Behavior of dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides toward powdered sodium hydroxide and aqueous alkali

Under the influence of a twofold molar quantity of powdered sodium hydroxide in the presence of a few drops of methanol at room temperature dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides undergo a Stevens rearrangement with transfer of the reaction center, forming substituted amino alcohols with an allene group. Intramolecular cyclization of the products and concurrent hydration lead to the formation of a mixture of dialkyl(4-allyl-2,5-dihydrofuran-2-yl)amines and dialkylamino-3-allyl-4-hydroxybutanones with overall yields of 37-41%. During the aqueous-alkali cleavage of dialkylallyl(4-hydroxybut-2-ynyl)ammonium bromides the products from intramolecular cyclization were obtained with yields of 38-41%. Under the conditions both of Stevens rearrangement and of aqueous-alkali cleavage the secondary amines are also formed with yields of 15-17%. As nonamine products mixtures of compounds, which according to the IR spectra contain unconjugated and conjugated carbonyl groups, were obtained. The presence of an aldehyde group was established by a silver mirror reaction.