Thermal Si-C coupling reaction of allyl chloride with trichlorosilane and their mechanistic aspects

Title
Thermal Si-C coupling reaction of allyl chloride with trichlorosilane and their mechanistic aspects
Authors
정영애한준수유복렬
Keywords
Si-C coupling; allyl chloride; trichlorosilane
Issue Date
2013-04
Publisher
제111회 대한화학회 학술발표회
Abstract
Thermal Si-C coupling reaction of allyl chloride with trichlorosilane was studied without catalyst at temperatures ranging from 150 to 250℃. In this reaction, the organosilicon compounds are formed from the dehydrochlorination reaction and hydrosilylation reaction. In particular, 3-chloropropyltrichlorosilane of hydrosilylation reaction products and allyltrichlorosilane of the dehydrochlorination reaction products were obtained mainly. Except for two substances, 1,3-bis(trichlorosilyl)propane was obtained by the hydrosilylation reaction of allyltrichlorosilane. 3-chloropropyltrichlorosilane and allyltrichlorosilane compounds were competitively obtained each other in competition reaction. When the temperature is low, the 3-chloropropyltrichlorosilane were mainly produced and when the temperature is high, the allyltrichlorosilane were mainly produced. And 1,3-bis(trichlorosilyl)propane was produced through continuous hydrosilylation reactions. Compounds was analyzed by GC and GC/MSD, 1H NMR, 13C NMR, DEPT-135 NMR, 29Si NMR and FT-IR. Thermal reaction of allyl chloride with trichlorosilane gives complex products because of the above-mentioned two reactions occur competitively.In order to investigate the reaction mechanism, we calculated the energy of the unstable intermediates using the Gaussian program. Dissociation energy of trichlorosilane when decomposed the radical or ion was calculated at 298.2K. Gibbs free energy of ions and radicals are 273.77kcal/mol and 143.21kcal/mol, respectively. This energy is too high and can not happen in the experimental conditions of this paper. Gibbs Free Energy of the transition state in a reaction that produces 3a is 64.28kcal/mol. 3a is 4 membered ring transition state with Si-H and C-C double bond.
URI
http://pubs.kist.re.kr/handle/201004/44758
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KIST Publication > Conference Paper
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