GAS-PHASE SUBSTITUTION-REACTIONS BY RADICAL CATIONS .4. METHYLENE TRANSFER BY THE C-C RING-OPENED OXIRANE RADICAL-CATION TO CHLOROBENZENE -PRODUCT ION ANALYSIS

Under the conditions of chemical ionization, the alpha-distonic C-C ri ng-opened oxirane radical cation transfers a methylene group to chloro benzene. The [M+14](+) product ions formed are benzyl chloride (82%) a nd meta (16%), and para (2%) chlorotoluene radical cations. The struct ures of these products have been established from their collisionally induced dissociation in comparison with reference ions. Application of principal component analysis (PCA) shows that no other product ions a re being formed. The possible formation of the distonic methylene (phe nyl)chloronium radical ion C6H5ClCH2+ can therefore be excluded; moreo ver, its calculated (#UHF/3-21G//MNDO) heat of formation is 561 kJ mo l(-1) higher than that of benzyl chloride.