14585-46-7Relevant articles and documents
Nitrosamine Photolysis as a Synthetic Method: The Addition of Aminium Radicals to Unsaturated Carbon-Carbon Bonds
Chow, Yuan L.,Colon, Carlos J.,Chang, Dawid W. L.,Pillay, K. Somasekharen,Lochart Robert D.,Tezuka, Takahiro
, p. 622 - 634 (2007/10/02)
Acid complexed nitrosamines decompose from their lowest singlet excited state to gine aminium radicals and nitric oxide radical transients.Aminium radicals initiate addition of various unsaturated groups to give 1-amino-2-nitroso compounds under an inert atmosphere, or 1-amino-2-nitrates under oxygen.In this report, photoaddition of nitroamines to olefins, acetylenes and fused aromatic hydrocarbons, and the subsequent transformations of the intermediates are described.Aminium radical initiated intramolecular cyclization to prepare tetracyclic aza compounds is also described.While photoaddition of nitrosamines to 4-propenylanisole or 3-butenol wes efficient, that to 3-butenyl benzoates under oxidative conditions was only fair, obviously due to the presence of a benzene ring.The oxidative photoaddition to 3-butenyl halide was followed by spontaneous cyclization to an azaspiro compound.The photoaddition to phenyl-substituted acetylenes gave β-nitroso enamines which hydrolyzed to diketomonoximes under neitral conditions but decomposed extensively under acidic conditions.Certain fused aromatic hydrocarbons acted as singlet sensitizers as well as substrates to induce similar addition giving amino nitroso adducts.These adducts took different courses of conversion dependent on reaction conditions, and on steric and electronic factors.
