ABSTRACT:
The two novelcomplexes between Lead (II) w88 win Mercury (II)ion w88 win ligand, 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) hydrazine carbothioamide (PTZBS), a novel thiosemicarbazone were performed from starting material,Phenothiazine, which was conducted via methylation, , forming double bond C=O (Vilsmeier - Haak - Arnol’d reaction), bromination by NBS, nucleophile addition reaction of thiosemicarbazone to C=O double bond yielding thiosemicarbazone compound. Final state made the oxidation reaction, which formed a novel thiosemicarbazone compound. The novel ligand, 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) indicated the complexes with Pb (II) w88 win Hg (II) ion, respectively. The structure of ligand was checked IR,1H,13C, DEPT- NMR, 2D-NMR (COSY w88 win HMBC), w88 win HR-MS.
Keywords:complexes of lead (II) w88 win mercury (II), phenothiazine.
1. Introduction
Chemistry of phenothiazine has been fully reported in review article[1]w88 win new derivatives of phenothiazine, w88 win carbazole has indicated in previous article[2]. Many applications of phenothiazine groups show as photovoltaic applications[3], solar cell performance[4], synthesis, electrochemistry, light-emitting properties[5], w88 win phototherapeutic agents[6]. Some significant bioactivates have revealed antitubercular[7]w88 win cancer chemo preventive effect[8-10]. The important phenothiazine derivatives have applied in biochemistry w88 win coordinate chemistry, which were thiosemicarbazone derivatives. These thiosemicarbazone compounds have made the complexes with metal ions[11]. The bonding w88 win structure trends of thiosemicarbazone derivatives of metals have presented in many articles[12]. Some analytical applications of the thiosemicarbazone w88 win semi carbazones have indicated in previous article[11]. Few significant applications of metal complexes of thiosemicarbazones in imaging w88 win therapy[13], anticancer[14-16], antibacterial of Mn(II), Co(II), Zn(II), Fe(III) w88 win U (VI) complexes, w88 win 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT), w88 win antitumor of thiosemicarbazone- functionalized organ ruthenium (II)-arene, antioxidant, w88 win antidiabetic of nickel complex of vanillin-4-Methyl-4-phenyl-3-thiosemicarbazone have mentioned,[17-18]. The complexes of thiosemicarbazone w88 win metal ions as Cu (II), Zn(II), Ni (II), Mn(II), Fe (II), Bi (III) Co (III), Ga(III), Cd (II), Ru(II), Pd (II) w88 win Pt (II) have studied strategy in many articles in synthesis, structure, w88 win application in biochemistry, analytical chemistry, w88 win optical applications[19-27]. The complexes of Hg (II) w88 win thiosemicarbazone have reported in few article as spectroscopic studies[28], DNA[29], electrodes modified with clickable thiosemicarbazone ligands for sensitive voltametric detection of Hg(II) ions[30], w88 win structural review[31]. The complex of Pb(II) w88 win thiosemicarbazone derivatives have been rarely research article[32], [31]. As interesting about coordinate chemistry, analytical chemistry, the pollutions of heavy metals in wastewater, printing, w88 win paper making, we continue to make synthesis of novel water-soluble ligand (thiosemicarbazone derivative) w88 win conduct the complexes of Hg (II) w88 win Pb(II) ions with ligand, respectively.
2. Materials w88 win methods
The chemical reagents w88 win solvents for reactions were obtained from Sigma- Aldrich, the solvents for chromatography column, ethyl acetate, n-hexane, dichloromethane, chloroform, w88 win others were bought from Viet Nam suppliers. The TLC was received from Merk company. The synthesis compounds via ethylation (1), bromination (2), carbonylation (3), w88 win nucleophile addition of thiosemicarbazone (4) to a derivative carbonyl were followed thescheme 1[33]except for oxidation reaction (5), which was based on article[1]. The complexes of metal ions (Hg2+or Pb2+) w88 win ligand (5) w88 win assessment of effects to form the derivative thiosemicarbazone complexes were performed based on previous article[20].
Procedure for synthesis of Ethyl phenothiazine(1): 16g (0.08 mol) of phenothiazine was dissolved in 175 mL (2.46 mol) of DMF solvent w88 win 5 g NaH (0.08 mol), then slowly added 11.7 mL of C2H5Br (0,15 mol). The reaction mixer was heated w88 win stirred for 8 hours. When the reaction was finished, it was added more water, stirred, w88 win waited for the forming solid. The mass of solid was filtered through the vacuum filtration system to get the light purple solid. The solid was washed with MeOH solvent w88 win heated to 500C. After washing, the solid was filtered to yield the white solid. The yield of reaction was 86.36%.
Procedure for synthesis of 10-ethyl-10H-phenothiazine-3-carbaldehyde(2): 5 g of ethyl phenothiazine (1) in 7,5 ml of CHCl3solvent added 25 mL of DMF in a two neck round bottom flask w88 win made the mixture in ice bath. 7,5 mL of CHCl3solvent w88 win 41 mL of POCl3were taken into a separating funnel. The separating funnel were slowly dropped in a two-neck flask, allowing the mixture to run for approximately 1 hour. After one hour, the ice bath was replaced with an oil tank w88 win started heating the system at about 70-75oC. After completing of the reaction (checking TLC) was 22 hours, it was transferred the entire mixture to the separating funnel, added 10% NaOH solution, w88 win shacked well to separate the two phases, which the water phase was above layer, w88 win the organic phase was below layer. The organic phase was repeated the wash with amount of water until it has pH 7.0. The Na2SO4was added to organic phase to dry the residual water in organic layer. The organic layer was vacuum filtration to obtain the solution. The obtained extract was evaporated in vacuum to obtain solid. The yellow solid was washed in hot hexane at 40-50°C). After 2 hours of stirring, the vacuum filtration was conducted w88 win obtained 5.25 grams of solid. The yield was obtained 93.42%.Procedure for synthesis of 7-bromo-10-ethyl-10H-phenothiazine-3-carbaldehyde (3):2.3 grams of compound (2) (0.09 mol) added into a two neck round bottom flask, inserted the condenser system, w88 win made exactly 9 mL of CHCl3into it. The reaction mixer was heated w88 win stirred. To weigh 1.61 grams (0.09 mol) of NBS added to a two neck round bottom flask. The system started to heat at 70-750C. At the end of the reaction, the entire mixture was poured to the separating funnel, added water, w88 win shacked to separate two phases. The layer of organic was repeated to wash with water from 2-3 times. The solution was dried with Na2SO4 to a solution. The obtained extract was subjected to vacuum evaporation to obtain a viscous mixture. The solid was washed in warm hexane. After 2 hours of stirring w88 win vacuum filtration, the pure solid was obtained 2.34 grams of light yellow solid. The yield was 76.47%.
Procedure for synthesis of 2-((7-bromo-10-ethyl-10H-phenothiazin-3-yl) methylene) hydrazine carbothioamide (4):2.34 gram of compound (3) w88 win 0.808 gram of thiosemicarbazone added into a two neck round bottom flask, installed a condenser system, poured 50 mL of EtOH solvent into it, w88 win added 0.8 mL of AcOH (ice). The mixer of reaction was started to heat to 800C w88 win stirred continuously. After few hours of reaction, the reaction was checked TLC. After completing reaction, the solid, being formed in reaction was filtered to separate the solid. The solid was washed in warm ethanol at 55-60oC. The vacuum filtration w88 win drying yielded 2.5 gram of yellow solid. The yield was 88.23%.
Procedure for synthesis of 2-((7-bromo-10-ethyl-5-oxido-10H-phenothiazin-3-yl)methylene) hydrazine carbothioamide (5):2.5 gram of compound (4) was added a two neck round bottom flask, inserted the condenser system, w88 win taken exactly 10 mL of CHCl3into it. When the solid was completely dissolved in CHCl3solvent, it added 1.1 mL AcOH (ice) w88 win 0.2 mL H2O2. The reaction was increased temperature to 500C w88 win stirred. When the temperature of reaction was desired, reaction time was started counting, w88 win added 0.2 mL H2O2every hour. The entire mixture was transferred to the separating funnel, added 10% of a NaOH solution, w88 win shake well to separate into the two phases. The organic layer below was kept w88 win repeated to wash until pH 7. The Na2SO4 was used to dry residual water in solution. The obtained solution was subjected to vacuum evaporation to obtain a viscous mixture. The yellow solid was washed in warm hexane at 55-60°C. After completing stirring, the solid was performed the vacuum filtration w88 win obtained 2.53 gram of yellow solid. The yield was 78.82%.
Results w88 win Discussions
Results: Ethyl phenothiazine (1): FT-IR cm-1): 2982(CH3), 2932(CH2), 2860(C-H), 1574, 1447 (C=C), 1121 C-N, 750 (substitute phenothiazine);1H-NMR (500 MHz, Acetone,d6):d(ppm): 1.36 (t,J =7.5, 3H; CH3), 3.39 (q,J=7.5 Hz, 2H, CH2), 6.90–6.93 (m, 2H, Phenothyazine–H), 6.97–6.99 (m, 2H, Phenothiazine–H), 7.10–7.12 (m, 2H, Phenothiazine–H), 7.16–7.19 (m, 2H, Phenothiazine–H);13C-NMR (125 MHz, acetone,d6), DEPT 90, 135 w88 win CPD:d(ppm): 13.3 (CH3), 42.2 (CH2), 116.2 (CH), 123.1(CH), 125.0 (quaternary carbon), 127.9 (CH), 128.2 (CH) và 145.8 (quaternary carbon);10-ethyl-10H-phenothiazine-3-carbaldehyde (2): FT-IR cm-1): 2976 (CH3) 2825 (CH2), 1667 (C=O), 1567, 1460 (C=C), 1242 (C-N), 747 (substitute phenothiazine);1H-NMR (500 MHz, Acetone,d6):d(ppm): 1.40 (t,J=7.0 Hz, 3H; CH3), 4.09 (q,J=7.5 Hz, 2H, CH2), , 6.97–6.99 (m, 1H, Phenothiazine–H), 7.05–7.07 (m, 1H, Ar–H), 7.10–7.13 (m, 2H, Ar–H), 7.56 (d,J = 5.0 Hz, 1H, Phenothiazine–H), 7.19–7.23 (m, 1H, Phenothiazine–H), 7.69–7.71 (m, 1H, Phenothiazine–H), 9.82 (s, 1H, CH=O);13C-NMR (125 MHz, acetone,d6), DEPT 90, 135 w88 win CPD:d(ppm): 13.05 (CH3), 42.90 (CH2), 115.8 (CH), 116.8 (CH), 123.7(quaternary carbon), 124.3 (CH), 124.9 (quartenary carbon), 128.0 (CH), 128.3 (CH), 128.6 (CH), 130.9 (CH), 132.3 (quaternary carbon), 144.1(quaternary carbon), 150.9 (quaternary carbon), 190.4 (CH=O);7-bromo-10-ethyl-10H-phenothiazine-3-carbaldehyde (3):FT-IR cm-1): 2969 (CH3), 2830 (CH2), 1670 (C=O), 1463 (C=C), 1240 (C-N);1H-NMR (500 MHz, Acetone,d6):d(ppm): 1.38 (t,J=5.0 Hz, 3H, CH3), 4.01(q,J= 5.0 Hz, 2H, CH2), 6.96 (d,J=10.0 Hz,1H, Phenothiazine-H), 7.13 (d,J=10.0 Hz, 1H, Phenothiazine–H), 7.23 (d,J = 5.0 Hz,1H, Phenothiazine-H), 7.30–7.32 (m, 1H, Phenothiazine-H), 7.54 (d,J = 5.0 Hz, 1H, Phenothiazine-H), 7.70–7.71 (m, 1H, Phenothiazine-H), 9.82 (s, 1H, CH=O);13C-NMR (125 MHz, acetone,d6), DEPT 90, 135 w88 win CPD:d(ppm): 12.9 (CH3), 43.0 (CH2), 116.0 (CH), 118.3 (CH), 115.9 (quaternary carbon), 124.0 (quaternary carbon), 128.4 (CH), 129.9 (CH), 131.1 (CH), 131.2 (CH), 126.2 (quaternary carbon), 132.5 (quaternary carbon), 143.4 (quaternary carbon), 150.3 (quaternary carbon), 190.4 (CH=O);2-((7-bromo-10-ethyl-10H-phenothiazin-3-yl) methylene) hydrazine carbothioamide (4):FT-IR cm-1): 3402 (N-H of NH2), 3345(N-H of NH2), 2881 (CH2), 1594 (azomethine, C=N), 1509 (C=C, Phenothiazine), 1458 (C-H, bending), 1240 (C-N), 1097 (C=S), 547 (C-Br);1H-NMR (500 MHz, Acetone,d6):d(ppm): 1.22 (t,J =7.0 Hz, 3H, CH3), 3.62 (q,J=7.0 Hz, 2H, CH2), 6.5 (s, 1H, CH=N), 6.69 (d,J= 8.5 Hz, 1H, Phenothiazine-H), 6.81(d,J= 8.5 Hz,1H, Phenothiazine-H), 7.19–7.23 (m, 3H, Phenothiazine-H), 7.32 (d,J=2.0 Hz, 1H, Phenothiazine–H), 7.34 (s, 1H, NH2), 7.69 (s, 1H, NH2), 9.67 (s, 1H, NH);13C-NMR (125 MHz, acetone,d6), DEPT 90, 135 w88 win CPD:d(ppm): 12.3 (CH3), 41.4 (CH2), 113.5 (CH), 113.9 (quaternary carbon), 115.2(CH), 117.1 (CH), 122.5 (C quaternary carbon), 124.7 (CH), 124.8 (quaternary carbon), 127.9 (quaternary carbon), 128.8 (CH), 130.2 (CH) w88 win 141.0 (CH), 142.8 (quaternary carbon), 144.9 (quaternary carbon), 177.7 (quaternary carbon);2-((7-bromo-10-ethyl-5-oxido-10H-phenothiazin-3-yl)methylene) hydrazine carbothioamide (5):FT-IR cm-1): 3067(N-H of NH2), 2930(CH3), 1684, 1603 (C=N), 1492 (C=N), 1464 (C-H, bending), 1196(C=S), 1070 (S=O), 517 (C-Br);1H-NMR (500 MHz, Acetone,d6):d(ppm): 1.59 (t,J= 7.25 Hz, 3H, CH3), 4.32 (q,J= 7.25 Hz, 2H, CH2), 7.45 (s, 1H, CH=N), 7.33 (d,J= 9.0 Hz,1H, Phenothiazin-H), 7.49 (d,J= 9.0 Hz,1H, Phenothiazine-H), 7.76 (dd,J=10.0, 2.5 Hz, 1H, Phenothiazine-H), 8.15–8.17 (m, 1H, Phenothiazine-H), 8.25 (d,J= 2.0 Hz,1H, Phenothiazine-H), 8.46 (s, 1H, NH2), 8.59 (d,J= 2.0 Hz,1H, Phenothiazine-H), 8.85 (s, 1H, NH2), 10.01 (s, 1H, NH);13C-NMR (125 MHz, acetone,d6), DEPT 90, 135 w88 win CPD:d(ppm): 12.61(CH3), 43.99 (CH2), 115.74 (quaternary carbon), 116.5 (CH), 118.1 (CH), 123.9 (quaternary carbon), 126.0 (quaternary carbon), 126.5 (CH), 128.0 (CH), 130.2 (quaternary carbon), 132.4 (CH), 138.8 (quaternary carbon), 144.1(quaternary carbon), 189 (CH=N) ,189.3 (C=S); HR-MS (ESI, MS-MS): theory value , [M+H]+ = 423.0103, experiment value, [M+H]+= 423.0118.Assessment of forming the complex of Hg(II), Pb(II) with ligand (5): the experiment to find the maximum absorption wavelength (λmax) of ligand: 0.0025 g of ligand was dissolved completely with pure ethanol solvent w88 win diluted up to 250 mL to obtain a ligand solution of 10 ppm concentration. The ligand solutions between 1 ppm w88 win 5 ppm were prepared w88 win samples of solutions with concentrations from 1 ppm to 5 ppm was scan in the wavelength range λ = 200-600 nm. As shown in figure.4, ligand (5) obtained maximum absorption, which corresponded the value of 203 nm in maximum absorption wavelength.
Effect of concentration on the forming complex:The complex PbL2was conducted at Amaxof 1.7876, λ = 217 nm, the volume ratio , mol ratio, w88 win : = 1: 2. The complex PbL2was conducted at Amaxof 1.7876, λ = 217 nm, the volume ratio , mol ratio, w88 win : = 3: 1. The complex HgL3was performed at , λ = 218 nm.
Discussions:COSY(H,H) was 2D spectrum as shown in Figure.1, H-15 w88 win H-16 indicated a correlation via 3 bonds, which matched the signal on the spectrum map at 1.59 ppm (t) with 4.32 ppm (q). The H-3 w88 win H-4 showed the correlation via 3 bonds, which were consistent with the signal on the spectrum at 8.15-8.17 ppm (m) with 7.5 ppm (d,J= 9 Hz), orto coupling. The correlation via 4 bonds between H-1 w88 win H-3 was matched with the signal on the spectrum at 8.59 ppm (d,J= 2 Hz), meta coupling with 8.15-8.17 ppm (m). The correlation via 3 bonds made the resonance between H-5 w88 win H-6, which was consistent with the signal on the spectrum at 7.33 ppm (d,J= 9,0 Hz) with 7.76 ppm (dd,J= 9.0, 2.5 Hz), orto coupling. The coupling correlation of 4 bonds was formed between H-6 w88 win H-8 that was consistent the resonance signals at 7.76 ppm (dd,J= 9.0, 2.5 Hz) with 8.25 ppm (d,J= 2.5 Hz), meta-coupling. The HMBC spectrum was 2D spectrum as showed in Figure.2. it presented the H-C correlations via many bonds. Based on1H,13C, DEPT, COSY, HMBC, w88 win HR-MS, the structure of compound (5) was determined in Figure.3.
CONCLUSIONS:
The compound (5), 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) hydrazine carbothioamide(PTZBS) was synthesized via 5 reactions w88 win checked physical chemistry. The two novel complexes between Lead (II) w88 win Mercury (II) w88 win ligand, 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) hydrazine carbothioamide were performed.
REFERENCES:
[1] S. P. Massie. (1954). The chemistry of phenothiazine, Chem. Rev., 54(5),797–833.
[2] M. Lu, Y. Zhu, K. Ma, L. Cao, K. Wang. (2012). Facile synthesis w88 win photo-physical properties of cyano-substituted styryl derivatives based on carbazole/phenothiazine. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., 95, 128-134.
[3] Y. Li. (2009). Energy level w88 win molecular structure engineering of conjugated donor-acceptor copolymers for photovoltaic applications. Macromolecules, 42(13), 4491-4499.
[4] Y. Hua. (2013). Significant improvement of dye-sensitized solar cell performance using simple phenothiazine-based dyes. Chem. Mater., 25(10), 2146-2153.
[5] X. Kong, A. P. Kulkarni, S. A. Jenekhe. (2003). Phenothiazine-Based Conjugated Polymers: Synthesis, Electrochemistry, w88 win Light-Emitting Properties. Macromolecules, 36(24), 8992-8999.
[6] R. Rajagopalan, T. Lin, A. S. Karwa, A. R. Poreddy, B. Asmelash,R. B. Dorshow. (2012). Studies of Tricyclic Diarylamines. Med. Chem. Lett., 3, 284-288.
[7] D. Addla, A. Jallapally, D. Gurram, P. Yogeeswari, D. Sriram, S. Kantevari. (2014). Rational design, synthesis w88 win antitubercular evaluation of novel 2-(trifluoromethyl)phenothiazine-[1,2,3]triazole hybrids. Bioorganic Med. Chem. Lett., 24(1), 233-236.
[8] M. A. Azuine. (2004). Cancer chemopreventive effect of phenothiazines w88 win related tri-heterocyclic analogues in the 12-O-tetradecanoylphorbol-13-acetate promoted Epstein-Barr virus early antigen activation w88 win the mouse skin two-stage carcinogenesis models. Pharmacol. Res., 49, (2), 161-169.
[9] C. M. Abuhaie. (2013). Synthesis w88 win anticancer activity of analogues of phenstatin, with a phenothiazine A-ring, as a new class of microtubule-targeting agents. Bioorganic Med. Chem. Lett., 23(1), 147-152.
[10] A. Bisi, M. Meli, S. Gobbi, A. Rampa, M. Tolomeo, L. Dusonchet, Multidrug resistance reverting activity w88 win antitumor profile of new phenothiazine derivatives, Bioorganic Med. Chem., Vol. 16, No. 13, 6474-6482, 2008.
[11] B. S. Garg, V. K. Jain. (1988). Analytical applications of thiosemicarbazones w88 win semicarbazones. Microchem. J., 38(2), 144-169.
[12] T. S. Lobana, R. Sharma, G. Bawa, S. Khanna. (2009). Bonding w88 win structure trends of thiosemicarbazone derivatives of metals-An overview. Coord. Chem. Rev., 253(7-8), 977-1055.
[13] J. R. Dilworth, R. Hueting. (2012). Metal complexes of thiosemicarbazones for imaging w88 win therapy. Inorganica Chim. Acta, 389, 3-15.
[14] J. Qi. (2018). Synthesis, antiproliferative activity w88 win mechanism of gallium(III)-thiosemicarbazone complexes as potential anti-breast cancer agents. Eur. J. Med. Chem., 154, 91-100.
[15] J. Deng. (2018). Designing anticancer copper (II) complexes by optimizing 2-pyridine-thiosemicarbazone ligands, Eur. J. Med. Chem., 158, 442-452.
[16] N. K. Singh, A. A. Kumbhar, Y. R. Pokharel, P. N. Yadav. (2020). Anticancer potency of copper(II) complexes of thiosemicarbazones. J. Inorg. Biochem., 210, 111134.
[17] L. V Kumar, S. Sunitha, G. Rathika Nath. (2020). Antioxidant, antidiabetic w88 win anticancer studies of nickel complex of Vanillin-4-Methyl-4-Phenyl-3-Thiosemicarbazone. Mater. Today, Proceeding.
[18] T. Bal-Demirci, Ş. Güveli, S. Yeşilyurt, N. Özdemir, w88 win B. Ülküseven. (2020). Thiosemicarbazone ligand, nickel(II) w88 win ruthenium(II) complexes based on vitamin B6 vitamer: The synthesis, different coordination behaviors w88 win antioxidant activities. Inorganica Chim. Acta, 502, 119335.
[19] J. Haribabu. (2021). N-substitution in isatin thiosemicarbazones decides nuclearity of Cu(II) complexes – Spectroscopic, molecular docking w88 win cytotoxic studies. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., 246, 118963.
[20] A. A. El-Asmy, O. A. El-Gammal, H. S. Saleh. (2008). Spectral, thermal, electrochemical w88 win analytical studies on Cd(II) w88 win Hg(II) thiosemicarbazone complexes. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., 71(1), 39-44.
[21] F. A. Beckford w88 win K. R. Webb. (2017). Copper complexes containing thiosemicarbazones derived from 6-nitropiperonal: Antimicrobial w88 win biophysical properties. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., 183, 158-171.
[22] S. Eğlence-Bakır. (2020). Palladium (II) complexes with thione w88 win thioalkylated thiosemicarbazones: Electrochemical, antimicrobial w88 win thermogravimetric investigations. Spectrochim. Acta - Part A Mol. Biomol. Spectrosc., 237.
[23] S. Kumar. (2017). Co(II), Ni(II), Cu(II) w88 win Zn(II) complexes of acenaphthoquinone 3-(4-benzylpiperidyl)thiosemicarbazone: Synthesis, structural, electrochemical w88 win antibacterial studies. Polyhedron, 134, 11-21.
[24] S. J. Sardroud, S. A. Hosseini-Yazdi, M. Mahdavi, M. Poupon, E. Skorepova. (2020). Synthesis, characterization w88 win in vitro evaluation of anticancer activity of a new water-soluble thiosemicarbazone ligand w88 win its complexes. Polyhedron, 175, 114218.
[25] S. Huang, H. Luo, Y. Liu, W. Su, Q. Xiao. (2020). Comparable investigation of binding interactions between three arene ruthenium (II) thiosemicarbazone complexes w88 win calf thymus DNA. Polyhedron, 192, 114864.
[26] A. M. Palve, P. V. Joshi, V. Puranik, S. S. Garje. (2013). Synthesis w88 win X-ray single crystal structure of a cadmium (II) acetophenone thiosemicarbazone complex w88 win its use as a single-source precursor for the preparation of CdS nanocrystallites w88 win thin films. Polyhedron, 61, 195–201.
[27] B. Amritha, O. Manaf, M. Nethaji, A. Sujith, M. R. Prathapachandra Kurup, S. Vasudevan. (2020). Mn(II) complex of a di-2-pyridyl ketone-N(4)-substituted thiosemicarbazone: Versatile biological properties w88 win naked-eye detection of Fe2+w88 win Ru3+ions’. Polyhedron, 178, 114333.
[28] A. Basu, G. Das. (2011). Zn(II) w88 win Hg(II) complexes of naphthalene based thiosemicarbazone: Structure w88 win spectroscopic studies. Inorganica Chim. Acta, 372(1), 394-399.
[29] T. A. Yousef, G. M. Abu El-Reash, R. M. El Morshedy. (2013). Structural, spectral analysis w88 win DNA studies of heterocyclic thiosemicarbazone ligand w88 win its Cr(III), Fe(III), Co(II) Hg(II), w88 win U(VI) complexes. J. Mol. Struct., 1045, 145-159.
[30] M. D. Raicopol. (2000). Electrodes modified with clickable thiosemicarbazone ligands for sensitive voltammetric detection of Hg (II) ions, Sensors Actuators. B Chem., 313(April), 128030.
[31] J. S. Casas, M. S. García-Tasende, J. Sordo. (2000). Main group metal complexes of semicarbazones w88 win thiosemicarbazones. A structural review. Coord. Chem. Rev., 209(1), 197-261.
[32] N. M. Quang, T. X. Mau, N. T. Ai Nhung, T. N. Minh An, P. Van Tat. (2019). Novel QSPR modeling of stability constants of metal-thiosemicarbazone complexes by hybrid multivariate technique: GA-MLR, GA-SVR w88 win GA-ANN. J. Mol. Struct., 1195, 95-109.
[33] T. N. M. An. (2019). Synthesis, Docking Study, Cytotoxicity, Antioxidant, w88 win Anti-microbial Activities of Novel 2,4-Disubstituted Thiazoles Based on Phenothiazine. Curr. Org. Synth., 17(2), 151-159.
Các phức mớicủa Chì (II), Thủy ngân (II) và ligand, 2-((7-Bromo-10-Ethyl-5-Oxido-10h-Phenothiazin-3-Yl)Methylene) Hydrazine carbothioamide: Tổng hợp và ứng dụng trong phân tích quangtrắc
K Lê Thị Thảo Uyên1
GS.TS.Lê Văn Tán1
PGS.TS. Trần Nguyễn Minh Ân 1
1 Đại học Công nghiệp Thành phố Hồ Chí Minh, Thành phố Hồ Chí Minh,
Việt Nam
TÓM TẮT:
Hai phức chất mới giữa ion Chì (II) và Thủy ngân (II) với phối tử, 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl) methylene) hydrazine carbothioamide (PTZBS), được tổng hợp từ nguyên liệu ban đầu, Phenothiazine, ngang qua ethyl hóa, hình thành liên kết C=O (phản ứng Vilsmeier - Haak- Arnol'd), brom hóa bởi NBS, phản ứng cộng nucleophile với thiosemicarbazone để tạo ra liên kết đôi, C=O tạo hợp chất thiosemicarbazone. Cuối cùng thực hiện phản ứng oxy hóa, tạo thành hợp chất thiosemicarbazone mới. Ligand, 2 - ((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl) methylene) được tạo phức với hai ion Pb (II) và Hg (II). Các cấu trúc của ligand đã được xác định bằng các phương pháp hóa lý hiện đại: IR,1H,13C, DEPT, NMR và kỹ thuật NMR 2 chiều: 2D, COSY và HMBC) và HR-MS.
Từ khóa:phức chất giữa ion Chì (II) và Thuỷ ngân (II), Phenothiazine.
[Tạp chí Công Thương - Các kết quả nghiên cứu khoa học và ứng dụng công nghệ, Số 2, tháng 1 năm 2021]