF TRIORGANOCHLOROSILANES
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Kopylov, V. M.,Agashkov, S. P.,Mosin, A. M.,Glukhova, M. A.
p. 940 - 947
(2007/10/02)

DISPROPORTIONATION OF METHYLDICHLOROSILANE UNDER THE ACTION OF SPEIER CATALYST
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Belyakova, N. R.,Mileshkevich, V. P.
p. 640
(2007/10/02)

SELECTIVE REDUCTION OF DICHLORODIMETHYLSILANE TO CHLORODIMETHYLSILANE
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Sluchevskaya, N. P.,Soldatov, V. M.,Sheludyakov, V. D.
p. 1647 - 1650
(2007/10/02)

SILYL AND SILYLMETHYL RADICALS, SILYLENES, SILA-ALKENES, AND SMALL RING SILACYCLES IN REACTIONS OF ORGANOCHLOROSILANES WITH ALKALI METAL VAPOURS
Dehalogenation of the organochlorosilanes Me3SiCl (I), Me2PrSiCl (II), Me3SiSiMe2Cl (III), Me3SiCH2SiMe2Cl (IV), ClCH2SiMe3 (V), ClCH2SiMe2SiMe3 (VI), ClCH2Me2SiSiMe2CH2Cl (VII), Me2SiCl2 (VIII), MePrSiCl2 (IX), Me3SiCH2SiMeCl2 (X), Me3SiCH2CH2SiMeCl2 (XI), Me3SiCH2CH2CH2SiMeCl2 (XII), ClCH2Si(H)MeCl (XIII), ClCH2SiMe2Cl (XIV), ClMe2SiSiMe2Cl (XV), ClCH2CH2CH2Si(H)MeCl (XVI), ClCH2CH2CH2SiMe2Cl (XVII), ClCH2CH2OSiMe2Cl (XVIII), ClMe2SiCH2SiMe2Cl (XIX), ClMe2SiCH2CH2SiMe2Cl (XX), and ClMe2SiCH2CH2CH2SiMe2Cl (XXI) with K/Na alloy vapours at 0.1-1 Torr and 300-320 deg C yields products derived from the reactions of short-lived intermediates, such as silyl and silylmethyl radicals, silylenes, and sila-alkenes.In addition, small-ring silacycles of low stability are formed as the intermediates in some of the dehalogenation reactions.Combination and H-atom abstraction are the main reactions of silyl and silyl-methyl radicals.These radicals are not prone to decomposition reactions when C-H, C-C, or Si-C bonds are at the β(Si-Si) bond with the formation of Me2Si=CH2 and the trimethylsilyl radical.The generation of alkylmethylsilylenes is accompanied by their decomposition processes, which involves intramolecular β(C-H) insertion of alkylmethylsilylenes and 2+1>-thermocyclodecomposition of intermediate silacyclopropanes.The contribution of δ(C-H) and ε(C-H) insertion reactions is much less pronounced, and in the formation of five- or six-membered silacycles.We did not succeed in obtaining monosilacyclobutanes, as the intramolecular γ(C-H) insertion is not typical for silylenes with alkyl substituents.Dehalogenation of chloromethylchlorosilanes with alkali metal vapours yields sila-alkenes, and that of 1,2-dichlorodisilanes gives disilenes. 1-Methyl-1-silaethylene, obtained by this method, does not rearrange into dimethylsilene, but dimerizes to give 1,3-dimethyl-1,3-disilacyclobutane.The formation of 1,3,5-trisilacyclohexanes takes place due to subsequent radical addition at the silicon-carbon double bond and cyclization of 1,6-biradicals.Dehalogenation of organochlorosilanes XVI, XVII, and XX opens up possibilities for the gas-phase synthesis of small organosilicon heterocycles: monosilecyclobutanes and 1,2-disilacyclobutanes.A new, low-stability heterocycle, i.e. 1,1,2,2-tetramethyl-1,2-disilacyclobutane, has been obtained, which enables a new, high polymer, polyethylenetetramethyldisilene, to be obtained.In the case of organochlorosilanes XVIII and XIX, cyclization is accompanied by secondary reactions of silacycles, rearrangements, dimerization, or decomposition.
Gusel'nikov, L. E.,Polyakov, Yu. P.,Volnina, E. A.,Nametkin, N. S.
p. 189 - 204
(2007/10/02)

Hydroalkenyloxysilanes
The invention provides a novel class of organosilicon compounds which are hydrogenalkenyloxysilanes represented by the general formula STR1 in which R1 is a monovalent hydrocarbon group having from 1 to 8 carbon atoms, R2, R3 and R4 are each a hydrogen atom or a monovalent hydrocarbon group having from 1 to 8 carbon atoms and n is a number of zero, 1 or 2. The silane compounds are readily obtained by the dehydrochlorination reaction between a corresponding hydrogen-containing chlorosilane compound and an α, β-unsaturated aldehyde compound or a ketone compound in the presence of an acid acceptor. The compounds are useful as a modifying agent in the silicone technology and also serve as a curing agent.
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(2008/06/13)