Mechanisms for aromatic photocyanation: naphthalene and biphenyl

Abstract
Photocyanation of naphthalene and biphenyl has been studied in the systems ArH–KCN–aqueous CH3CN and ArH–NaCN–CH3OH. The reaction is first order in CN and in ground state ArH as well as in excited ArH. The proposed mechanism involves the formation of a singlet excimer, which dissociates into radical ions before the attack of cyanide ion. Photocyanations in the presence of oxidants such as p-dicyanobenzene and persulphate ion proceed by oxidation of the singlet excited hydrocarbon to form a radical cation directly.

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