Interconversion of Methyltropyl and Xylyl Radicals: A Pathway Unavailable to the Benzyl-Tropyl Rearrangement

Abstract

The products of an electrical discharge containing toluene are interrogated using resonance-enhanced multiphoton ionization and laser-induced fluorescence spectroscopies. A previously unreported electronic spectrum recorded at m/z = 105, with a putative origin band at 26053 cm-1, is assigned to methyltropyl radical, which appears to be a major product of the toluene discharge, plausibly arising from CH insertion. All three o-, m-, and p-xylyl isomers are also identified. These isomers are detected in electrical discharges containing various xylenes, where it is also found that interconversion occurs: A discharge of o-xylene produces some m-xylyl; a discharge of m-xylene produces some o-xylyl..