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Azabicyclo chemistry II. Synthesis of 1,5‐methano‐2,3,4,5‐tetrahydro‐1 H ‐2‐benzazepines. B‐norbenzomorphans
Author(s) -
Mokotoff Michael,
Jacobson Arthur E.
Publication year - 1970
Publication title -
journal of heterocyclic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.321
H-Index - 59
eISSN - 1943-5193
pISSN - 0022-152X
DOI - 10.1002/jhet.5570070404
Subject(s) - chemistry , acetic anhydride , benzazepine , benzazepines , oxime , acetic acid , catalytic hydrogenation , hydrolysis , derivative (finance) , organic chemistry , stereochemistry , medicinal chemistry , catalysis , financial economics , economics
The syntheses of the B‐norbenzomorphans, 1,5‐methano‐2,3,4,5‐tetrahydro‐1 H ‐2‐benzazepine (1a) and its N ‐methyl derivative (Ib) were accomplished. Phenylsuccinic anhydride (III) was cyclized to 3‐carboxy‐1‐indanone (IVa), which was converted by the Arndt‐Eistert method to the homologous methyl indanone‐3‐acetate (V). One experiment in the synthesis of V led to the by‐products 3‐carboxamido‐1‐indanone (IVd) and 3‐( N ‐methylcarboxamido)‐1‐indanone (IVe), identified by physical and chemical means. Methyl 1‐aminoindan‐3‐acetate (VII) was prepared by catalytic reduction of methyl indanone‐3‐acetate oxime (VI). Hydrolysis of VII afforded 1‐aminoindan‐3‐acetic acid (VIII), which was cyclized with dicyclohexylcarbodiimide to 1,5‐methano‐2,3,4,5‐tetrahydro‐1 H ‐2‐benzazepin‐3‐one (IX). Reduction (lithium aluminum hydride) of IX gave amine Ia which was then methylated to Ib. The mass spectral fragmentation patterns of IX and Ia are discussed.