The pyrolysis of neopentyl chloride has been reported to decompose by an ionhyphen;pair mechanism in a gashyphen;phase homogeneous reaction at about 450deg;C. It is shown that a Ricemdash;Herzfeld mechanism involving the principal radical chain:Clplus;lpar;CH3rpar;3CCH2Clrarr;2HClplus;lpar;CH3rpar;2Clpar;CH2rpar;lpar;CH2Clrpar;,Complex chemical formulaaccounts well for the products and rate. It is followed by the fast unimolecular isomerization of 1,1hyphen;dimethyl cyclopropane to the isomeric methylbutenes. It is shown that the system is quite complex, involving autocatalysis by HCl (one of the major products) and very likely inhibition by the concomitantly produced olefins.
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