SYNTHESIS OF ADAMANTANE DERIVATIVES .47. PHOTO-CHEMICAL SYNTHESIS OF 4-AZAHOMOADAMANT-4-ENES AND FURTHER-STUDIES ON THEIR REACTIVITY IN SOME CYCLOADDITIONS

Direct photolysis of 2-azidoadamantanes (2a, b, e, f) in cyclohexane and/or in benzene afforded predominantly ring-expanded 4-azahomoadamant-4-enes (3a, b, e, f) and N-adamantylideneamines (5a, b, e, f) resulting from migration of H or a nonring carbon atom as minor products. The benzyl derivative 3e was particularly air-sensitive and was isolated as the 5-benzoyl derivative 3e'. The 79C NMR spectra of 3a, b, e', f are reported. The reactions of imines 3 with diphenylketene, benzonitrile oxide, diphenylnitrilimine, and tosylmethyl isocyanide afforded the corresponding cycloadducts 11, 14a-c, 15a, b, and 17, respectively. © 1979, American Chemical Society. All rights reserved.