Riboflavin-sensitized photochemical radical ion chain reaction of sulfo-group substitution for halogen in halogenated hydroxynaphthalenes

Abstract

It was shown that riboflavin (RF) is a sensitizer for the radical ion chain reaction of sulfo group substitution for halogen in halogenated hydroxynaphthalenes. The initaition mechanism involves the electron transfer reaction between the sulfite ion and excited riboflavin. The quantum yields of RF radical anions from the singlet and the triplet states upon excitation in an aqueous sodium sulfite solution are 0.01 and 0.15, respectively, as determined by means of flash photolysis. The principal decay reaction for RF radical anions is their recombination with sulfite radical anions in the bulk of solution at a rate constant of (3.8 ± 0.5) × 109 dm3 mol−1 s−1. The quantum yields of the riboflavin-sensitized substitution reaction increases in the presence of electron scavengers (chloranil, dinitrobenzene) and inorganic salts in the system.