Studies on Antitumor Substances. IX. Chemical Behaviors of Thiosulfonate toward Active Methylene Compound

Abstract

The reactivities of phenyl benzenethiosulfonate, o-nitrophenyl benzenethiosulfonate and 1, 2-bis (benzenesulfonylthio) ethane toward several active methylene compounds were examined. Consequently, bis (phenylmercapto) malondiamide obtained by the reaction of phenyl benzenethiosulfonate with malondiamide at room temperature was found to eliminate readily one of carboxamide and phenylmercapto group by warming at the temperature above 35°. On the other hand, bis (phenylmercapto) malonate was similarly eliminated one of phenylmercapto group under the same condition, without elimination of carboxylate group. 1-Benzylmercapto-1-phenylmercaptomalondiamide and 1-ethyl-1-phenylmercaptomalondiamide were eliminated one of carboxamide group, without elimination of any mercapto group. Moreover, 1, 2-bis (benzenesulfonylthio) ethane was allowed to react with malondiamide and acetylacetone to give cyclic compound, ethylenedithiomalondiamide and ethylenedithioacetylacetone, respectively. With comparison of these reactions, the reaction of benzyl benzenesulfonate with cyanoacetamide was carried out to result in the benzylation of cyanoacetamide.