Interaction between the Cation Radicals and Weak-Nucleophilic Reagent in Photochemical Electron Transfer Systems.

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The interaction between the cation radicals generated by the photochemical electron transfer and various nucleophiles has been investigated.(1)An Interaction with Acetate Anion. The photooxygenation of naphthalene derivatives in the presence of acetate anion gave pothalic acids whereas the photooxygenation in the absence of the salts gave naphthoquinone derivatives. Thus the acetate ion accelerate the reaction of the cation radicals with oxygen molecule.(2)An Interaction with Amines. Regiochemistry on photoamination via the reaction of the cation radical with amines has been investigated for a dozen 1, 2-arylphenylethenes. A regioselective photoamination occurred in the stilbenes having the methoxy group at para position on aryl group. The amine added to 9-alkoxyphenanthrene mainly in trans manner to give cis-9-amino-10-alkoxy-9, 10-dihydrophenanthrene.(3)An Interaction with Trialkylphosphites. The preparation of arene phosphonates was performed by the reaction of the cation radicals of phenanthrene or naphthalene with trialkyl phosphites.(4)An Interaction with Acetonitrile. Cyanomethylation of 1, 1-diphenylalkenes was performed by the photoreaction in the presence of p-dicyanobenzene and t-butylamine in acetonitrile.