Polychlorination of thiophene. A reinvestigation

Abstract Some old controversies in the literature with regard to the structures of trichlorothiophenes have been elucidated. In the course of these studies, we found that the best method for the preparation of 2,3,5‐trichlorothiophene is the direct chlorination of thiophene in the presence of catalytic amounts of ferric chloride. If 2,5‐dichlorothiophene is available 2,3,5‐trichlorothiophene can also be obtained in good yields through chlorination with thionyl chloride and sulfuryl chloride, using aluminum trichloride as catalyst.