Cytotoxic compounds. Part XIX. Allylic rearrangements in the reactions of 3-(phenylthio)prop-2-enyl chloride, 3-(p-nitrophenylthio)prop-2-enyl methanesulphonate, and 3-(p-nitrophenylthio)prop-2-enyl chloride with nucleophiles

Abstract

Addition of arenethiols to prop-2-yn-1-ol proceeds in both directions, to give 2- and 3-(arylthio)prop-2-en-1-ols. From the latter, the title compounds were prepared; in their reactions with sodium methoxide, potassium acetate, and tetramethylammonium acetate, mixtures of normal and allylically rearranged products were obtained, the proportions depending on the nature of the reagent and of the leaving group. With sodium azide, only the normal (primary) azide was formed. Solvolysis of the two nitro-compounds in methanol gave a mixture of normal and rearranged ethers, but under the same conditions 3-(phenylthio)prop-2-enyl chloride gave the dimethyl acetal of 3-(phenylthio)propanal.

The ¹H n.m.r. spectra of all the allylic compounds (both cis- and trans-isomers in most applicable cases) are tabulated.