Add time:08/21/2019         Source:sciencedirect.com

A study has been made of the formation of C4 and C5 products in the radiolysis of 1-chloropropane in the vapour phase. The yield of C4 products is considerably more important than that of C5 products and is much less influenced by cyclohexene, which acts as a positive ion scavenger under the experimental conditions used in the study. The disproportionately large formation of C4 products is attributed to ionic fragmentation of excited chloropropane ions into ethyl carbonium ions and chloromethyl radicals, 1.(1)C3H7Cl+∗→C2H+5 + CH2Cl which leads to much higher yields of chloromethyl than of ethyl radicals, because ethyl carbonium ions react mainly by hydride transfer with 1-chloropropane. Cyclohexene does not influence reaction (1) to an important extent, because of the high rate of this reaction. C5 radiolysis products are to some extent formed from excited chloropropane ions, by ionic fragmentation into ethyl radicals and chloromethyl carbonium ions:2.(2)C3H7Cl+∗→C2H5 + CH2Cl+The strong influence of cyclohexene on the yield of C5 products indicates however that some other process must be predominant during electron irradiation of 1-chloropropane, probably neutralization of positive ions by electrons, followed by dissociation of the excited molecules so-formed.

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