76-86-8Relevant academic research and scientific papers
Flash Photolysis Study for Halogen Abstraction of Ph3Sn* and Ph3Si* from Alkyl Halides
Ito, Osamu,Hoteiya, Kiyohiko,Watanabe, Akira,Matsuda, Minoru
, p. 962 - 965 (1991)
The reaction rate contants for halogen abstraction of Ph3Sn* and Ph3Si* have been determined by xenon-flash photolysis method.The absolute rate constants for the reactivity of Ph3Sn* with several alkyl halides have been compared with the relative ones; the agreement between the both methods was fairly good.For Ph3Sn*, the rate constant (in unit of mol-1 dm3 s-1) of n-BuCl (5.2*102) was smaller than that of n-BuBr (3.1*106) by a factor of ca. 1/104.With changing the alkyl halides, the rate constants for Ph3Si* and Ph3Sn* varied similarly, although the rate constants for Ph3Si* were larger than those for Ph3Sn* by factors of 50 - 100.The reactivity of alkyl halides increased with a decrease in the bond-dissociation energy of the R-X (X=Cl, Br).
METHOD FOR PRODUCING ARYLSILANE COMPOUND CONTAINING HALOSILANE COMPOUND AS RAW MATERIAL
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Paragraph 0080-0084, (2020/03/06)
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
Neutral-Eosin-Y-Photocatalyzed Silane Chlorination Using Dichloromethane
Fan, Xuanzi,Xiao, Pin,Jiao, Zeqing,Yang, Tingting,Dai, Xiaojuan,Xu, Wengang,Tan, Jin Da,Cui, Ganglong,Su, Hongmei,Fang, Weihai,Wu, Jie
supporting information, p. 12580 - 12584 (2019/08/16)
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.
Kinetic and Theoretical Investigation of Iron(III)-Catalyzed Silane Chlorination
Savela, Risto,Grnman, Henrik,Sundelin, Heidi,Norrby, Per-Ola,Yu. Murzin, Dmitry,Leino, Reko
, p. 584 - 592 (2016/02/23)
A highly versatile, robust, and efficient methodology for chlorination of silanes, methoxysilanes and silanols using low loadings of FeCl3 or Fe(acac)3 as the catalyst in the presence of 1-1.5?equivalents of acetyl chloride as the chlorine source was recently developed. The aim of the present paper is to evaluate and derive the reaction mechanisms involved in this reaction by calculating substrates, intermediates, products, and selected transition states, as well as by employing mathematical modeling of the reaction kinetics. The results obtained required reconsideration of the originally proposed overall reaction mechanism. Based on the kinetic and molecular modeling, a new revised reaction mechanism was developed giving a very good correspondence between the experimental data and calculations.
Reaction of chloro(ethyl)silanes with chloro(phenyl)silanes in the presence of aluminum chloride. Synthesis of chloro(ethyl)(phenyl)silanes
Lakhtin,Eremeeva,Gordeev,Ushakov,Bykovchenko,Kirilin,Chernyshev
, p. 595 - 599 (2015/05/13)
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.
Iron-catalyzed chlorination of silanes
Savela, Risto,Zawartka, Wojciech,Leino, Reko
experimental part, p. 3199 - 3206 (2012/06/04)
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.
SOLVENTLESS PROCESS TO PRODUCE AROMATIC GROUP-CONTAINING ORGANOSILANES
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Page/Page column 2-3, (2012/03/10)
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.
Hexachloroethane: a highly efficient reagent for the synthesis of chlorosilanes from hydrosilanes
Pongkittiphan, Veerachai,Theodorakis, Emmanuel A.,Chavasiri, Warinthorn
scheme or table, p. 5080 - 5082 (2009/12/01)
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.
Modular approach to silicon-bridged biaryls: Palladium-catalyzed intramolecular coupling of 2-(arylsilyl)aryl triflates
Shimizu, Masaki,Mochida, Kenji,Hiyama, Tamejiro
supporting information; body text, p. 9760 - 9764 (2009/05/30)
(Chemical Equation Presented) Bridge of Si: Intramolecular direct arylation of 2-(arylsilyl)aryl triflates is catalyzed smoothly by Pd(OAc) 2/PCy3 in the presence of Et2NH in dimethylacetamide (DMA), giving rise to the corresponding silicon-bridged biaryls in good to excellent yields. The new approach has led to the synthesis of a silicon-bridged 2-phenylindole (see scheme) that exhibits blue photoluminescence in the solid state with extremely high quantum yields.
Utility of trichloroisocyanuric acid in the efficient chlorination of silicon hydrides
Varaprath, Sudarsanan,Stutts, Debra H.
, p. 1892 - 1897 (2007/10/03)
The potential of trichloroisocyanuric acid (TCCA) as a chlorination agent for efficient conversion of Si-H functional silanes and siloxanes to the corresponding Si-Cl functional moieties was explored. In comparison to methods using other chlorinating agents, TCCA is inexpensive, results in a much faster reaction and produces a high purity product with a conversion that is essentially quantitative. A variety of chloro derivatives of linear and cyclic structures have been synthesized from silicon hydrides using this reagent with impressive yields that typically exceed 90%: PhSiCl3 (97.5%); PhMeSiCl2 (95.5%); Ph3SiCl (97.5%); Vi3SiCl (98.7%); (EtO)3SiCl (99.7%); t-Bu3SiCl (～100%); (MeClSiO)4 (86.5%); (MeClSiO)5 (95%); (MeClSiO)7 (96.5%); Ph(OEt)2SiCl (98%); ClMe2SiOSiMe2Cl (98.6%); ClMe2SiOSiMeClOSiMe2Cl (94.6%); ClMe2Si(OSiMeCl)2OSiMe2C l (92.3%); (Me3SiO)3SiCl (97%); Me3SiOSiClPhOSiMe3 (99%); Me3SiO(SiMeClO)3SiMe3 (95.7%); ClSi(OSiMe3)2OSi(OSiMe3) 2Cl (93.6%). For monohydridosilanes, dichloromethane (CH2Cl2) was a suitable solvent in which nearly quantitative conversion was observed within several minutes following the addition of the silanes to TCCA. For certain cyclic and linear siloxanes, and especially silanes containing multiple hydrogen atoms on the same silicon for which the reaction is sluggish in CH2Cl2, tetrahydrofuran (THF) was the preferred solvent. For a sterically demanding silane that did not undergo chlorination even in THF viz., HSi(OSiMe3)2O-Si(OSiMe3)2H, 1,2-dichloroethane was the best solvent.
