Chemistry of α‐diazosulfones, XII: α‐Alkoxy‐α‐chloro‐sulfones from tert‐butyl hypochlorite and α‐diazosulfones

The reaction of α-diazosulfones with tert-butyl hypochlorite in tert-butyl alcohol/dichloromethane gives α-tert-butoxy-α-chloro-sulfones (II) in good yields. In dichloromethane as solvent the same compounds were obtained, while in ethanol/dichloromethane the corresponding α-chloro-α-ethoxy-sulfones were formed (Scheme 1, Table I). α-Diazo-carbonyl compounds and tert-butyl hypochlorite give acetals in alcoholic solvents and α-tert-butoxy-α-chloro-carbonyl compounds in dichloromethane (Scheme II, Table I). An ionic pathway for the reaction of these diazo compounds with t-BuOCI is proposed. The initially formed ion pair RSO2CH(Cl)N2⊖. t-BuO⊖ solvolyses or collapses with liberation of nitrogen.