1.Trinitromethyl sulfides (R′-S-C(NO2)3) when treated with electrophilic reagents (halogens, HCl, BrONO2, N-chloramines) are cleaved at the C-S bond to give trinitromethane and sulfenic acid derivatives. Here the electrophilic portion of the reagent always attaches itself to the carbon atom of the polynitroalkyl group, which is a new type of electrophilic substitution in the sulfide series.2.A theory was expressed regarding the role of internal nucleophilic cooperation due to coordination of the nucleophilic portion of the electrophilic reagent with the sulfur atom in polynitroalkyl sulfide