85121-42-2Relevant articles and documents
Direct synthesis of organodichlorosilanes by the reaction of metallic silicon, hydrogen chloride and alkene/alkyne and by the reaction of metallic silicon and alkyl chloride
Okamoto, Masaki,Onodera, Satoshi,Yamamoto, Yuji,Suzuki, Eiichi,Ono, Yoshio
, p. 71 - 78 (2007/10/03)
Dichloroethylsilane was synthesized by the reaction of metallic silicon, hydrogen chloride and ethylene using copper(I) chloride as the catalyst, the silicon conversion and the selectivity for dichloroethylsilane being 36 and 47%, respectively. At a lower reaction temperature or at a higher ratio of ethylene: hydrogen chloride a higher selectivity was obtained, however the silicon conversion was lower. The silicon-carbon bond formation is caused by the reaction of a surface silylene intermediate with ethylene. The reaction with propylene in place of ethylene gave dichloroisopropylsilane (22% selectivity) and dichloro-n-propyl-silane (8% selectivity) together with chlorosilanes. A part of the dichloroisopropylsilane is formed by the reaction of silicon, hydrogen chloride and isopropyl chloride formed by hydrochlorination of propylene. Use of acetylene instead of alkenes resulted in dichlorovinylsilane formation with a 34% selectivity. Alkyldichlorosilanes were also produced directly from silicon with alkyl chlorides, propyl and butyl chlorides. During the reaction the alkyl chloride is dehydrochlorinated over the surface of copper originating from the catalyst to afford hydrogen chloride and alkene. The hydrogen chloride formed participates in the formation of the silicon-hydrogen bond in alkyldichlorosilane, and the reaction of silicon, hydrogen chloride and alkene also causes alkyldichlorosilane formation. The reaction with isopropyl chloride gave a very high selectivity (85%) for dichloroisopropylsilane, the silicon conversion being 86%. The Royal Society of Chemistry 2001.
Silaethane XIII. Erzeugung von SiC-Doppelbindungen in der Koordinationssphaere von Eisencarbonylkomplexen
Auner, Norbert,Grobe, Joseph,Schaefer, Thomas,Krebs, Bernt,Dartmann, Mechtild
, p. 7 - 24 (2007/10/02)
The suitability of the vinylsilyliron complexes RSi(Cl)CH=CH2 t (3), Fe(CO)2cp (4)> and of MeSi(Cl)CMe=CH2 (14) as precursors for the generation of silaethane derivatives has been investigated.The starting compounds 1 to 4 and 14 can be obtained from Me(Vi)SiCl2, Ph(Vi)SiCl2, HSiCl3 and MeSiCl3, respectively, by judicious combination of published procedures.They have been characterized by analytical and spectroscopic studies as well as by comparison with known data.The generation of the Si=C intermediates was attempted by treating the vinylsilyl iron complexes with LiBut at low temperatures (-10 deg C).Only with 1 was a smooth reaction observed with formation of the Z/Z dimer 1,3-bis(cyclopentadienyl-dicarbonyliron)-1,3-dimethyl-2,4-dineopentyl-1,3-disilacyclobutane (16) of the expected silaethane MeSi=CHCH2But.This intermediate also seems plausible on the basis of trapping experiments, using 2,3-dimethyl-1,3-butadiene, isoprene or 1,3-cyclohexadiene.However, since 16 is formed as the main product even in the presence of an excess of these dienes, the cyclization of the lithiated precursor ClSiMeCH(CH2But)SiMeCH(Li)CH2But must be regarded as an alternative route to 16.The crystal and molecular structure of 16 indicate a Z/Z configuration of the bulky ring substituents.The disilacyclobutane skeleton is nonplanar with a dihedral angle of 18.7 deg.Similar to other 1,3-disilacyclobutane derivatives, 16 shows a fairly short transannular Si(1)...Si(2) distance of 2.641(1) Angstroem.Due to the -I effect of the phenyl substituent reaction of 2 with LiBut yields oligomeric coupling products, whereas in 3, 4 or 14 for steric reasons LiBut clearly attacks the carbonyl ligand instead of the CC double bond to give black, pyrophoric solids of low solubility.