Nitroso compounds. Part XXI: Photolysis of gem-chloronitrosoadamantane in benzene and in alcohols

摘要: Photolysis in benzene of gemchloronitrosoadamantane-a model compound with no “active” α-hydrogen - yields adamantanone (51%) and gem-dichloro-adamantane (44%). In hydrogen-donating solvents like methanol or isopropanol the dichloro derivative is not formed, main products are ketone (38%) its oxime (55%). In inert excited nitroso group releases nitric oxide, which interacts ground-state starting material to give presumably an unstable diazonium nitrate, a logical precursor all stable end-products observed. On other hand, first reacts alcohol, followed by loss chlorine formation oxime. This mechanism explains better than do existing theories, reaction solvent proposed occur after initial release from chloronitroso compound.