Synthesis of 6-(Phenanthrene-3-yl)-2,3-dihydro-1,2,4,-triazine-3-thione as a New Reagent for the Non-Extractive Spectrophotometric Determination of Cu(II)

Document Type: Research Article


Department of Medicinal Chemistry, Faculty of Pharmacy and Pharmaceutical Sciences Research Center, Tehran University of Medical Sciences, P.O. Box 14155-6451 Tehran, I.R. IRAN


A simple, sensitive, and non-extractive spectrophotometric method was developed for the determination of copper (II) using a newly synthesized chromogenic reagent, 6-(phenanthrene-3-yl)-1,2,4,-triazine-3-thione(PhDTT), in Tween 80 neutral surfactant. To synthesize the reagent (PhDDT), amyl nitrite was added to 3-acethylphenanthrene and refluxed for 26 hours to produce 2-oxo-2-(phenanthren-3-yl) acetaldehyde oxime (I). The reaction of compound (I) with thiosemicarbazide yielded the reagent (PhDDT). Copper (II) forms a red colored complex with 6-(phenanthrene-3-yl)-1,2,4,-triazine-3-tion which shows maximum absorbance at 460 nm in the pH range 9.0-11.0. Beer’s law was obeyed over the concentration range of 1.4-10 µg/mL Cu2+ with r2 = 0.999.  The limit of detection was 0.48 μg/mL of copper (II). The within-day and between-day precision values were in the range of 0.38-3.3%. The method was tested by analyzing the amalgam samples. The results were in good agreement with the atomic absorption.


Main Subjects

[1] Strausak D., Mercer J. F. B., Dieter H. H., Stremmel W., Multhaup G., Copper in Disorders with Neurological Symptoms: Alzheimer's, Menkes, and Wilson Diseases, Brain Res. Bul., 55(2): 175-185 (2001).
[2] Gyawali R., Ibrahim S.A., Abu Hasfa S.H., Smqadri S.Q., Haik Y., Antimicrobial Activity of Copper Alone and in Combination with Lactic Acid Against Escherichia coli O157:H7 in Laboratory Medium and on the Surface of Lettuce and Tomatoes, Journal of Pathogens, Article ID 650968: 9 Pages (2011).
[5] Faúndez G., Troncoso M., Navarrete P., Figueroa G., Antimicrobial Activity of Copper Surfaces Against Suspensions of Salmonella Enterica and Campylobacter Jejuni, BMC Microbiology, 4(19): 1-7 (2004).
[6] Klaassen C.,  Watkins J.B., Casarett & Doull's Essentials of Toxicology”, Chapter 23, Toxic Effects of Metals (Jie Liu, Robert A. Goyer, and Michael P. Waalkes), Second Edition, McGraw-Hill, 323-335(2010).
[7] El-Asmy A.A., Al-Hazmi G.A.A., Synthesis and Spectral Feature of Benzophenone-Substituted Thiosemicarbazones and Their Ni(II) and Cu(II) Complexes, Spectrochimica Acta Part A, 71: 1885–1890 (2009).
[9] Ghazy S.E., El-Shazly R.M., El-Shahawi M.S., Al-Hazmi G.A.A., El-Asmy A.A., Spectrophotometric Determination of Copper (II) in Natural Waters, Vitamins and Certified Steel Scrap Samples Using Acetophenone -p- chlorophenylthiosemicarbazone, Journal of the Iranian Chemical Society, 3(2):
140-150 (2006).
[10] Ravindhranath K., A Simple Method for Spectrophotometric Determination of Traces of Copper, Rasayan J. Chem., 5(1): 38-41 (2012).
[11] Dehghani Z., Dadfarnia S., Haji Shabani A.M., Ehrampoush M.H., Determination of Iron Species by Combination of Solvent Assisted-Dispersive Solid Phase Extraction and Spectrophotometry, Anal. Bioanal. Chem. Res., 2(1): 13-21 (2015).
[15] Shamsa F., Barazandeh Tehrani M., Mehravar H., Mohammadi E., Spectrophotometric Determination of Cu2+ and Monitoring of Hg2+ and Ni2+ in some Iranian Vegetables Using 6-(2-Naphthyl)-2, 3-Dihydro-as-triazine-3-thione, Iranian Journal of Pharmaceutical Research, 12 (1): 9-13(2013).
[16] Barazandeh Tehrani M., Ghanbari H., Souri E., Shamsa F., Amini M., Synthesis of 6-(2-Methoxynaphthyl)-2,3-dihydro-1,2,4-triazine-3-thione as a New Reagent for Spectrophotometric Determination of Copper, International Journal of Analytical Chemistry, Article ID 260179, 6 pages,(2014).
[17] Barazandeh Tehrani M., Tahmasebi M., Souri E., Shamsa S.H.,  Synthesis of 5,6-Diphenyl-2,3-dihydro-1,2,4-triazine-3-thione as a New Reagent for Spectrophotometric Determination of Palladium. Chem. Sci. Trans., 4(1): 227-233 (2015).
[18] Barazandeh Tehrani M ., Mirkamali S.M.S., Souri E., Foroumadi A.,Derivative Spectrophotometric Method for Simultaneous Determination of Nickel(II) and Copper(II) Using 6-(Anthracen-2-yl)-2,3-dihydro-1,2,4-triazine-3-thione, Asian Journal of Chemistry24(10): 4517-4521(2012).
[19] Shrivastava A., Gupta V.B., (R.)Methods for the Determination of Limit of Detection and Limit of Quantification of Analytical Methods, Chron Young Sci, 2(1): 21-25 (2011).
[20] Armbruster D.A.,  Pry T., Limit of Blank, Limit of Detection and Limit of Quantitation, Clin. Biochem. Rev., 29(Supplement (i): S49–S52 (2008).