- 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 0080-0084
(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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- Preparation method of phenyl chlorosilane
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The invention discloses a preparation method of phenyl chlorosilane. The preparation method comprises the following steps: (1) adding silicon powder, a copper catalyst and a sodium-containing compoundinto a reactor; (2) introducing a silicon-copper contact body modifier to pre-treat a silicon-copper contact body at a temperature of 300-500 DEG C; (3) mixing the pretreated silicon-copper contact body with a Cu-CuO-Cu2O-CuCl quaternary copper powder catalyst, and adding the mixture into the reactor; and (4) introducing chlorobenzene, controlling the reaction temperature to be 400-700 DEG C, andcarrying out a reaction to prepare phenyl chlorosilane monomers. According to the method, the use amount of the copper catalyst is low, the conversion rate of chlorobenzene is high, selectivity of phenyl chlorosilane is good, and the yield of diphenyl dichlorosilane with relatively high economic value is high in the product, so that economical efficiency of the phenyl chlorosilane prepared by thedirect method is improved.
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Paragraph 0041-0050
(2019/07/04)
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- Electrochemical properties of arylsilanes
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In the past, the electrochemical properties of organosilicon compounds were investigated for both fundamental reasons and synthesis purposes. Little is, however, known about the electrochemical behaviour of hydrogen-bearing arylsilanes. Here, we throw light on the electrochemical properties of 11 arylsilanes compounds, 2 of them synthesized for the first time. The oxidation potentials are found to depend on both the nature and number of the aryl groups. Based on these findings it was possible to establish some variation trends that match the expected structure–property correlations. Furthermore, we present first insights into the electrochemical reaction kinetics behind and identify several soluble electrochemical oxidation products.
- Biedermann, Judith,Wilkening, H. Martin R.,Uhlig, Frank,Hanzu, Ilie
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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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- Tempo-spatial chirogenesis. Limonene-induced mirror symmetry breaking of Si[sbnd]Si bond polymers during aggregation in chiral fluidic media
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Herein, we designed photoluminescent polymer aggregates surrounded by organic media containing (S)-/(R)-limonene and (1S)-/(1R)-α-pinene as an artificial model of an open-flow cell-wall free coacervate in a fluidic medium in the ground and photoexcited states. The aggregates were build-up of stiff circular dichroism (CD)-silent and circularly polarized luminescence (CPL)-silent bis(p-n-butylphenyl)polysilanes, nBuPS, and four other diarylpolysilanes. (S)- and (R)-limonene induced more efficiently to their chirality to nBuPS during aggregation, as proven by CD and CPL spectral analysis, compared to (1S)- and (1R)-α-pinene. The nBuPS aggregates generated in a mixture of limonene, methanol, and chloroform had a dissymmetry factor (gabs) as high as +0.04 for (R)-limonene and ?0.03 for (S)-limonene at the first Cotton band and a weak dissymmetry factor (glum) of +0.004 for (R)-limonene and ?0.003 for (S)-limonene. The gabs factor, however, greatly depended on the volume fraction and chirality of limonene in the tersolvents. These behaviors were ascribed to the tempo-spatial stability and instability of the aggregates suspension in the fluidic media, as revealed by time-course dynamic light scattering measurement.
- Fujiki, Michiya,Yoshida, Keisuke,Suzuki, Nozomu,Rahim, Nor Azura Abdul,Jalil, Jalilah Abd
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p. 120 - 129
(2016/11/16)
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- Reaction of chloro(ethyl)silanes with chloro(phenyl)silanes in the presence of aluminum chloride. Synthesis of chloro(ethyl)(phenyl)silanes
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Abstract Substituent exchange at the silicon atom between chloro(phenyl)silanes (PhSiCl3, MePhSiCl2, Ph2SiCl2) and chloro(ethyl)silanes (EtSiCl3, Et2SiCl2, Et3SiCl, Et4Si) in the presence of aluminum chloride has been studied. The examined compounds, except for PhSiCl3 and Et4Si, react fairly readily to give chloro(ethyl)-(phenyl)silanes in up to 48-52% yield. A probable mechanism has been proposed.
- Lakhtin,Eremeeva,Gordeev,Ushakov,Bykovchenko,Kirilin,Chernyshev
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p. 595 - 599
(2015/05/13)
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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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- Reaction of tetrachlorogermane with thienyl- and phenylchlorosilanes in presence of aluminum chloride. Synthesis of thienylchlorogermanes
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Reaction of tetrachlorogermane with 2-thienylchlorosilane and methyl(2-thienyl)dichlorosilane in presence of AlCl3 is studied. It was shown that in the reaction with 2-thienyltrichlorosilane 2-thienyltrichlorogermane mainly formed, while in the reactions with methyl(2-thienyl)dichlorosiulane aromatic germaniumcontaining compounds like 2-thienyltrichlorogermane and di(2-thienyl)dichlorogermane were obtained. Quantum-chemical calculations showed that the reaction of chlorine atoms exchange in GeCl4 with aromatic moiety formed from arylchlorosilanes in the presence of AlCl3 proceeds through a four-membered activated complex.
- Lakhtin,Vorob'Eva,Gordeev,Ushakov,Kirillin,Bykovchenko,Golub,Chernyshev
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p. 280 - 284
(2014/04/17)
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- PROCESS FOR PREPARING ORGANOSILANES
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The invention relates to a process for preparing diorganyldihalosilanes of the general formula (1) R2SiX2 (1), in which dihalodihydrosilanes of the general formula (2) X2SiH2 (2), in a mixture with silanes of the general formula (3) R′3SiH (3), are reacted with halogenated hydrocarbons of the general formula (4) R-X (4), in the presence of a free-radical initiator, which is selected from alkanes, diazenes and organodisilanes, where R is a monovalent C1-C18 hydrocarbon radical, R′ is a monovalent C1-C18 hydrocarbon radical, hydrogen or halogen, and X is halogen.
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Page/Page column 3
(2012/12/13)
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- SOLVENTLESS PROCESS TO PRODUCE AROMATIC GROUP-CONTAINING ORGANOSILANES
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Disclosed herein is a process for producing an aromatic group-containing organosilane, The process includes reacting a reaction mixture comprising an aromatic organic compound of the formula R1X and a halosilane or alkoxysilane represented by the formula R2aSiZ4-a in the presence of magnesium metal in order to produce the organosilane with the proviso that said reaction mixture is essentially free of any organic solvent, wherein R1 is an aryl group, each R2 is independently a phenyl group, a vinyl group or a C1-C4 alkyl group, X is chlorine or bromine, Z is chlorine, bromine or alkoxy, and a has a value of 0, 1, 2, or 3.
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Page/Page column 2-3
(2012/03/10)
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- 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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experimental part
p. 712 - 714
(2012/03/26)
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- Hexachloroethane: a highly efficient reagent for the synthesis of chlorosilanes from hydrosilanes
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A new and efficient chlorination protocol is presented for the preparation of chlorosilanes from hydrosilanes. A variety of chlorinating agents in combination with palladium(II) chloride as the catalyst are examined. Among them, hexachloroethane is found to be the best choice, furnishing the desired product in good to quantitative yields under mild conditions. Various hydrosilanes are used as starting materials to explore the scope of this reaction.
- Pongkittiphan, Veerachai,Theodorakis, Emmanuel A.,Chavasiri, Warinthorn
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scheme or table
p. 5080 - 5082
(2009/12/01)
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- Making of contact mass for organohalosilane preparation and preparation of organohalosilanes
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Organohalosilanes are prepared by charging a reactor with a contact mass comprising metallic silicon and a catalyst and feeding an organohalide-containing gas to the reactor. The contact mass is prepared by premixing metallic silicon and a tin compound and heat treating the premix at 300-600° C. in an inert gas atmosphere.
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Page/Page column 5
(2008/06/13)
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- Preparation of organohalosilanes
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Organohalosilanes are prepared by charging a reactor with a contact mass of metallic silicon and a catalyst and feeding an organohalide-containing gas to the reactor. Tin or a tin compound is used as the catalyst. Then organohalosilanes can be produced quite efficiently at a high reaction rate while maintaining a low T/D ratio and minimizing the deposition of by-products and carbon.
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Page/Page column 6
(2008/06/13)
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- Synthesis of di- and trisilanes with potentially chelating substituents
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Silylenes 2 or 4, generated by thermolysis of cyclotrisilanes 1 and 3, were inserted into the Si-Cl or Si-H bonds of monosilanes to yield a variety of disilanes, which can be further functionalized subsequently. In a few cases, trisilanes are accessible by the reaction of 1 with disilanes. The reaction of a metalated silane with a chlorosilane is an alternative method for the formation of Si-Si bonds, which turned out to be especially useful for the synthesis of bulkily substituted disilanes. Some of the new dichlorodiand trisilanes themselves serve as thermal precursors of silylenes 2 or 4, the extrusion of which can be catalyzed by 1 or 3 in certain cases.
- Belzner, Johannes,Dehnert, Uwe,Sch?r, Dirk,Rohde, Bernhard,Müller, Peter,Usón, Isabel
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- Process for heat-fractionation of organosilanes
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An improved process for the heat-fractionation of a mixture comprising an organosilane and a borane or borane forming compound. The improvement comprises the presence of a tertiary organoamine or tertiary phosphorous compound at a concentration sufficient to reduce modification of the organosilane during the heat-fractionation process.
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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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- 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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- Macrocyclic polyether compounds
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Macrocyclic polyether "crown" compounds of the formula EQU1 WHEREIN T is a C2 -C3 alkylene, A is EQU2 R being H or C1 -C18 alkyl, R2 and R3 being independently C1 -C18 alkyl, C2 -C4 alkenyl, or C6 -C14 aryl; Q and Z are independently 1,2-arylene (or saturated derivatives thereof) or substituted 1,2-arylene (or saturated derivatives thereof); a is 0, 1, 2, or 3; b is an integer from 3 to 20; y is 1 or zero; x1, x2, x3, and x4 are integers independently selected to give a 15-60 atom ring. Such crown compounds are generally useful in the formation of complexes with ionic metal compounds, thus making it possible to use certain chemical reagents in media wherein they are normally insoluble.
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