Photolysis of 3-chloro-3-aryldiazirines in the presence of amines and allyl alcohol

When photolysis of arylchlorodiazirines is performed in the presence of either alkyl- or allyl-substituted amines, either N-alkyl- or N-allyl-substituted amines result as the sole high-yield (64-93%) products. Photolysis in the presence of phenylallylamine produces a rearranged product in poor yield (11-15%) whereas the reaction of allyl alcohol with arylchlorocarbene gives exclusively diallyl acetals in high yield (70%). The rate constants for these reactions were obtained by laser flash photolysis. Allyl phenyl ether forms a cyclopropanated product when treated with arylchlorocarbene. The different behaviour of these compounds may be attributed to the nucleophilicity at the nitrogen and oxygen centres of these compounds, when the latter are subjected to the substitutions described above. The formation of a cyclopropanated product when allyl phenyl ether is used differs from the reaction of bis (methoxycarbonyl) carbene with allyl ethers, as reported in the literature. The formation of this cyclopropanated product demonstrates the absence of an oxonium ylide intermediate during the reaction.