Abstract
Beckmann rearrangement of 1, 2, 3, 4, 5, 6, 7, 8-octahydro-2, 5-dioxoquinoline oxime (Ia, b) and 1, 2, 3, 4, 5, 6, 7, 10-octahydro-2, 7-dioxoquinoline oximes (VIa, b) with PPA gives 1, 2, 3, -4, 5, 6, 7, 8, 9-nonahydro-2, 5-dioxopyrido [3, 2-c] azepine (IIa, b) and 1, 2, 3, 4, 5, 6, 7, 8, 10-nonahydro-2, 8-dioxopyrido [2, 3-d] azepine (VIIa, b), respectively. Under the same reaction conditions, 3-acetylamino-2-methyl-2-cyclohexen-1-one oxime (X) and 1-acetyl-1, 2, 3, 4, 5, 6, 7, 8-octahydro-5-oxoquinoline oxime (XIII) undergo a Semmler-Wolff aromatization to give 2-methyl-1, 3-phenylenediamine (XI) and 5-amino-1, 2, 3, 4-tetrahydroquinoline (XIV), respectively.
