A. Vogel, F. Troxler, A. Lindenmann
1969
Citations
0
Influential Citations
10
Citations
Journal
Helvetica Chimica Acta
Abstract
BECKMANN or SCHMIDT rearrangement of ethyl trans-4-oxo-1-phenyl-2-tetralincarboxylate (2) affords ethyl trans-2,3,4,5-tetrahydro-2-oxo-5-phenyl-1H-benzo [b] azepine-4-carboxylate (4). Mild treatment of trans-2,3,4,5-tetrahydro-1-methyl-2-oxo-5-phenyl-1 H-benzo-[b] azepine-4-carboxylic acid (7) with thionyl chloride and pyridine in dimethylformamide and subsequent reaction with an amine yields the corresponding benzazepine-4-carboxamide. If he it is applied during the preparation of the acid chloride, rearrangement occurs yielding cis and trans derivatives of hydrocarbostyril. 2,3,4,5-Tetrahydro-1,4-methano-1-methyl-5-phenyl-1 H-benzo-[b] azepinium chloride (25) reacts with primary or secondary amines to cis-tetrahydroquinoline derivatives. When heated above its melting point, trans-4,5-dihydro-2-methylamino-5-phenyl-3H-benzo-[b] azepine-4-carboxylic acid (29) rearranges with elimination of water to a mixture of cis-and trans-2,3,3a,4-tetrahydro-1-methyl-2-oxo-4-phenyl-1H-pyrrolo [2,3-b] quinoline (32 and 31). The reduction of 31 was investigated. The mechanisms of the rearrangements are discussed.