- 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 54; 57
(2021/12/08)
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- Borohydride catalyzed redistribution reaction of hydrosilane and chlorosilane: A potential system for facile preparation of hydrochlorosilanes
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Various borohydrides were found to catalyze the redistribution reaction of hydrosilane and chlorosilane in different solvents to produce hydrochlorosilanes efficiently and facilely. The redistribution reaction was affected by solvent and catalyst. The substrate scope was investigated in HMPA with LiBH4 as catalyst. A possible mechanism was proposed to explain the redistribution process.
- Ai, Liqing,Chen, Yi,Li, Yongming,Xu, Caihong
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p. 17404 - 17407
(2020/06/19)
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- Facile preparation of hydrochlorosilane by alkali metal halide catalyzed Si-H/Si-Cl redistribution reaction
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Various alkali metal halides were found to catalyze the Si-H/Si-Cl redistribution reaction in different polar solvents efficiently. The scope of silane substrate was studied using KF as catalyst and 18-crown-6 as cocatalyst in DMI. The alkali metal halides catalyzed redistribution system provides a useful method to prepare hydrochlorosilanes more facilely. A possible mechanism was proposed to explain the process.
- Chen, Yi,Li, Yongming,Xu, Caihong
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supporting information
(2020/09/21)
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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; 39; 40
(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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- By the hydrogen-containing silane-efficient and controllable synthetic chlorosilane method (by machine translation)
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The invention relates to a method of synthesizing chlorosilane from hydrogen-containing silane. The method comprises the step of enabling the hydrogen-containing silane to react with copper chloride in the presence of inert material particles. Dosage of a solvent is greatly lowered (only 0-150 ml of solvent is needed for synthesizing every 0.1 mol of chlorosilane), and even the solvent can be not used, and the reaction can be carried out as long as liquid silane can completely soak solid materials. Reaction time is greatly shortened and side reactions are less. Meanwhile, conversation rate of the reaction is greatly improved, and yield of a purified product is higher.
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Paragraph 0047; 0048
(2017/12/02)
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- B(C6F5)3-Catalyzed Selective Chlorination of Hydrosilanes
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The chlorination of Si?H bonds often requires stoichiometric amounts of metal salts in conjunction with hazardous reagents, such as tin chlorides, Cl2, and CCl4. The catalytic chlorination of silanes often involves the use of expensive transition-metal catalysts. By a new simple, selective, and highly efficient catalytic metal-free method for the chlorination of Si?H bonds, mono-, di-, and trihydrosilanes were selectively chlorinated in the presence of a catalytic amount of B(C6F5)3 or Et2O?B(C6F5)3 and HCl with the release of H2 as a by-product. The hydrides in di- and trihydrosilanes could be selectively chlorinated by HCl in a stepwise manner when Et2O?B(C6F5)3 was used as the catalyst. A mechanism is proposed for these catalytic chlorination reactions on the basis of competition experiments and density functional theory (DFT) calculations.
- Chulsky, Karina,Dobrovetsky, Roman
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supporting information
p. 4744 - 4748
(2017/04/11)
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- An efficient method to synthesize chlorosilanes from hydrosilanes
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An efficient, highly selective and productive synthesis of chlorosilanes from hydrosilanes is reported. Ceramic spheres were added to chlorination reaction systems and found to greatly increase the efficiency and yields of the reactions. PhSiH2Cl, PhSiHCl2, PhSiCl3, Ph 2SiHCl, Ph2SiCl2, PhMeSiHCl and PhMeSiCl 2 were synthesized from the corresponding hydrosilanes in only a few hours with yields that typically exceeded 90%. This is the first time PhSiCl3, Ph2SiHCl, Ph2SiCl2 and PhMeSiCl2 have been synthesized by this method. The factors that affect the rate of the chlorination reaction were studied. In addition the rate constant, reaction order and apparent activation energy of the chlorination reaction were also determined by kinetics study. The reaction was found to have an induction period.
- Wang, Wenchao,Tan, Yongxia,Xie, Zemin,Zhang, Zhijie
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- Iron-catalyzed chlorination of silanes
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A simple and highly efficient iron-catalyzed method for the chlorination of silanes has been developed. By use of 0.5-2% of the Fe(III)-based catalyst FeCl3 or Fe(acac)3 in the presence of 1-1.5 equiv of acetyl chloride as the chlorine donor, a large number of silanes, alkoxysilanes, and silanols were converted to the corresponding chlorosilanes in 50-93% yields. In contrast to earlier reported methods often suffering from expensive catalysts or use of stoichiometric metal salts, hazardous reagents, and reaction conditions, the presently described methodology allows benign reaction conditions and simple workup while using only catalytic amounts of a readily available and economically viable iron catalyst.
- Savela, Risto,Zawartka, Wojciech,Leino, Reko
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experimental part
p. 3199 - 3206
(2012/06/04)
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- Synthesis of 2-methylidene-1-silacyclohexanes by intramolecular hydrosilylation
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The preparation of various (hex-5-ynyl)silanes was achieved following two different synthetic approaches from readily available materials such as 4-bromobutene, 6-iodohexyne and chlorosilanes. Different reaction conditions for intramolecular hydrosilylation were tested to prepare the corresponding 2-methylidene-1-silacyclohexanes. Notably, the use of Speier's catalyst allowed the regioselective formation of the desired products in moderate yields.
- Díez-González, Silvia,Blanco, Luis
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p. 2033 - 2040
(2008/09/19)
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- METHOD OF MAKING PHENYL-CONTAINING CHLOROSILANES WITH ALIPHATIC OR CYCLOPARAFFINIC HYDROCARBON SOLVENTS
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Phenylmethyldichlorosilanes and diphenylmethylchlorosilanes are prepared by a Grignard process involving the step of contacting a phenyl Grignard reagent, an ether solvent, a trichlorosilane, and an aliphatic or cycloparaffinic hydrocarbon coupling solvent; in a mole ratio of the ether solvent to the phenyl Grignard reagent is 2 to 5, the mole ratio of the trichlorosilane to the phenyl Grignard reagent is 0.1 to 10, and the mole ratio of the aliphatic or cycloparaffinic hydrocarbon coupling solvent to the phenyl Grignard reagent is 3 to 7. Preferred reactants include phenylmagnesium chloride as the phenyl Grignard reagent; diethyl ether as solvent; n-heptane as the aliphatic hydrocarbon coupling solvent, or cyclohexane as the cycloparaffinic hydrocarbon coupling solvent; and methyltrichlorosilane.
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Page/Page column 5-7
(2008/06/13)
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- Selective synthesis of halosilanes from hydrosilanes and utilization for organic synthesis
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Selective synthesis of halosilanes has been examined. Various types of halosilanes and halohydrosilanes, such as R3SiX, R2SiHX, R2SiX2, RSiH2X, RSiHX2 (X=Cl, Br, F), were obtained by the reactions of the corresponding hydrosilanes with Cu(II)-based reagents selectively in high yields. This method could be also applied to the synthesis of chlorofluorosilanes and chlorohydrogermanes. On the other hand, iodo- and bromosilanes and germanes were obtained by Pd- or Ni-catalyzed hydride-halogen exchange reactions of hydrosilanes with alkyl or allyl halides. Their synthetic applications have been demonstrated by using iodo- and bromosilanes and chlorofluorosilanes.
- Kunai, Atsutaka,Ohshita, Joji
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- A novel route to chlorodimethylsilane
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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
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p. 1405 - 1411
(2007/10/03)
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- Redistribution of dichlorosilanes and dihydridosilanes. Synthesis of chloro hydridosilanes
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The redistribution of dichlorosilanes RSi(CH3)Cl2 and dihydridosilanes RSi(CH3)H2, prepared by reduction of the homologues dichlorosilanes, in the presence of a quaternary ammonium salt is presented. The influence of the nature of R (fluoroalkyl chain RFCH2CH2 with RF = CF3, C4F9, C8F17, alkyl chain R = C6H13 or aromatic R = C6H5) and of the temperature on the rate of the reaction is studied. The equilibrium constants and free enthalpies are calculated and discussed taking into account the nature of R. The new products described were characterized from I.R, 1H, 19F and 29Si NMR spectroscopies.
- Benouargha,Boulahia,Boutevin,Caporiccio,Guida-Pietrasanta,Ratsimihety
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- On the Thermal Behaviour of Some (Methylphenylsilyl)methyl Carbonate Derivatives
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The synthesis and the thermal behaviour of the (methylphenylsilyl)methyl carbonates CH3(C6H5)Si(H)CH2OC(O)X (6: X = OCH3; 7: X = Cl; 8: X = N(CH3)2) is described. 8 rearranges in toluene solution at 100 deg C quantitatively to give the carbamoyloxysilane C6H5(CH3)2SiOC(O)N(CH3)2 (11), whereas neat 6 and 7 at 135 deg C undergo quantitative formation of C6H5(CH3)2SiOCH3 (12) and C6H5(CH3)2SiCl (13), respectively.The formation of 12 and 13 is explained by a rearrangement reaction (by analogy to the rearrangement of 8), followed by a decarboxylation.The thermally induced transformations 6-->12, 7-->13, and 8-->11 were found to be first-order reactions with half-lifes of ca. 2.6 h (135 deg C, neat), ca. 4.5 h (135 deg C, neat), and ca. 3.7 h (100 deg C, in toluene), respectively. - Keywords: (Methylphenylsilyl)methyl Carbonates, Rearrangement, Dimethylphenylsilyl Carbonates, Decarboxylation
- Tacke, Reinhold,Link, Matthias,Bentlage-Felten, Anke,Zilch, Harald
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p. 942 - 947
(2007/10/02)
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