Electrochemical oxidation of clomipramine drug in the absence and presence of 1, 3 dimethyl barbituric acid nucleophile: Electrochemical synthesis of new dibenzazepine derivative

Document Type : Original Article


Department of Chemistry,Faculty of Sciences, Payame Noor University (PNU), Tehran, Iran


Electrochemistry due suitable performance (selectivity, speed, sensitivity, and high accuracy) provides very interesting and versatile means for the study of pharmaceutical and biological compounds. In this study, electrochemical oxidation of clomipramine in the absence and presence of 1,3 dimethyl barbituric acid as a nucleophile in acidic medium with mechanistic studies has been investigated and synthesis a new dibenzazepine derivative electrochemically. Electrochemical oxidation of clomipramine drug has been studied in aqueous solution and various pHs using cyclic voltammetry and controlled-potential coulometry. Based on electrochemical results, dimerization is the main reaction of electro-oxidation of clomipramine in the absence of nucleophile via an ECE mechanism. Also, voltammetric results indicate that the oxidized dimeric form of clomipramine participation in Michael addition reaction with the1,3 dimethyl barbituric acid via an ECEC electrochemical mechanisms. However, the voltammetry and coulometry results imply existence of a catalytic (EC’) electrochemical mechanism in parallel with ECEC electrochemical mechanism. Finally, the product has been characterized by IR, 1H NMR, 13C NMR and MS methods


[1] H. Lund, O. Hammerich, “Organic Electrochemistry”, 4th ed.; Marcel Dekker, New York, (2001).
[2] M. Ebadi, Electrochim. Acta, 48 (2003) 4233.
[3] A. J. Bard, L. R.  Faulkner, “Electrochemical Methods”, 2nd ed.; Wiley, New York, (2001).
[4] B. Habibi, Z. Aiazi, J. Rostami, J. Of Applied Chemistry, 46 (1397) 9, in Persian.
[5] H. Beiginejad, D. Nematollahi, S. Khazalpour, J. Of Applied Chemistry, 48 (1397) 75, in Persian.
[6] W. Reimann, H. Schlutz, N. Selve, Anesth. Analg. 88 (1999)141-145.
[7] A. Rousseau, P. Marquet, J. F. Lagorce, M. F. Sauvage, J. Buxeraud, G. Lachatre, C. Raby, Pharmacology, 57 (1998) 242.
[8] Fa. Hamidi, M R. Hajmohammadi, Ali B.G. Aghaie,   J.  Chromatography B, 1063 (2017) 18.
[9] T. Noguchi, K. Shimoda, S. Takahashi, J. affective disorders, 29 (1993) 267.
[10] M. Saraji, A.A.H. Bidgoli, T. Khayamian, A. Moradmand, J. Chromatography A, 1218 (2011) 8600.
[11] R. Esmaili, D. Nematollahi, Electrochim. Acta, 56 (2011) 3899.
[12] E. Tammari, M. Bashiri, F. Ganjeizadeh Rohani, J. Of Applied Chemistry, 51 (1398) 177, in Persian.
[13] D. Nematollahi, A. Amani, E. Tammari, J. Org. Chem., 72 (2007) 3646.
[14] Sh. Lotfi, E. Tammari, A. Nezhadali, Materials Science and Engineering C, 76 (2017) 153.
[15] D. Nematollahi, M. S. Workentin, E. Tammari, Chem. Commun., (2006) 1631.
[16] S. Besbes-Hentati, H. Said, M. Bouvet, Electrochim. Acta, 52 (2007) 4715.
[17] J. Rault-Berthelot, E. Raoult, F. L. Floch, J. Electroanal. Chem., 546 (2003) 29.
[18] E. Tammari, A.Nezhadali, Sh. Lotfi, Electroanalysis, 27 (2015) 1693.
[19] B. Mirzaei, A. Zarrabi, M. Rafienia, J. Of New Materials, 7 (1396) 113, , in Persian.
[20] M. Singh Jat, K. Meena, K.K. Jhankal and D. K. Sharma, J. Pharm. Sci. & Res. 11(3) (2019) 700.
[21] E. Bioship, W. Hussein, Analyst, 109 (1984) 73.
[22] S.N. Frank, A. Bard, A. Ledwith, J. Electrochem. Soc., 122 (1975) 898.
[23] W. Misiuk,  J. Pharm. Biomed. Anal. 22 (2000) 189.
[24] A.J. Bard, L.R. Faulker, Electrochemical Methods, second ed. Wiley, New York, (2001).
[25] E. Laviron, J. Electroanal. Chem.101 (1979)19.
[26] K. Izutsu, Electrochemistry in Nonaqueous Solutions, Wiley-VCH Verlag GmbH & Co. KGaA, (2002).
[27] M.D., Rayan, A.Y., Ueh, C. Wen-yu, J. Electrochem. Soc., 17(1980) 1489.