1958 年 78 巻 4 号 p. 407-410
The dihydro compound (IV), abtained by catalytic reduction of adnamine hydrochloride, was methylated with dimethyl sulfate and sodium hydroxide, and the methosulfate (XIII), m.p. 258-260°, C24H35NS, so obtained was submitted to the Hofmann degradation, affording the des-N compound (XIV), m.p. 184-186°, C20H22O4. This was catalytically reduced to the dihydro compound (XV), m.p. 128-129°, C20H24O4. It was confirmed through admixture, and ultraviolet and infrared absorption spectra that (XIII), (XIV), and (XV) were respectively identical with 5-dimethylaminomethyl-2, 3, 7, 8-tetramethoxydibenzo [a, d] cyclohepta-1, 4-diene methosulfate, 5-methylene-2, 3, 7, 8-tetramethoxydibenzo [a, d] cyclohepta-1, 4-diene, and 5-methyl-2, 3, 7, 8-tetramethoxydibenzo [a, d] cyclohepta-1, 4-diene synthesized by Battersby and others.
It was found by consideration of experimental results reported to date that adnamine is 5-methylaminomethyl-2, 3, 7, 8-tetrahydroxydibenzo [a, e] cycloheptatriene. The seven-membered ring in methyladnamine is hardly hydrogenated but the dihydro compound (VII) of its des-N compound forms (XV) in 20% yield on catalytic reduction over palladium charcoal, at 190° and 65 atm., together with recovery of 10% of (VIII).