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The chlorination of C7H16, C8H18, C10H22, and (Me2CH)2 with N-Chlorosuccinimide, tert-BuOCl, CCl3SO2Cl, CCl4, CCl3SCl, PCl5, and Cl2 in C6H6 or CS2 which both form loose complexes with Cl2 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.
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