Condensation of 1, 2, 3, 4, 5, 6-hexahydrobenzo[
b][1, 5]diazocine (IV) with formaldehyde, benzaldehyde, or acetaldehyde afforded respectively 3, 4-dihydro-2
H, 6
H-1, 5-methanobenzo[
b][1, 5]diazocine (Va), its 11-phenyl (Vb), and 11-methyl derivatives (Vc). Reaction of 2, 3, 45, -tetrahydro-1
H-benzo[
e][1, 4]diazecine (VII) with formaldehyde or benzaldehyde afforded 2, 3-dihydro-5
H-1, 4-methanobenzo[
e][1, 4]diazepine (VIIIa) and its 10-phenyl derivative (VIIIb).
From their nuclear magnetic resonance spectra and Dreiding models, it was assumed that the substituent at the 11-position of Vb and Vc had configuration of A-formula, and the phenyl group at the 10-position of VIIIb had configuration of B-formula.
Whereas the phenyl derivatives (Vb and VIIIb) were hydrolyzed to IV or VII and benzaldehyde by merely being dissolved in 0.1
N hydrochloric acid, Va, Vc, and VIIIa were found to be not hydrolyzed by this acidity.
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