Single and double hydrogen rearrangements in the mass spectra of O‐ethyl, S‐alkyl methanephosphonothioates

Whereas the oxygen analogues of the title series gives rise to double hydrogen rearrangement on electron‐impact, alkylthiophosphonates show in addition a McLafferty rearrangement. The quantitative relationship between these two rearrangements in the thio series is dependent upon the chain length and branching on the alkyl group attached to sulphur. Comparison of the mass spectra of these compounds indicates that in the pathway of the double hydrogen rearrangement the hydrogen transferred to the sulphur atom originates primarily from the carbon δ to sulphur.