Electrochemical oxidation of some dihydroxybenzoic acid derivatives in the presence of various nucleophiles: Experimental and theoretical analysis

Document Type : Original Article


1 Scientific board

2 Faculty board


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.


Main Subjects

[1] V.P. Kotsaki-Kovatsi, A.J. Vafiadou, G. Koehler-Samuilidou and A. Kovatsis, Vet. Hum. Toxicol.39, (1997) 211.
[2] R.H. Lima Leite, P. Cognet, A.M. Wilhelm and H. Delmas, J. Appl. Electrochem. 33, (2003) 693.
[4] C. Litos, A. Terzis, C. Raptopoulou, A. Rontoyianni and A. Karaliota, Polyhedron 25, (2006) 1337.
[5] D. M. Price, S. Bashir and P. R. Derrick, Thermochim. Acta 327, (1999) 167.
[6] W.P. Griffith, H.I.S. Nogueira, B.C. Parkin, R.N. Sheppard, A.J.P. White and D.J. Williams, J. Chem. Soc., Dalton Trans (1995) 1775.
[7] H.K. Chae, W.G. Klemperer and T.A. Marquart, Coordin. Chem. Rev. 128, (1993) 209.
[8] S. Vecchio, B. Brunetti, Thermochim. Acta 515, (2011) 84.
[9] D. Orhon, E. U. Cokgor, T. Katipoglu, G. Insel and O. Karahan, Bioresource Technology 101, (2010) 2665.
[10] C. Litos, V. Aletras, D. Hatzipanayioti, M. Kamariotaki and A. Lymberopoulou-Karaliota, Inorg. Chim.Acta 360, (2007) 2321.
[11] H. Karimi-Maleh, A. L. Sanati, V. K. Gupta, M. Yoosefian, M. Asif, A. Bahari, Sensors and Actuators B 204, (2014) 647.
[12] H. Karimi-Maleh, M. Moazampour, A. A. Ensafi, S. Mallakpour, M. Hatami, Environ. Sci. Pollut. Res. 21, (2014) 5879.
]13 [عربعلی، وحید، مجله شیمی کاربردی، شماره 40 (1395) ص 9.
]14[ حسنی نژاد درزی، سید کریم; شجیع، فرشاد، مجله شیمی کاربردی، شماره 43 (1396) ص 121.
[15] D. Nematollahi, S. Dehdashtian, A. Niazi, J. Electroanal. Chem. 616, (2008) 79.
[16] D. Nematollahi, H. Shayani-jam, J. Org. Chem. 73, (2008) 3428.
[17] D. Nematollahi, M. Alimoradi, S. Waqif-Husainc, Electroanalysis 16, (2004) 1359.
[18] A. Amani, D. Nematollahi, J. Org. Chem. 77, (2012) 11302.
[19] D. Nematollahi, E. Tammari, J. Org. Chem. 70, (2005) 7769.
[20] H. Beiginejad, D. Nematollahi, M. Bayat, F. Varmaghani and A. Nazaripour, J. Electrochem. Soc. 160, H693 (2013).
[21] M. J. Frisch et al., Gaussian 03, revision B. 04, Gaussian, Inc., Pittsburgh, PA (2003).
[22] D. Nematollahi, A. Ariapad, M. Rafiee, J. Electroanal. Chem. 602, (2007) 37.
[23] D. Nematollahia, M. Hesaria, S. S. Hosseiny-Davarani, ARKIVOC x, (2006) 129.
[24] D. Nematollahi, M. Alimoradi, S. Waqif Husain, Electrochim. Acta 51, (2006) 2620.
[25] S. Yannai, Dictionary of food compounds, 2nd edn (2010). CRC Press, Boca Raton.