Studies on Diazabenzobicyclo [3.3.1] nonane System. VII. Synthesis of 1, 2, 3, 4, 5, 6-Hexahydro-1, 5-methanobenzo [e][1, 2] diazocine Derivatives and an Example of Abnormal Cleavage of Hydrazide by Lithium Aluminum Hydride

Abstract

3-Oxo-1, 2, 3, 4-tetrahydro-1-naphthoic acid obtained by reduction of 3-methoxy-1-naphthoic acid with sodium amalgam was condensed with N-methyl-N-acetylhydrazine to give the corresponding hydrazone (VIII). VIII was submitted to catalytic reduction over Adams catalyst, methylation with formic acid-formalin, hydrolysis with hydrochloric acid, esterification with methanol and intramolecular cyclization to afford 3, 4-dimethyl-3, 4, 5, 6-tetrahydro-1, 5-methanobenzo [e][1, 2] diazocin-2(1H)-one(XII). Treatment of XII with lithium aluminum hydride gave an abnormally cleft product, 4-methyl-5, 6-dihydro-1H, 4H-1.5-methanobenzo [e][1, 2] diazocine (XVII). XVII was reduced with lithium aluminum hydrode to give 4-methyl-1, 2, 3, 4, 5, 6-hexahydro-1, 5-methanobenzo-[e][1, 2] diazocine (XVIII). Structures of XII, XVII and XVIII were confirmed by chemical as well as spectral methods.