- Preparation of methylphenyldichlorosilane through a catalytic cracking reaction of 1,2-dimethyl-1,1,2,2-tetrachlorodisilane with halobenzene
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Catalytic cracking reaction of 1,2-dimethyl-1,1,2,2-tetrachlorodisilane with a halobenzene (PhCl, PhBr) to prepare methylphenyldichlorosilane has been investigated. Pd(PPh3)4 exhibited the best catalytic activity among the catalysts used. The activity of chlorobenzene was significantly lower than that of bromobenzene. With the latter and toluene as solvent, in the presence of 0.3 mol % Pd(PPh3)4, the conversion of disilane was 100% with a selectivity to MePhSiCl2 of 97.1%.
- Pi, Yong-Rui,Tan, Jun,Liu, Hui,Chen, Jie,Qun, Zhu-You,Zeng, Yan-Bo,Li, Lei
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Read Online
- METHOD FOR PRODUCING ARYLSILANE COMPOUND CONTAINING HALOSILANE COMPOUND AS RAW MATERIAL
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PROBLEM TO BE SOLVED: To provide a method for producing an arylsilane compound with low production cost. SOLUTION: A method for producing an arylsilane compound includes a reaction step for the cross-coupling reaction of a halosilane compound represented by general formula (A-1), (A-2), or (A-3) and an arylboronic acid pinacol ester in the presence of a nickel catalyst, a Lewis acid catalyst, and an organic base (R independently represent an aromatic hydrocarbon group, a heteroaromatic ring group, or a C1-20 hydrocarbon group; X independently represent a halogeno group or a trifluoromethanesulfonyloxy group). SELECTED DRAWING: None COPYRIGHT: (C)2020,JPOandINPIT
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Paragraph 0073-0077
(2020/03/06)
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- Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
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Chlorosilanes are versatile reagents in organic synthesis and material science. A mild pathway is now reported for the quantitative conversion of hydrosilanes to silyl chlorides under visible-light irradiation using neutral eosin Y as a hydrogen-atom-transfer photocatalyst and dichloromethane as a chlorinating agent. Stepwise chlorination of di- and trihydrosilanes was achieved in a highly selective fashion assisted by continuous-flow micro-tubing reactors. The ability to access silyl radicals using photocatalytic Si?H activation promoted by eosin Y offers new perspectives for the synthesis of valuable silicon reagents in a convenient and green manner.
- Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
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supporting information
p. 12580 - 12584
(2019/08/16)
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- Nickel-Catalyzed Selective Cross-Coupling of Chlorosilanes with Organoaluminum Reagents
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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.
- Naganawa, Yuki,Guo, Haiqing,Sakamoto, Kei,Nakajima, Yumiko
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p. 3756 - 3759
(2019/09/12)
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- Rh(iii)-Catalysed solvent-free hydrodehalogenation of alkyl halides by tertiary silanes
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Efficient catalytic reduction of CDCl3 and other alkyl halides, including persistent organic pollutants, by different tertiary silanes using the unsaturated silyl-hydrido-Rh(iii) complex {Rh(H)[SiMe2(o-C6H4SMe)](PPh3)2}[BArF4] as a pre-catalyst is accomplished. The reactions are performed in a solvent-free manner. On account of experimental evidence, a simplified catalytic cycle is suggested for the hydrodehalogenation of CDCl3.
- Almenara,Azpeitia,Garralda,Huertos
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supporting information
p. 16225 - 16231
(2018/11/30)
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- DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl
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The room temperature reactions between R3SiH (R3?=?Et3, PhMe2, Ph2Me) and R′3SiCl (R′3?=?Me3, PhMe2, Ph2Me), with an excess of dimethylformamide (DMF) in the presence of (Me3N)Mo(CO)5 as a catalyst, result in the initial formation of R3SiCl, R′3SiOSiR′3 and Me3N as detected by 29Si, 13C, 1H NMR spectroscopy and GC/MS. As the reaction proceeds, the more so if the reaction temperature is raised, mixed disiloxanes R3SiOSiR′3 and ultimately lesser amounts of R3SiOSiR3 may be detected. A mechanism involving the activation of chlorosilanes by the nucleophilic DMF is proposed to produce transient imminium siloxy ion pairs, [Me2N[dbnd]CHCl]+[R′3SiO]? ? [Me2N[dbnd]CH(OSiR′3)]+Cl? which react with R3SiH to form Me2NCH2OSiR′3 and R3SiCl. A secondary reaction of Me2NCH2OSiR′3 with R′3SiCl produces the symmetrical disiloxane R′3SiOSiR′3 and ClCH2NMe2. The final stage of the reaction is the reduction of ClCH2NMe2 by R3SiH, a reaction which is reported for the first time. The newly created chlorosilane R3SiCl can become involved in the initial DMF activation chemistry thereby forming the other disiloxanes observed as the reaction proceeds.
- Gonzalez, Paulina E.,Sharma, Hemant K.,Pannell, Keith H.
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p. 376 - 381
(2017/06/30)
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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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- Intermolecular chirality transfer from silicon to carbon: Interrogation of the two-silicon cycle for Pd-catalyzed hydrosilylation by stereoisotopochemical crossover
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A "two-silicon cycle" for the highly efficient intermolecular chirality transfer from silicon to carbon (98-99% ct) in the palladium-catalyzed hydrosilylation of norbornenes emerges from an investigation involving catalytic crossover experiments with isotopically labeled silicon-stereogenic silanes. A key outcome of these experiments, which are supported by product-distribution modeling, is the conclusion that the chirality transfer arises from thermodynamically controlled reversible silapalladation of the alkene rather than from kinetic control during irreversible σ-bond metathesis of the resulting β-silyl σ-alkyl palladium complex with chiral silane. Copyright
- Rendler, Sebastian,Oestreich, Martin,Butts, Craig P.,Lloyd-Jones, Guy C.
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p. 502 - 503
(2007/10/03)
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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 7-9
(2008/06/13)
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- GRIGNARD PROCESSES WITH INCREASED CONTENT OF DIPHENYLCHLOROSILANES
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Three improved Grignard processes are used for preparing phenyl-containing chlorosilane products wherein the yield of diphenylchlorosilanes as a product is maximized, while the yield of phenylchlorosilanes as a product is minimized. In one embodiment, the process involves contacting a phenyl Grignard reagent, an ether solvent, an aromatic halogenated coupling solvent and a trichlorosilane. In another embodiment, the process involves contacting a phenyl Grignard reagent, an ether solvent, an aromatic halogenated coupling solvent, a trichlorosilane, and a phenylchlorosilane. In yet another embodiment, the process involves contacting a phenyl Grignard reagent, an ether solvent, an aromatic halogenated coupling solvent, and a phenylchlorosilane. In each embodiment, the reactants are present in particular mole ratios of the components.
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Page/Page column 8
(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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- Synthesis and properties of novel dialkylaminocarbenium salts
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Novel dialkylaminocarbenium salts with metallocomplex counter ions were prepared by the reaction of phosgene with either DMF or tetramethylurea in the presence of metal chlorides. Reactions of organosilicon amides with phosgene gave corresponding carbenium salts, while organosilicon ureas yielded aminoiminocarbenium salts. Dialkylaminochlorocarbenium salts were reduced with hydrosilanes to give dialkylaminocarbenium salts and can be easily hydrolyzed to afford either amides or ureas. Pathways of the reaction with water and alcohols depend on the nature of reagent and the reaction conditions.
- Sheludyakov,Belyakova,Shevchenko,Chernyshev
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p. 997 - 1002
(2007/10/03)
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- 9,10-Dihydro-9-sila-10-heteroanthracenes as new radical-based reducing agents
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9,10-Dihydro-9-silaanthracenes 1 containing a heteroatom at the 10-position have been prepared and their reducing abilities for the reduction of some organic compounds under radical conditions have been investigated. Derivatives possessing a silicon, tin, oxygen or sulfur atom at the 10-position exhibited enhanced reactivities compared with the open-chain models. Among them, 9,10-dimethyl-9,10-dihydro-9,10-disilaanthracene 1a proved to be the most effective reagent for AIBN-initiated dehalogenation of organic halides and deoxygenation of aliphatic alcohols via O-thiocarbonyl derivatives. The rate constants for hydrogen abstraction from the Si-H moiety of these silaanthracenes 1 were determined using the neophyl rearrangement as a free radical clock in order to estimate their reactivities.
- Oba, Makoto,Kawahara, Yoko,Yamada, Ryo,Mizuta, Hidetaka,Nishiyama, Kozaburo
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p. 1843 - 1848
(2007/10/03)
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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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- GAS-PHASE REACTIONS OF ORGANOSILICON HYDRIDES WITH (BENZYLOXY)TRICHLOROSILANE
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Dichlorosilanone generated by the pyrolysis of (benzyloxy)trichlorosilane undergoes an insertion reaction at the Si-H bond in organosilicon hydrides with the formation of new hydride organosiloxanes.It was shown that gas-phase reactions of organosilicon hydrides with (benzyloxy)trichlorosilane go by a radical chain mechanism.
- Chernyshev, E. A.,Mudrova, N. A.,Krasnova, T. L.,Petrunin, A. B.
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p. 832 - 837
(2007/10/02)
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- Transition-Metal Silyl Complexes. 37.1 Reaction of Anionic Silyl, Germyl, and Stannyl Complexes [(η5-C5H4Me)(CO)2MnER 3]- (E = Si, Ge, Sn) with Geminal Organic Dihalides: A Novel Route for the Preparation of Carbene Complexes
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The anionic complexes Na[MeCp(CO)2MnER3] (E = Si, Ge, Sn) (MeCp = η5-C5H4Me), obtained by deprotonation of the corresponding hydrido complexes MeCp(CO)2Mn(H)ER3, react with 3,3-dichlorocyclopropenes to give the cyclopropenylidene complexes MeCp(CO)2Mn=C-CR=CR (2) by NaCl and R3ECl elimination. Aminocarbene complexes MeCp(CO)2Mn=C(NR2)R′ (5), including the N-methylpyridinylidene complex MeCp(CO)2Mn=CN(Me)CHCHCHCH (5h) and a thiazolinylidene derivative, MeCp(CO)2Mn=CN(Me)C(Me)CHS (5i), were alalogously prepared from [MeCp(CO)2MnSiMePh2]- and [R2N=C(R′)Cl]+. In these reactions, the anionic complexes Na[MeCp(CO)2MnER3] act as preparative equivalents to the dianionic complex MeCp(CO)2Mn2-. The X-ray structure analysis of 5i is reported (Mn-C(carbene) 197.0 (3) pm): monoclinic, space group P21/c (Z = 4), a = 736.4 (1) pm, b = 1418.4 (3) pm, c = 1304.6 (1) pm, β = 95.58 (1)°.
- Kirchg?ssner, Uwe,Piana, Hermann,Schubert, Ulrich
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p. 2228 - 2232
(2007/10/02)
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- Method for the cleavage of organic siloxanes, and products and applications thereof
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A method for the cleavage of organosiloxanes with chlorosilanes in the presence of ferric chloride and hydrogen chloride as catalysts resulting in chloroalkyl silanes or chloroaryl silanes, and organosiloxanes, which are characterized by one or more --O--Si--R3 groups, (R=alkyl or aryl), which are directly bound to a silicon atom which in turn is bound either to the same grouping or to an alkyl or aryl moiety.
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- REACTIONS OF TELLURIUM(IV) CHLORIDES WITH SOME ORGANOSILICON HYDRIDES
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The reactions of several organosilicon hydrides PhnSiH(4-n), n = 1, 2; R3SiH, R3 = Ph3, Ph2Me, PhMe2, (n-C6H13)3; (p-Me2HSi)2C6H4, with TeCl4 in benzene resulted in the formation of tellurium metal and chlorosilanes in 75-90percent yields.Similar reactions with aryltellurium trichlorides (RTeCl3, R = Ph, p-MeOC6H4, p-EtOC6H4) proceeded in two different ways.On stirring at room temperature for 6-8 h, diaryl ditellurides and chlorosilanes were obtained in 70-95percent yields whereas on refluxing for 6-10 h, tellurium powder and diaryltellurium dichlorides were obtained along withthe chlorosilanes in 80-95percent yields.Diaryltellurium dichlorides (R2TeCl2, R = Ph, p-MeOC6H4) did not react readily with PhSiH3 nor with Ph3SiH.
- Chadha, Raj K.,Drake, John E.,Neo, Mary K. H.
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