Journal of the Korean Chemical Society (대한화학회지)

Korean Chemical Society (대한화학회)
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Isomer Formation in the Chlorination of Highmolecular Paraffinic Hydrocarbons by Various Halogenating Agents

여러 종류의 할로겐 화합물과 고분자량 파라핀계 탄화수소의 염소화에서 생기는 이성질화에 관한 연구

  • Li-Hoan Kung (Korea Research Institute of Chemical Technology)
  • Published : 1988.08.20
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Abstract

The chlorination of $C_7H_16,\;C_8H_18,\;C_10H_22,\;and\;(Me_2CH)_2$ with N-Chlorosuccinimide, tert-BuOCl, $CCl_3SO_2Cl,\;CCl_4,\;CCl_3SCl,\; PCl_5,\;and\;Cl_2\;in\;C_6H_6\;or\;CS_2$ which both form loose complexes with $Cl_2$ atoms yielded mixtures of isomeric monochloroalkanes which were analyzed quantitatively. An isomer ratio differing from that known for the substitution of paraffinic hydrocarbons was observed. The isomer distribution observed is the result of the combined effects of the differing C-H dissociation energies of the different types of H atoms of the alkane and of the free energy of the attacking radical with polar effects of the attacking radical as well as of the hydrocarbon.

n-Heptane, n-Octane, n-Decane, 2,3-Dimethyl Butane을 chlorination agent인 N-chlorosuccinimide, tert-Butylhypochloride, Trichloromethanesulfonylchloride, Carbontetrachloride, Trichloromethanesulfenyl chloride, Phosphorous pentachloride Chlorine등으로 benzene 또는 $CS_2$ 용매중에서 염소화시킬때 생기는 Mono-chloro alkane의 이성질화 혼합물을 정량적으로 고찰하였다. 여기에서 파라핀계 탄화수소의 치환비율에 대한 지금까지 알려진 사실과 일치하지 않는 놀라운 이성질화 분포(Isomerization distribution)를 확립하였다. 이러한 결과는 극성효과를 갖는 공격하는 라디칼의 free energy, 그리고 alkane의 개개의 수소 원자가 지니는 여러가지 서로다른 C-H bond 해리에너지의 상호작용을 통하여 얻어졌다.

Keywords

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