Thermal Si-C coupling reaction of allyl chloride with trichlorosilane and their mechanistic aspects
- Thermal Si-C coupling reaction of allyl chloride with trichlorosilane and their mechanistic aspects
- 정영애; 한준수; 유복렬
- Si-C coupling; allyl chloride; trichlorosilane
- Issue Date
- 제111회 대한화학회 학술발표회
- 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.
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