75-77-4Relevant articles and documents
A General and Selective Synthesis of Methylmonochlorosilanes from Di-, Tri-, and Tetrachlorosilanes
Naganawa, Yuki,Nakajima, Yumiko,Sakamoto, Kei
supporting information, p. 601 - 606 (2021/01/13)
Direct catalytic transformation of chlorosilanes into organosilicon compounds remains challenging due to difficulty in cleaving the strong Si-Cl bond(s). We herein report the palladium-catalyzed cross-coupling reaction of chlorosilanes with organoaluminum reagents. A combination of [Pd(C3H5)Cl]2 and DavePhos ligand catalyzed the selective methylation of various dichlorosilanes 1, trichlorosilanes 5, and tetrachlorosilane 6 to give the corresponding monochlorosilanes.
Platinum-Templated Coupling of B=N Units: Synthesis of BNBN Analogues of 1,3-Dienes and a Butatriene
Arrowsmith, Merle,Braunschweig, Holger,Brunecker, Carina,Fantuzzi, Felipe
supporting information, p. 16864 - 16868 (2021/06/28)
The 1:2 reaction of [μ-(dmpm)Pt(nbe)]2 (dmpm=bis(dimethylphosphino)methane, nbe=norbornene) with Cl2BNR(SiMe3) (R=tBu, SiMe3) yields unsymmetrical (N-aminoboryl)aminoboryl PtI2 complexes by B?N coupling via ClSiMe3 elimination. A subsequent intramolecular ClSiMe3 elimination from the tBu-derivative leads to cyclization of the BNBN unit, forming a unique 1,3,2,4-diazadiboretidin-2-yl ligand. In contrast, the analogous reaction with Br2BN(SiMe3)2 leads, via a twofold BrSiMe3 elimination, to a PtII2 A-frame complex bridged by a linear BNBN isostere of butatriene. Structural and computational data confirm π electron delocalization over the entire BNBN unit.
SYNTHESIS OF ORGANO CHLOROSILANES FROM ORGANOSILANES
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Page/Page column 36; 37, (2019/04/16)
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.
METHOD FOR PRODUCING HALOSILANE
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Paragraph 0028; 0035; 0036, (2019/07/31)
PROBLEM TO BE SOLVED: To provide a method for producing halosilane that can efficiently produce halosilane. SOLUTION: Alkoxy halomethane is used as a halogenating agent and reacted with oxysilane having a structure represented by formula (a), to efficiently produce halosilane having a structure represented by formula (b) (In the formula (b), X is a chlorine atom, a bromine atom, or an iodine atom). SELECTED DRAWING: None COPYRIGHT: (C)2019,JPOandINPIT
A preparation method of the trimethyl chlorosilane (by machine translation)
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Paragraph 0020-0033, (2019/05/02)
The invention provides a preparation method of the trimethyl chlorosilane, six-hexamethyl disilane, double-(trichloromethyl) carbonate, catalyst is added to the solvent, thereby obtaining a reaction mixture, said reaction mixture is added to the initiator, the reaction is carried out, after the reaction is finished after treatment can get trimethylchlorosilane. The method of the invention is safe and controllable, and easy to operate, is friendly to the environment, the resulting high purity of the product, by-product is only carbon dioxide gas, the elimination of industrial production in significant corrosion source - hydrogen chloride, greatly improve the working environment in the production process, and the solvent, catalyst and initiator can be used repeatedly, is a green-friendly chlorination process, has wide industrial application prospect, is suitable for application. (by machine translation)
DISILANE-, CARBODISILANE-AND OLIGOSILANE CLEAVAGE WITH CLEAVAGE COMPOUND ACTING AS CATALYST AND HYDROGENATION SOURCE
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Page/Page column 39; 40, (2019/04/16)
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)
Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents
Naganawa, Yuki,Guo, Haiqing,Sakamoto, Kei,Nakajima, Yumiko
, p. 3756 - 3759 (2019/09/12)
Nickel-catalyzed cross-coupling reactions of chlorosilanes with organoaluminum reagents were developed. An electron-rich Ni(0)/PCy3 complex was found to be an effective catalyst for the desired transformation. The reaction of dichlorosilanes 1 proceeded to give the corresponding monosubstituted products 2. Trichlorosilanes 4 underwent selective double substitution to furnish the corresponding monochlorosilanes 2. Overall, the selective synthesis of a series of alkylmonochlorosilanes 2 from di- and trichlorosilanes was achieved using the present catalytic systems.
Synthesis of Functional Monosilanes by Disilane Cleavage with Phosphonium Chlorides
Santowski, Tobias,Sturm, Alexander G.,Lewis, Kenrick M.,Felder, Thorsten,Holthausen, Max C.,Auner, Norbert
supporting information, p. 3809 - 3815 (2019/02/13)
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.
CLEAVAGE OF METHYLDISILANES TO METHYLMONOSILANES
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Page/Page column 29, (2019/04/16)
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.
Making Use of the Direct Process Residue: Synthesis of Bifunctional Monosilanes
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)
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.
