Hydrogen-carbon, carbon-carbon double rearrangement induced by proximity effects. 1-formation of methoxybenzyl ions in the electron impact mass spect…

1991

The 75 eV electron impact mass spectra of 1,1-bis(dimethoxyphenyl)methanes bearing o-methoxy groups are dominated by intense peaks corresponding, at least formally, to benzyl ions [(CH3O)2C6H3CH2]+(b). They arise from ions [((CH3O)2C6H3)2CH]+(a), which are in turn formed from molecular ions by loss of an alkyl radical through benzylic cleavage. The analysis of compounds labelled with 2H or 13C at methoxy groups led to the determination of the mechanism. Hydrogen migration, as hydride, followed by electrophilic substitution by the methylene carbon of the phenyl methylene ether cation through a six-centred transition state is responsible for the formation of benzylic ions b.