Two novel Lead (II) nhà cái w88 Mercury (II) complexes of 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) hydrazine carbothioamide: synthesis, structure nhà cái w88 optical analysis

ABSTRACT:

The two novelcomplexes between Lead (II) nhà cái w88 Mercury (II)ion nhà cái w88 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) nhà cái w88 Hg (II) ion, respectively. The structure of ligand was checked IR,¹H,¹³C, DEPT- NMR, 2D-NMR (COSY nhà cái w88 HMBC), nhà cái w88 HR-MS.

Keywords:complexes of lead (II) nhà cái w88 mercury (II), phenothiazine.

1. Introduction

Chemistry of phenothiazine has been  fully reported in review article^[1]nhà cái w88 new derivatives of phenothiazine, nhà cái w88 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], nhà cái w88 phototherapeutic agents^[6]. Some significant bioactivates have revealed antitubercular^[7]nhà cái w88 cancer chemo preventive effect^[8-10]. The important phenothiazine derivatives have applied in biochemistry nhà cái w88 coordinate chemistry, which were thiosemicarbazone derivatives. These thiosemicarbazone compounds have made the complexes with metal ions^[11]. The bonding nhà cái w88 structure trends of thiosemicarbazone derivatives of metals have presented in many articles^[12]. Some analytical applications of the thiosemicarbazone nhà cái w88 semi carbazones have indicated in previous article^[11]. Few significant applications of metal complexes of thiosemicarbazones in imaging nhà cái w88 therapy^[13], anticancer^[14-16], antibacterial of  Mn(II), Co(II), Zn(II), Fe(III) nhà cái w88 U (VI) complexes, nhà cái w88 2-acetylpyridine 4N-(2-pyridyl) thiosemicarbazone (HAPT), nhà cái w88 antitumor of thiosemicarbazone- functionalized organ ruthenium (II)-arene,  antioxidant, nhà cái w88 antidiabetic of nickel complex of vanillin-4-Methyl-4-phenyl-3-thiosemicarbazone have mentioned,^[17-18]. The complexes of thiosemicarbazone nhà cái w88 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) nhà cái w88 Pt (II) have studied strategy in many articles in synthesis, structure, nhà cái w88 application in biochemistry, analytical chemistry, nhà cái w88 optical applications^[19-27]. The complexes of Hg (II) nhà cái w88 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], nhà cái w88 structural review^[31]. The complex of Pb(II) nhà cái w88 thiosemicarbazone derivatives have been rarely research article^{[32], [31]}. As interesting about coordinate chemistry, analytical chemistry, the pollutions of heavy metals in wastewater, printing, nhà cái w88 paper making, we continue to make synthesis of novel water-soluble ligand (thiosemicarbazone derivative) nhà cái w88 conduct the complexes of Hg (II) nhà cái w88 Pb(II) ions with ligand, respectively.

2. Materials nhà cái w88 methods

The chemical reagents nhà cái w88 solvents for reactions were obtained from Sigma- Aldrich, the solvents for chromatography column, ethyl acetate, n-hexane, dichloromethane, chloroform, nhà cái w88 others were bought from Viet Nam suppliers. The TLC was received from Merk company. The synthesis compounds via ethylation (1), bromination (2), carbonylation (3), nhà cái w88 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⁺) nhà cái w88 ligand (5) nhà cái w88 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 nhà cái w88 5 g NaH (0.08 mol), then slowly added 11.7 mL of  C₂H₅Br (0,15 mol). The reaction mixer was heated nhà cái w88 stirred for 8 hours. When the reaction was finished,  it was added more water, stirred, nhà cái w88 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 nhà cái w88 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 nhà cái w88 made the mixture in ice bath. 7,5 mL of CHCl₃solvent nhà cái w88 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 nhà cái w88 started heating the system at about 70-75^oC. After completing of the reaction (checking TLC) was 22 hours, it was transferred the entire mixture to the separating funnel, added 10% NaOH solution, nhà cái w88 shacked well to separate the two phases, which the water phase was above layer, nhà cái w88 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 nhà cái w88 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, nhà cái w88 made exactly 9 mL of CHCl₃into it. The reaction mixer was heated nhà cái w88 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, nhà cái w88 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 nhà cái w88 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) nhà cái w88 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, nhà cái w88 added 0.8 mL of AcOH (ice). The mixer of reaction was started to heat to 80⁰C nhà cái w88 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 55-60^oC. The vacuum filtration nhà cái w88 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, nhà cái w88 taken exactly 10 mL of CHCl₃into it. When the solid was completely dissolved in CHCl₃solvent, it added 1.1 mL AcOH (ice) nhà cái w88 0.2 mL H₂O₂. The reaction was increased temperature to 50⁰C nhà cái w88 stirred. When the temperature of reaction was desired, reaction time was started counting, nhà cái w88 added 0.2 mL H₂O₂every hour. The entire mixture was transferred to the separating funnel, added 10% of a NaOH solution, nhà cái w88 shake well to separate into the two phases. The organic layer below was kept nhà cái w88 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 nhà cái w88 obtained 2.53 gram of yellow solid. The yield was 78.82%.

Results nhà cái w88 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 nhà cái w88 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 nhà cái w88 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 nhà cái w88 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 nhà cái w88 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) nhà cái w88 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 nhà cái w88 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 nhà cái w88 diluted up to 250 mL to obtain a ligand solution of 10 ppm concentration.  The ligand solutions between 1 ppm nhà cái w88 5 ppm were prepared nhà cái w88 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 A_maxof 1.7876, λ = 217 nm, the volume ratio , mol ratio, nhà cái w88   : = 1: 2. The complex PbL₂was conducted at A_maxof 1.7876, λ = 217 nm, the volume ratio , mol ratio, nhà cái w88   : = 3: 1. The complex HgL₃was performed at , λ = 218 nm.

Discussions:COSY(H,H) was 2D spectrum as shown in Figure.1, H-15 nhà cái w88 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 nhà cái w88 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 nhà cái w88 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 nhà cái w88 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 nhà cái w88 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, nhà cái w88 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 nhà cái w88 checked physical chemistry. The two novel complexes between Lead (II) nhà cái w88 Mercury (II) nhà cái w88 ligand, 2-((7-bromo-10-ethyl-5-oxido-10h-phenothiazin-3-yl)methylene) hydrazine carbothioamide were performed.

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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]