Ceric ammonium nitrate and manganese(III) acetate mediated radical oxidation and addition reactions of anthracene and 9-substituted anthracenes

Abstract

Radical oxidation and addition reactions of anthracene (1), 9-methylanthracene (2) and 9-phenylanthracene (3) were investigated with dimethyl malonate (4) in the presence of ceric ammonium nitrate (CAN) and manganese(III) acetate (Mn(OAc)3). Although mostly anthraquinone derivatives and bianthrone were obtained with CAN, substituted 9,10-dihydroanthracene and 9,10-substituted anthracene derivatives were obtained with Mn(OAc)3. Dimethylmalonyl addition products (5a, 33 % and 5b, 42 %) were obtained in higher yield than quinones (5d, 8 % and 5e, 3 %) using Mn(OAc)3 as oxidant. 9a (96 %) and 9b (84 %) were synthesized in high yield and substitution products (7a, 44 % and 8b, 56 %) were obtained in higher yields than quinones (5d and 5e) using CAN as oxidant. The reactions were carried out in non-acidic medium (dichloromethane and methanol). Based on the structures of the isolated products a mechanism for these transformations was proposed.