Thermolysis of several p-substituted aryl azides (p-RC 6 H 4 N 3; R= COCH 3, CO 2 CH 3, COPh) in methanol gave 5-substituted 2-methoxy-3H-azepines in moderate yields. Thermolysis of m-substituted aryl azides (m-RC 6 H 4 N 3; R= COCH 3, CO 2 CH 3, COPh, NO 2) gave 4-substituted 2-methoxy-3H-azepines and 6-substituted 2-methoxy-3H-azepines in good yields. In contrast, thermolysis of p-azidoacetophenone in piperidine gave 5- ...