SYNTHESIS CHARACTERIZATION AND ANTIMICROBIAL STUDIES ON NITROGEN AND OXYGEN-BASED BI DENTATE MANNICH BASE LIGAND OF TRANSITION METAL COMPLEXES

SYNTHESIS CHARACTERIZATION AND ANTIMICROBIAL STUDIES ON NITROGEN AND OXYGEN-BASED BI DENTATE MANNICH BASE LIGAND OF TRANSITION METAL COMPLEXES

A. M. Anusuya ^* and B. S. Krishna

Department of Chemistry, Sapthagiri College of Engineering Affiliated to Visveswaraya Technological University, Bangalore - 560057, Karnataka, India.

ABSTRACT: 1-{3-[2, 3dihydro-1H-imidazol-1-yl (8-hydroxyquinolin-7-yl) methyl] phenyl-l} ethanon, nitrogen and oxygen-based bi-dentate mannich base heterocyclic ligand synthesized and complexed with biologically significant transition metals like copper, cobalt, nickel, and zinc by the melt condensation three-component one-pot synthesis. All the synthesized potential compounds characterized by spectral methods by using NMR, IR, UV-visible mass, and elemental analysis. The antimicrobial analysis investigated for all the synthesized compounds using some bacterial and fungal cultures used by the disc diffusion method, and the activity proved in proportion with the standard drugs used as a reference. The main significant part of the work involved in mannich base reaction of one-pot synthesis three-component reactions prove better synthetic procedure and improved product yield. The ligand and the complexes of transition metals proved better microbial activities of biologically important and to prove the efficiency of the present work. Continuation of research work is to investigate significant heterocyclic molecules and transition metal complexes to prove potential microbial activities play an important role in pharmaceutical and biological applications.

Heterocyclic molecules melt condensation, Mannich base, Transition metals, and antimicrobial activities

INTRODUCTION: The innovative drug discovery and efficiency of biological activity is the interest of the pharmacological era, so there is great importance for the synthesis of structurally and quantitatively significant drug molecules. Transition metals exhibit variable oxidation state, and such properties possess therapeutic value in the field of medicinal chemistry ^1-2. The coordination behavior of the structurally derived compounds mainly depends on the multi chelating and complexation behavior such a potential biological molecule prepared by the process of mannich base reaction, which gives significant molecules of biological interest ^3-4.

The hydroxy Quinoline which has potential chelating properties complexes with many of metal ions on protonation of hydroxyl group and the Quinoline nitrogen coordinate to form bi liganding sites such two molecules of 8-hydroxy Quinoline molecule to form tetradentate complexes with transition metal ions to respond to bacterial and fungal action to be used in the treatment of bacterial and fungal infectious deceases is the important part of this research work studied with the use of various bacterial and fungal culture uses with the disc diffusion method ^5-8. The benzene ring fused with 4, 5 positions of imidazole is called as benzimidazole. Benzimidazole is sparingly soluble in water but more soluble in organic solvents, the basic nature of pyridine nitrogen makes to accept hydrogen ⁹. Many substituted benzimidazole structures are the source of natural compounds like vitamin B12, and such compounds are of biologically active compounds against bacteria, fungi and viruses.

Benzimidazole has amphoteric behavior by loss or gain of proton ¹⁰. Due to the diverse range of biological, analytical, and industrial application, mannich base coordination chemistry plays a very important role for Pharmacists and industrialists ¹¹. Nitrogen-containing heterocyclic compounds are the important class of chemotherapeutic and biologically active compounds for various bacterial and fungal microorganisms ^12-13.

EXPERIMENTAL:

Materials and Methods: All the chemicals and solvents used were AR grade. The micro elemental analyses were performed using a caroler 1108 CHN analyzer. Metals were estimated by conventional wet chemical analysis. FT-IR spectral measurements were made with a Bruker FTIR spectrometer as KBr pellets. Mass spectra were recorded using Maldi Mass spectrometer IISER Pune. 1H NMR-600MHZ Using DMSO d6 as a solvent.

General Procedure:

Synthesis of ligand: 1-{3-[2, 3dihydro-1H-imidazol-1-yl (8-hydroxyquinolin-7-yl) methyl] phenyl-l} ethanone: Equimolar amount of benzaldehyde (1.061 g), imidazole (0.6807 g) and 8-hydroxyquinoline (1.45g) weighed and subjected for melt condensation at the different duration of 12 h, 15 h, 22 h and 24 h the product formed were confirmed by using thin-layer chromatography and finally the product recrystallized using ethanol repeatedly and washed with acetone. The synthesized mannich base and transition metal complexes analyzed by physical and spectral methods like NMR, UV-Visible, mass spectra, and elemental analysis ^14-19.

SCHEME-1: 1-{3-[2,3-DIHYDRO-1H-IMIDAZOL-1-YL(8-HYDROXYQUINOLIN-7-YL)METHYL]PHENYL}ETHANONE

Preparation of Metal Complexes of Ligand: To the stirred solution of prepared mannich base ligand equivalent amount of 0.5 g of copper, cobalt, nickel, and zinc acetate added dropwise and allowed to mixed at the room temperature for 1 h followed by refluxing over a period of 5 h. The precipitate formation observed and confirmed by thin-layer chromatography and repeatedly washed with acetone and water and dried, the expected yield calculated as 80-90% ^20-23.

SCHEME 2: SYNTHESIS OF COPPER, COBALT, NICKEL AND ZINC COMPLEXES OF THE LIGAND

RESULTS AND DISCUSSION:

Spectral Characterisation of Ligand:

1-{3-[2, 3dihydro-1H-imidazol-1-yl (8-hydroxy-quinolin-7-yl) methyl] phenyl} ethanone: IRKBr, 3347 cm^-1 (C=N), 825 cm^-1 (NH), 783 cm^-1 (C-N). NMR (600 MHz, DMSO-d₆ppm): 9.58 (s, OH), 8.16 (N=C), 6.26 (aromatic CH), 7.18-7.29 (aromatic Hs). Mass: m/z, 345.15 (100%), 346.15 (23.0%), 347.15 (3.1%), 346.14 (1.1%). UV-Visible: 330 nmn-ℿ*, m/z: 345.15 (100%), 346.15 (23.0%), 347.15 (3.1%), 346.14 (1.1%).

Spectral Characterisation of Complexes of Copper, Cobalt Nickel and Zinc Complexes of Ligand: ^{24, 25}

Cu-L Complex: 1705.18 cm^-1 (C=O), 1570.54 cm^-1 (aromatic CH), 1498 cm^-1 (C=N), 1446.67 cm^-1 (C=C), 711.12 cm^-1 (M-N), 824.08 cm^-1 (M-O). H-NMR, 500 MHZ DMSO(d6): 10.01 (s, Aromatic CH or aldehyde group), 9.58 (Phenolic OH), 8.16 (S, NH imidazole), 6.26 (s, carbonyl proton), 8.12, 8.06, 8.01 (aromatic H), 5.08-5.20 (aliphatic proton). UV-Visible; 330 nm ℿ-ℿ*. m/z, 753.23 (100.0%), 754.23 (46.0%), 755.22 (44.6%), 756.23 (21.1%), 755.23 (12.2%), 757.23 (5.0%) 754.22 (2.2%) 756.24 (1.5%).

Co-LComplex: IR KBr cm^-1, 2888.34 cm^-1 (aromatic NH), 1610.11 cm^-1 (aromatic C=O), 785 (aromatic C=C) 1366.72 cm^-1 (M-O), 787 cm^-1 (M-N). UV-visible- 313 nm ℿ-ℿ*. m/z, 749.23 (100.0%), 750.23 (48.2%), 751.24 (10.3%), 752.24 (1.9%), 751.23 (1.8%).

FIG. 1: IR SPECTRA OF LIGAND

FIG. 2: IR SPECTRA OF Cu-L COMPLEX

FIG. 3: IR SPECTRA OF Co-L COMPLEX

FIG. 4: IR SPECTRA OF Ni-L COMPLEX

FIG. 5: IR SPECTRA OF Zn-L COMPLEX

Ni-L Complex: IR KBr cm^-1 2884.54 cm^-1 (aromatic NH), 1610.94 cm^-1 (carbonyl C=O), 1514.75 cm^-1 (C=N), 1451.6 cm^-1 (C=C), 1364.52 cm^-1 (C-N), 786.57 cm^-1 (M-N), 1159.20 (M-O). UV-visible-330 nm ℿ-ℿ*. Mass m/z: 748.23 (100.0%), 749.23 (47.6%), 750.23 (39.5%), 751.23 (19.7%), 750.24 (11.2%), 752.23 (5.4%), 752.22 (5.4%), 752.22 (2.9%), 751.24 (1.9%), 764.22 (1.4%).

Zn-L Complex: IR KBr disc cm^-1, 2886.43 cm^-1 (aromatic NH), 1605.36 (carbonyl C=O), 1556.42 cm^-1 (C=N), 145.12 cm^-1 (C-N), 746.54 cm^-1 (M-N), 1146.24 cm^-1 (M-O). UV-visible-313 nm n-ℿ* Mass, m/z: 754.22 (100%), 756.22 (58.4%), 755.23 (46.0%), 758.22 (39.3%), 757.22 (35.8%), 759.22 (18.5%), 756.23 (11.2%), 758.23 (10.3%), 760.23 (4.3%), 757.23 (2.4%), 759.23 (2.3%), 7.2 (2%), 760.22 (2.0%).

FIG. 8: MASS SPECTRA OF LIGAND

FIG. 9: H-NMR SPECTRA OF LIGAND

Physico-chemico Characterisation of Ligands and Complexes:

TABLE 1: ELEMENTAL ANALYSIS

Antimicrobial Studies of Ligand and Complexes: Escherichia coli and Staphylococcus aureus bacterial cultures were used for antimicrobial studies followed by disc diffusion method for which molten agar culture media prepared and incubated at 45 °C then the agar was poured into Petridis allowed to solidifies in which 5 diameter holes were punched and each of the holes filled with 50 & 100 mg/ml of teas solution with respect to standard antibacterial drug ciprofloxacin. All the petridishes were autoclaved and subjected for antifungal confirmation followed by the same disc diffusion procedure by using Aspergillus niger and Candida albicans with reference of the standard amphotericin-B antifungal drug for which potato-dextrose agar culture media prepared at a temperature of 37 °C over a period of 48 h then all the observed bacterial and fungal inhibition activity measured and tabulated in Table 2 ^26-28.

TABLE 2: ANTIMICROBIAL STUDIES

CONCLUSION: Biologically potential mannich base ligand prepared by Multicomponent one-pot synthesis followed by melt condensation of benzaldehyde, imidazole, and 8-hydroxyquinoline with the objective of antimicrobial biological application it's observed and tabulated that synthesized ligand and its transition metal complexes exhibited inhibition zone of bacterial and fungal culture. In our earlier work, we studied with the multicomponent of substituted benzaldehyde, benzimidazole, and 8-hydroxy-quinoline by which antimicrobial activity was not exhibited.

ACKNOWLEDGEMENT: We are thankful IISER Hyderabad for providing spectral data for the compounds, the pure microbial culture provided by the Sapthagiri institute of medical science, and research Bangalore.

CONFLICTS OF INTEREST: The author has no conflict of interest regarding the publication of this article.

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    How to cite this article:

    Anusuya AM and Krishna BS: Synthesis characterization and antimicrobial studies on nitrogen and oxygen-based bi dentate mannich base ligand of transition metal complexes. Int J Pharm Sci & Res 2020; 11(11): 5753-59. doi: 10.13040/IJPSR.0975-8232.11(11).5753-59

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