Base catalysed rearrangements involving ylide intermediates. Part 6. The rearrangements of diallyl- and allyipropynyl-ammonium cations in protic media

Abstract

The base catalysed rearrangements of the cations, (1d–j) in aqueous solution yield the isomeric cations (15) or the aldehydes (10) and (11), or mixtures of (15), (10), and (11). This contrasts dramatically with the transformations observed for the cations (1) in aprotic solvents. The cations (15) undergo Hofmann elimination to the naphthalenic amines (12) or (13) and (14). The methiodide of amine (13g) shows a novel consequence, of restricted rotation. The n.m.r. spectrum of the methiodide shows that the two protons of the methylene group are diastereotopic.