Semnan University Press Applied Chemistry Today 2981-2437 13 48 2018 09 23 Electrochemical oxidation of some dihydroxybenzoic acid derivatives in the presence of various nucleophiles: Experimental and theoretical analysis Electrochemical oxidation of some dihydroxybenzoic acid derivatives in the presence of various nucleophiles: Experimental and theoretical analysis 75 88 2976 10.22075/chem.2018.2976 FA Hadi Beiginejad Scientific board Davood Nematollahi Faculty board Sadegh Khazalpour Faculty board Journal Article 2017 06 04 In this work, mechanistic study of the electrochemical oxidation of 2,5-dihydroxybenzoic acid (2,5-DHBA) and 2,3-dihydroxybenzoic acid (2,3-DHBA) in the presence of various nucleophiles have been investigated both experimentally and theoretically. The study was done by the use of cyclic voltammetry, controlled-potential coulometry and Density Functional Theory (DFT). The theoretical results were calculated at DFT (B3LYP and BP86) levels of theory and 6-311+G (p,d) basis set. Results showed that two-electron oxidation of studied species is followed by a Michael addition reaction of nucleophiles and new dihydroxybenzoic acids are produced. Considering several mechanisms indicates that electrochemical oxidation potentials (Ep) of studied species are directly dependent on the ΔGtot of electrochemical oxidation. It was found that the products which are produced on the surface of electrode, depending on their ΔGtot of the electrochemical oxidation, will participate in the electrochemical or chemical following reactions. In this work, mechanistic study of the electrochemical oxidation of 2,5-dihydroxybenzoic acid (2,5-DHBA) and 2,3-dihydroxybenzoic acid (2,3-DHBA) in the presence of various nucleophiles have been investigated both experimentally and theoretically. The study was done by the use of cyclic voltammetry, controlled-potential coulometry and Density Functional Theory (DFT). The theoretical results were calculated at DFT (B3LYP and BP86) levels of theory and 6-311+G (p,d) basis set. Results showed that two-electron oxidation of studied species is followed by a Michael addition reaction of nucleophiles and new dihydroxybenzoic acids are produced. Considering several mechanisms indicates that electrochemical oxidation potentials (Ep) of studied species are directly dependent on the ΔGtot of electrochemical oxidation. It was found that the products which are produced on the surface of electrode, depending on their ΔGtot of the electrochemical oxidation, will participate in the electrochemical or chemical following reactions. https://chemistry.semnan.ac.ir/article_2976_de77dc45b8e47efb0e2dbf80227e55ec.pdf