Hydrogen rearrangements in cyclic phosphates during the electron impact‐induced fragmentation

Abstract

AbstractThe fragmentation upon electron impact of a cyclic phosphate, 5,5‐dimethyl‐2‐oxo‐2‐phenoxy‐1,3,2‐dioxaphosphorinane, was investigated. Using its deuterated analogue, it was shown that no randomization of hydrogen atoms among methyl, methylene and phenyl groups occurred within the molecular ion. The majority of the fragmentations involved single, double or triple hydrogen transfers. The origin of hydrogen(s) transferred in the formation of C‐5 ions was also estimated. The existence both specific and nonspecific hydrogen rearrangement mechanisms was also revealed. The specific hydrogen rearrangement involves a methyl hydrogen transferring to the PO group and this process seemed to be the initial step in the formation of many of the ions.