Treatment of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-7, 8-dimethoxy-2-methyl-1H-2-benzazepine (7a) with dimsylsodium afforded 5, 6, 7, 8, 13, 14-hexahydrotrans-13, 14-methano-2, 3, 10, 11-tetramethoxy-5-methyldibenzo [b, f] azecine (8) and its cisisomer (9). The structure of the former was confirmed by direct comparison with the authentic sample prepared by the Simmons-Smith reaction of the 13, 14-trans-5, 6, 7, 8-tetrahydrodibenzo [b, f] azecine (11). 5, 6, 7, 8, 13, 14-Hexahydro-11-hydroxy-cis-13, 14-methano-2, 3, 10-trimethoxy-5-methyldibenzo [b, f] azecine (15) was obtained by the reaction of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-8-hydroxy-7-methoxy-2-methyl-1H-2-benzazepine (7b) with dimsylsodium. The same reaction by the use of 1-(2-bromo-4, 5-dimethoxyphenethyl)-2, 3, 4, 5-tetrahydro-7-hydroxy-8-methoxy-2-methyl-1H-2-benzazepine (7e) afforded the 13-(methylsulfinyl) methyl-5H-dibenzo [b, g] azacycloundecine (16).