- 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; 38; 39; 40; 47; 48; 49; 50
(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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- SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE
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Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.
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Paragraph 0093
(2016/02/10)
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- A Strained Disilane-Promoted Carboxylation of Organic Halides with CO2 under Transition-Metal-Free Conditions
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By using a strained four-membered ring disilane (3,4-benzo-1,1,2,2-tetraethyldisilacyclobutene) and CsF, a wide range of aryl, alkenyl, alkynyl, benzyl, allyl, and alkyl halides was successfully carboxylated under an ambient CO2 atmosphere (CO2 balloon) at room temperature within 2 h. In this carboxylation, a highly reactive silyl anion, which is generated from the disilane and CsF, is a key to facilitating the formation of a carbanion equivalent. The resulting anionic species can be trapped with CO2 to produce carboxylic acids with high efficiency.
- Mita, Tsuyoshi,Suga, Kenta,Sato, Kaori,Sato, Yoshihiro
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supporting information
p. 5276 - 5279
(2015/11/18)
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- A direct method for preparing ethyldichlorosilane and its comparison with known alternative methods
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Various methods, alternative to direct synthesis, for preparing an important commercial organosilicon monomer, ethyldichlorosilane, were studied in detail. The methods, including organomagnesium and organoaluminum procedures, hydrosilylation, and combined methods, were analyzed from the viewpoint of feasibility of laboratory and small-tonnage commercial production, and their advantages and drawbacks were revealed.
- Lebedev,Sheludyakov,Lebedeva,Ovcharuk,Govorov,Kalinina
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p. 629 - 633
(2014/11/08)
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- The design, synthesis and validation of recoverable and readily reusable siloxane transfer agents for Pd-catalyzed cross-coupling reactions
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The development of competent, recoverable and reusable 1-oxa-2- silacyclopentene (siloxane) transfer agents for Pd-catalyzed cross-coupling reactions (CCRs) of organolithium reagents with aryl and alkenyl iodides has been achieved. Drawbacks of the first-generation siloxane-transfer agent (1), relating to facile recovery for potential recycling, have been addressed.
- Martinez-Solorio, Dionicio,Hoye, Adam T.,Nguyen, Minh H.,Smith, Amos B.
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supporting information
p. 2454 - 2457
(2013/07/05)
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- SILICON-BASED CROSS COUPLING AGENTS AND METHODS OF THEIR USE
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Compositions and methods using silicon-based cross-coupling agents in the formation of carbon-carbon and carbon-nitrogen bonds are described.
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Paragraph 0079
(2014/01/08)
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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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- Process for preparing alkylhydrogenchlorosilanes
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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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- 1,1,3,3-Tetraethyl-1,3-disilaisoindolines; Chromatographically Stable Silicon-Based Protection for Primary Amines
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The title compounds 4 have potential as protected derivatives of primary aliphatic amines.They are more stable to acid than the corresponding Stabase and Benzostabase derivatives 2 and 3, and are stable to flash chromatography on silica gel using all but the least polar solvent systems.
- Davis, Anthony P.,Gallagher, Patrick J.
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p. 3269 - 3272
(2007/10/02)
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- Method for the preparation of dialkylchlorosilanes
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A novel and effective method for the synthetic preparation of dialkylchlorosilanes as an important intermediate in the silicone industry is provided, which is based on the selectivity of a specific combination of a reaction solvent and a reducing agent in the dechlorination-reduction of one of the two silicon-bonded chlorine atoms present in a dialkyldichlorosilane to convert the Si-Cl linkages to Si-H. The reaction solvent used is either N,N'-dimethylimidazolidinone or N,N,N',N',N",N"-hexamethyl-phosphoric triamide, while the reducing agent is sodium borohydride, optionally in combination with sodium hydride.
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