Chemistry of sulfonyl isocyanates and sulfonyl isothiocyanates. IX. Routes to substituted oxazolidin-2-ones and oxazolidine-2-thiones

4-Chlorobenzenesulfonyl isocyanate (I) reacted with 2-chloroethanol and 1-chloro-2-propanol to give, respectively, 2-chloroethyl 4-chlorobenzenesulfonyl carbamate (III) and 1-chloro-2-propyl 4-chlorobenzenesulfonyl carbamate (VI). The carbamates III and VI cyclized under the influence of pyridine to afford, respectively, 3-(4-chlorobenzenesulfonyl)oxazolidin-2-one (IV) and 3-(4-chlorobenzenesulfonyl)-5-methyloxazolidin-2-one (VII). The oxazolidin-2-ones were stable toward hydrochloric acid but hydrolyzed in 2M sodium hydroxide solution to N-(2-hydroxyethyl)-4-chlorobenzenesulfonamide (V) and N-(2-hydroxy-1-propyl)-4-chlorobenzene-sulfonamide (VIII), respectively. 4-Toluenesulfonyl isothiocyanate (II) reacted with 2-chloroethanol to give 2-chloroethyl 4-chlorobenzenesulfonyl thiocarbamate (IX), which was converted by pyridine to 3-(4-toluenesulfonyl)oxazolidine-2-thione (X).