Abstract
Reductive cleavage of the sp3 carbon‐sulfur bond in alkyl‐or aryl‐substituted 2‐mercapto‐or 2‐amino‐6H‐1,3‐thiazines with sodium in liquid ammonia affords almost quantitative yields of the sodium salts of 1‐alkenyl‐dithiocarbamates and ‐thioureas, respectively. The dithiocarbamates can be converted into 1‐alkenyl isothiocyanates by reaction with chloroformates and subsequent pyrolysis to give overall yields of 54‐88%. Cis‐trans isomerization of the 1‐alkenyl isothiocyanates can only be achieved by irradiation.

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