- PROCESS FOR THE STEPWISE SYNTHESIS OF SILAHYDROCARBONS
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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 53; 55
(2021/12/08)
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- PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
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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 31; 32
(2019/04/16)
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- SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
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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; 38; 39; 40; 49; 50
(2019/04/16)
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- PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES
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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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Paragraph 31; 32; 35; 39
(2019/04/16)
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- Disilane Cleavage with Selected Alkali and Alkaline Earth Metal Salts
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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
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supporting information
p. 13202 - 13207
(2019/10/22)
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- Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
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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.
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supporting information
p. 8499 - 8502
(2019/06/13)
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- CLEAVAGE OF METHYLDISILANES TO METHYLMONOSILANES
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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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Paragraph 25-27
(2019/04/16)
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- PROCESS FOR THE PRODUCTION OF ORGANOHYDRIDOCHLOROSILANES FROM HYDRIDOSILANES
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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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Paragraph 44; 45
(2019/04/16)
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- INTEGRATED PROCESS FOR THE MANUFACTURE OF METHYLCHLOROHYDRIDOMONOSILANES
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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 35; 36; 37
(2019/04/16)
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- CLEAVAGE OF METHYLDISILANES, CARBODISILANES AND METHYLOLIGOSILANES WITH ALKALI-AND ALKALINE EARTH METAL SALTS
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The invention relates to a process for the manufacture of methylmonosilanes comprising the step of subjecting one or more methyldisilanes, one or more methyloligosilanes, one or more carbodisilanes, or mixtures thereof to cleavage conditions resulting in the cleavage of silicon- silicon bonds or silicon-carbon bonds in carbodisilanes, and optionally a step of separating the resulting methylmonosilanes.
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Page/Page column 53; 54
(2019/04/16)
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- Lewis Base Catalyzed Selective Chlorination of Monosilanes
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A preparatively facile, highly selective synthesis of bifunctional monosilanes R2SiHCl, RSiHCl2 and RSiH2Cl is reported. By chlorination of R2SiH2 and RSiH3 with concentrated HCl/ether solutions, the stepwise introduction of Si?Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si?H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.
- Sturm, Alexander G.,Schweizer, Julia I.,Meyer, Lioba,Santowski, Tobias,Auner, Norbert,Holthausen, Max C.
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supporting information
p. 17796 - 17801
(2018/11/23)
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- Process For Preparing Si-H-Containing Silanes
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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)
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- Process for preparing organohydrongenosilanes
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Preparation of organylhydrogensilanes comprises comproportionating a mixture of organylhalosilanes in the presence of a catalyst, which contains at least one completely organically substituted ammonium or phosphonium unit. Preparation of organylhydrogensilanes comprises: comproportionating a mixture of organylhalosilanes by reaction of a organylhalosilane compound of formula (Z-R aSiCl 4-a) with organylhalosilane compound of formula (SiH bCl 4-b) to give a organylhalosilane compound of formula (Z-R aSiCl 3-a) and a organylhalosilane compound of formula (SiH b-yCl 4-b +y) in the presence of a catalyst which contains at least one completely organically substituted ammonium or phosphonium unit. R : alkyl, aryl, or alkaryl radical (optionally substituted with halo); a : 1-3; y, Z : 1-4; and b : 2-4.
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Page/Page column 3; 7
(2008/06/13)
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- Method for making alkylhalosilanes
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A method for making alkylhalosilanes is provided comprising reacting an alkyl halide and silicon in the presence of a copper catalyst comprising copper powder, particulated copper, copper flake, or combinations thereof and at least one co-catalyst.
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- Hydrogenation of Silicium-Halogen-Compounds with Trialkylstannyl Chloride/Sodium Hydride
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Organotinchlorides of the general formula R3SnCl and R2SnCl2 (R = Me, n-Bu, Ph) can easily be converted into the corresponding hydrides R3SiH and R2SiH2 employing NaH in diethylene glycol dialkyl ethers.Using trialkyltinhydrides like Bu3SnH in combination with a catalyst (tertiary amines, N-heterocycles, phosphonium or ammonium salts), Si-Cl bonds in mono- and disilanes are hydrogenated.In the case of disilanes, Si-Si bond cleavage and concurrent hydrogenation can be afforded with strongly nucleophilic catalysts.Partial hydrogenation is also possible.The whole process can be run cyclically. - Keywords: Alkylstannylhydride; Hydrogenation; Organochlorsilane.
- Hengge, E.,Grogger, C.,Uhlig, F.,Roewer, G.,Herzog, U.,Paetzold, U.
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p. 549 - 556
(2007/10/02)
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- Process for preparing cyclopentadienyl group-containing silicon compound or cyclopentadienyl group-containing germanium compound
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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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- Neue Wege zu Polysilanen
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Disilane dervatives undergo disproportionation reactions to polysilanes.Investigated were 1,2-dimethyldisilane and 1,2-dimethyltetrachlorodisilane with catalysts like NH4Cl, AgCN, and Na-cyanamide.In case of 1,2-dimethylsilane, with more than catalytic amounts of NH4Cl, a nitrogen containing polysilane is formed.Two new compounds MeSiH(NCO)2 and Me2Si2(NCO)4 were synthesized and characterized.The last one leads to a polymer at heating.Additionally an electrochemical formation of polydimethylsilane is described.
- Hengge, Edwin,Kalchauer, Wilfried
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p. 793 - 802
(2007/10/02)
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- Infrared Laser Photochemistry of SiH4-CH3Cl Mixtures
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By use of a pulsed CO2 TEA laser at 944.19 cm-1 and fluences in the range of 0.49-0.71 J/cm2, the infrared photochemistry of SiH4-CH3Cl mixtures has been studied in a pressure range of 50-100 Torr and over a temperature range of 295-428 K.The gaseous products observed are H2, CH4, Si2H6, and SiH3Cl, with trace amounts of Si3H8 and perhaps CH3SiH2Cl.As is usual in silane decomposition, a brown solid product containing silicon, hydrogen, and under some conditions, chlorine was also produced.The photochemical conversion is best described by initial decomposition of SiH4 to SiH2 and H2 followed by competition of SiH4 and CH3Cl for SiH2 molecules.The production of CH4 is believed to occur via the decomposition of highly energized CH3SiH2Cl* (formed by SiH2 insertion into the C-Cl bond of CHCl3), yielding CH4 and SiHCl as products.SiH3Cl is then formed by the secondary reaction of SiHCl with SiH4.Studies of the temperature dependece of the rates of competing reactions suggest that the activation energy for insertion of SiH2 into the C-Cl bond of CH3Cl is, within experimental error, equal to that for SiH2 insertion into the Si-H bond of SiH4.
- Moore, C. B.,Lampe, F. W.
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p. 4094 - 4099
(2007/10/02)
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- THERMOCHEMISTRY OF SILICON-CONTAINING COMPOUNDS PART 1.-SILICON-HALOGEN COMPOUNDS, AN EVALUATION
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Literature data on the heats of formation of silicon-halogen compounds have been collected and reviewed.The coverage includes all tetravalent monosilicon compounds containing Si-H-X, where X is a single halogen, as well as the subhalides SiXn, where n = 1,2 or 3.The data are critically evaluated from the standpoints of bond addivity and general chemical reactivity of the species involved as well as by detailed consideration of individual studies.Earlier compilations or reviews are discussed.A set of recommended values (with uncertainties) is proposed.For the divalent species, SiX2, a self-consistent set of lone-pair stabilisation energies is obtained.
- Walsh, Robin
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p. 2233 - 2248
(2007/10/02)
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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
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p. 279 - 286
(2007/10/02)
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