Dibenzothiepin Derivatives and Related Compounds. I. Isolation of 11-Phenyl-6, 11-dihydrodibenzo [b, e] thiepin-11-ylium Salts and Their Novel Dehydrocyclization Reaction

• Published in: YAKUGAKU ZASSHI Vol. 98; no. 9; pp. 1189 - 1197
• Main Authors: HORI, MIKIO, KATAOKA, TADASHI, SHIMIZU, HIROSHI, ONOGI, KAZUHIRO
• Format: Journal Article
• Language: Japanese
• Published: The Pharmaceutical Society of Japan 25.09.1978
• Subjects: 11-phenyl-6, 11-dihydrodibenzo [b, e] thiepin-11-ylium salts; 5, 13b-dihydrofluoreno [1, 9a, 9-c, d] benzothiepin-13b-ylium hexachloroantimonate; 9-(o-tolyl)-9-fluorenol; desulfurization reaction; novel dehydrocyclization reaction
• ISSN: 0031-6903; 1347-5231
• DOI: 10.1248/yakushi1947.98.9_1189

As a fundamental study on dibenzothiepins, reaction of 11-phenyl-6, 11-dihydrodibenzo [b, e] thiepin-11-ol (10) or 11-chloro-11-phenyl-6, 11-dihydrodibenzo [b, e] thiepin (14) with triphenylmethyl cation or SbCl5 was examined under various conditions. 11-Phenyl-6, 11-dihydrodibenzo [b, e] thiepin-11-ylium salt (8) was isolated as a black powder (perchlorate) and a green powder (hexachloroantimonate), but BF4 salt was obtained only as a solution. Treatment of the hexachloroantimonate with excess of SbCl5 was found to result in a novel dehydrocyclization reaction to give selectively 9, 13b-dihydrofluoreno [1, 9a, 9-c, d] [2]-benzothiepin-13b-ylium hexachloroantimonate (19). Some discussions were made on the mechanism of the formation of 19.