Acid-Catalyzed Hydrolysis of Some N,N-Dibenzylalkanesulfinamides in 50% Acetonitrile-Water

Abstract

The hydrolysis of some N,N-dibenzylalkanesulfinamides (RSONH(CH2Ph)(2); 1, R=Me; 2, R=Pr-i; 3, R=Bu-t; 4, R=1-adamantyl) has been studied in 50% (v:v) acetonitrile-water solutions of hydrobromic and hydrochloric acids, mainly at 44.8 degrees C, using ultraviolet (UV) spectrophotometry to determine pseudo first-order rate constants. The compounds were found to hydrolyze by concurrent bimolecular neutral, acid-catalyzed, and acid-dependent nucleophilic (halide ion) catalysis pathways. The last-named is predominant in reactions in HBr solutions, but in HCl solutions, the acid-catalyzed pathway is predominant. The results indicate that both steric and electronic effects are important in these reactions. There appears to be no mechanistic switchover in the series 14.