Abstract New N-alkyl (trifluoromethyl) sulfonyl 1, 4-benzoquinone monoimines were synthesized, and their thiocyanation gave 5-alkyl (trifluoromethyl) sulfonylamino-1, 3- benzoxathiol-2-ones. An intermediate thiocyanation product, 5-trifluoromethylsulfonylamino- 1, 3-benzoxathiol-2-imine, was isolated for the first time.