Summauy. B E C K M A N N or SCHMIDT rearrangemcnt of ethyl tuans-4-oxo-l-phcnyl-2-tctralincarboxylate (2) affords ethyl tvans-2,3,4,5-tetrahydro-2-0~0-5-phenyl-l H-benzo [b] azcpine-4carboxylate ( 4 ) . Mild treatment ol tvans-2,3,4,5-tctrahpdro-l-methyl-2-oxo-5-phcnyl-l H-benzo- [b] azcpine-4-carboxylic acid (7) with thionyl chloride and pyritiine in dimethylformamide and s u b s q u e n t reaction with an aminc yields the corresponding henzazepitie-4-carboxamide. If heat is applied during the preparation of the acid chloride, rearrangement occurs yielding cis and trans derivatives of hydrocarbostyril.
2, 3,4,5-Tctrahydro-l, 4-mcttiaiio-1-incthyl-5-phenyl-1 H-bcnzo [l)] azc-piniuin chloridc (25) reacts with primary or scconclary amines to cis-tetrahydroquinoline derivatives.
When heated above its melting point, trans-4,5-dihydro-2-methylamino-5-phenyl-3 If-benzo-[b] azepine-4-carboxylic acid (29) rearranges with elimination of water to a mixture of cisand trarzs-2,3,3 a , 4-tetrahydro-1-rnethyl-2-oxo-4-phenyl-1 H-pyrrolo [2, 3-b] quinolinc (32 and 31). The reduction of 31 was investigated.
The mechanisms of the rearrangcmcnts are discussed.
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1 . Synthese der Benzazepine.
I rans-l-Phenyl-4-tetralon-2-carbonsaureathylester (2) fl] 121 wurde in das Oxim 3 iibergefiihrt und dieses nach BECKMANN mit Polyphosphorsaure in ein Benzazepinderivat umgelagert, das auch durch ScmiIur-Reaktion von 2 init Natriumazid und Polyphosphorsaure erhalten wurde. In analoger Weise liess sich auch die freie 'Tetraloncarbonsaure 1 1 I ] 121 umlagcrn. l) Teilweise vorgctragen an der Winterversammlung der Schweiz. Chcm. Gcsellschalt votn 15.