Journal of Atoms and Molecules An International Online Journal ISSN

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1 Research article Journal of Atoms and Molecules An International Online Journal ISS SYTESIS, ARATERIZATIO, ATIMIROBIAL ATIVITIES AD SPETRAL STUDIES OF SOME TRASITIO (II) OMPLEXES WIT SUBSTITUTED ALOE TIOSEMIARBAZOES Meena Shyam Kumar* 1, Jain Meenakshi 2 1 Department of hemistry, Govt. P.G. ollage, Dholpur, Rajasthan, Department of hemistry, University of Rajasthan, Jaipur, India Received on: Revised on: Accepted on: ABSTRAT: Zn, o, and u complexes were prepared by reacting metal chloride/acetate with halcone Thiosemicarbazone. The transition complexes were derived from the reaction between substituted chalcone Thiosemicarbazone with an aqueous solution of transition metal salt. The chalcone thiosemicarbazone ligands and their transition metal complexes have been screened for their IR, MR, analytical, and antifungal and antibacterial studies. All the transition-ligands 1:2 complexes have been isolated in the solid state, are stable in air, and characterized on the basis of their elemental and spectral data. These complexes were used as antifungal, antibacterial activity and important role in agriculture, pharmaceutical and industrial chemistry. KEY WORDS: Synthesis, Spectral studies, Transition metal complexes, chalcone thiosemicarbazone, Antibacterial activity. * orresponding author Meena Shyam Kumar, shyammeena_1984@yahoo.co.in ITRODUTIO: Schiff bases possess strong ability to form metal complexes 1 and they deserve a proper attention because of their biological properties 2 II II II. The Fe u and Zn complexes of Schiff bases are also biologically active 3 and they exhibit enhanced activities as compared to their parent ligands. The chemistry of chalcone thiosemicarbazone and their alied derivative has great interest due to theirdeverse pharmaceutical activities. These are used as antifungal 4 antibacterial 5 antituberculosis 6 antimicrobial 7 agents. Metal complexes play an essential role in agriculture, pharmaceutical and industrial chemistry. 6. The Schiff base and their metal chelate are effective anticancer, antitumor, ant All rights reserved

2 tuberculosis, antipyretic, agent as well as ant perfumes, polymers, lubricating agent 8-10 The Schiff s base and their metal chelates are effective anticancer, antitumor, anti tuberculosis, antipyretic as well as anti fertility agents. Schiff s bases possess industrial applications such as catalysts, dyes, fiber, perfumes an aesthetic, plant growth inhibitors cosmetics corrosion inhibitors, oxygen absorbents, polymers, lubricating agents, for removing metal impurities of oil and drying accelerators The metal complexes with Schiff s base derived from chalcone and thiosemicarbazone have been extensively studied and have exhibited medicinal properties 15. opper (II) complexes have been used in the treatment of many diseases including cancer 16. The role of semicarbazone of various transition metals has been investigated owing to their coordination capability and pharmaceutical activity Schiff s bases make them more effective in attaining high coordination structure. 20 MATERIALS AD METODS: The substituted chalcones thiosemicarbazone transition metal complexes were derived from the reaction on aqueous solution of metal salt. The substituted chalcones and thiosemicarbazone ligands were prepared by the reaction of substituted chalcones with thiosemicarbazide in the presence of hot ethanol. All the transition metal-ligands 1:2 complexes isolated in the solid state, were stable in air, and characterized on the basis of their elemental and spectral data. Thiosemicarbazone ligands behaved as bidentate ligands by coordinating through the Sulfur of the isocyanides group and nitrogen of the cyanide residue. The chalcones thiosemicarbazone ligands and their transition complexes were screened for their IR, MR, and antifungal and antibacterial studies. Synthesis of substituted chalcone (1a-d) 1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop-2-enone (chalcones) It was prepared by method of joshi et al by boiling the solution of o- chlorobenzaldehyde (1.40g, 10 mmol) and p- fluoroacetophenone (1.21 ml, 10 m mol) in ethanol (50ml) in a round bottomed flask and heated on a water bath for 5-10 minutes. Then 10% ao aqueous solution was added drop wise and stirred for 7-8 hours. After completion of the reaction, the mixture was acidified with ice cold hydrochloric acid and filtered to give crude product which was recrystallized with distilled ethanol. F O o o Fig. I (Z) l (Z) Fig. II l All rights reserved

3 Synthesis of substituted chalcone thiosemicarbazones complexes (2a-d) 1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop-2-ene-1-thiosemicarbazone 1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop- 2-ene-1-thiosemicarbazone was prepared by method of ompaigne and Archer (4- Fluorophenyl)-3-(-2-chlorophenyl) prop-2- enone (5.21g,20 mmol) was dissolved in ethanol (50ml) in a 250 ml round bottom flask and heated on a water bath for minutes. This hot solution was treated with hot ethanol solution (50ml) of thiosemicarbazide (1.82g, 20 m mol) and refluxed for 6-7 hrs on water bath. The change in colour from cream to yellow in the solution indicated the formation of 1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop-2-ene-1-thiosemicarbazone. On cooling the reaction mixture was obtained as yellow crystalline product which was filtered under water suction and further recrystallized from absolute ethanol and finally dried over fused cacl 2 in vacuum desiccators. l F Fig. III 2 S l O Fig. IV 2 Synthesis of substituted chalcone thiosemicarbazones metal complexes (3a-d) Bis[1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop-2-ene-1-thiosemicarbazone] cupper (II) 1-(4-Fluorophenyl)-3-(-2-chlorophenyl) prop- 2-ene-1-thiosemicarbazone (0.520g, 2mmol) was dissolved in ethanol (20ml) and heated on a water bath. This solution was mixed with an aqueous solution of metal salt u (OO 3 ) 2. 2 O (0.199g, 1mmol) in 2:1 molar ratio respectively. Then the whole mixture was refluxed on water bath for 2-3 hrs and then left over night to yield the crystalline dark brown coloured complex which was filtered out under suction and washed with water till filtrate became colourless. The product was finally washed with dilute ethanol and dried over fused calcium chloride in vacuum desiccators. All the compounds were prepared by using the same method. S All rights reserved

4 F l 2 (Z) S u (Z) Fig. V 2 S l Antibacterial and antifungal activities: Representative chalcone thiosemicarbazone ligands and their metal complexes were screened for their antibacterial activity and antifungal activity at 60, 80, and 100 ppm concentrations. RESULTS AD DISUSSIO: Substituted chalcone: In the IR spectra of substituted chalcone a sharp absorption band from cm_1 was observed due to acetophenone >=O and at 1620 cm-1 due to >=< stretching vibration. In the 1 MR spectra of substituted acetophenones a sharp singlet was found at δ7.90 ppm and δ 2.4 ppm whereas aromatic proton showed a multiplet in the range between δ 6.52and8.2 ppm. Formation of substituted chalcone thiosemicarbazones was confirmed by the disappearance of F intense absorption band at 1670 cm -1 due to carbonyl group (>=O) and appearance of new absorption bands at , cm -1 assigned to 2, >=S stretching vibrations. Similarly in 1 nmr spectra broad signal δ ppm appeared due to 2 protons and sharp singlet from δ7.0 ppm due to proton. Metal complexes of substituted chalcone thiosemicarbazones: In IR spectra of metal complexes of substituted chalcone-thiosemicarbazones the presence of absorption band at 3350cm-1 due to 2 (symmetric) and at 3400cm-1due to- 2 (asymmetric) modes remained almost unaltered. Sharp absorption band from cm-1 which was due to - in ligands disappeared in complexes indicating possible deprotonation on the β-nitrogen after complex formation with metal ion.appearance of new absorption band in the complexes at due to (M-) confirmed the metal nitrogen bond in the complexes. The 1MR spectra showed a sharp signal at δ2.5 ppm due to 2 protons and multiplet signals observed at δ ppm were due to aromatic protons. Discussion: All compounds have been characterized on the basis of spectral (IR, MR) studies and elemental analysis. IR spectra ( cm- 1) were recorded using a KBr. 1 MR spectra were recorded on Brucker spectrometer (300 Mz) at Department Of hemistry, University of Rajasthan, and Jaipur, using Dl 3 /DMSO as solvent. TMS was taken as internal standard.,, and S analysis of these compounds was carried out with the help of oleman and analyzer. Melting points were determined in open glass capillaries. The purity of compounds was checked by TL using silica gel-g as adsorbent and visualization was accomplished All rights reserved

5 by UV light or iodine adsorption. All compounds were crystalline dark coloured solids, having fairly high melting points and were sparingly soluble in common organic solvents and were insoluble in water. AKOWLEDGEMET: Authors are thankful to ead Department of hemistry, University of Rajasthan, Jaipur. entral Drug Research Institute (DRI), Lucknow, Seminal Applied Science Pvt. Ltd Jaipur for providing research facilities REFEREES: 1. Davies M.B. oord.hem. Rev., 1997, 164, 27, Smith D.R., oord. hem. Rev. 1998,172, 457, Yamda S., oord. hem. Rev., 1999,190, Mishra P., Gupta P.. and Shakya A.K., J.Indian hem. Soc., 1991, 68,618; W.Zieshen, L.Zhiping and Y.Zhenhaun, Transition Met. hem., 1993, 18, Zhong W., Zieshen W., Zhenhaun V. and Guinghuq., Transition Met. hem., 1994, 19, Jeragh B.J.A. and El-Dissouky A., J.oord. hem.2005, 58: 12/15, p Siddiqui. and Singh O. Indian J. Pharma. Sci.2005, 65:4, p ollins F.M., Klayman D.L. and Morrison.E. Am.Rev.Respir. Dis.1982, 125:1, p alli M.B. and Qureshi Z.S.S. Metal- Org. ano-metal hem.1755, 34: Domagk G. aturwissenschaften, 1946, 33, p Lovejoy D.B. and Richardson D.R., Blood 2002, 100:2, p Ergenc., Ilhan E. and Otuk G. Pharmazie, 1992, 47:1, p hohan Z.., i (II), u (II) and Zn (II) metal chelates with thiazole Schiff bases synthesis, characterization and bactericidal properties: Met.-Based Drugs.1999., 6, Kaul B.L., metal complex dyes and their use for dyeing plastic composition hem.abstr.1986, George R. S., Joseph R. and George K. E., Study of poly-schiff bases as a protective agent in natural rubber: Int. J. Polym. Mater.1993, 23, ohan Z.. and Kausar S., Synthesis, characterization and biological effect of anions on o (II) and i (II) chelates of tridentate Schiff base: J. hem. Soc. Pak.2001, 23, Marisa B.F., Franco B., laudio., Stephanie D., Irene M.-B., Giorgio P., Elisabetta P., Silvana P., and Pieralberto T., opper (II) and obalt (III) Pyridoxal Thiosemicarbazone omplexes with itroprusside as ounterion: J. Med. hem.2005, 48, Orvig. and Abrahams M. J., Biochemical and inorganic copper chemistry: hem. Rev.1999, 99, adkarny V. V., Rao R. S., and Fernandes P. S., Synthesis of a few acid hydrazides: sulfonyl hydrazides and their derivatives from 2-phenyl-1, 2, 3- triazole-4-carboxylic acid and [(4- nitrophenyl) thio] acetic acid as antibacterial: J. Indian hem. Soc.1976, 53, Garg A., Tendon J. P., Magnetic and spectroscopic studies of chromium (III) complexes of semicarbazones and thiosemicarbazones: Synth. React. Inorg. Met.-Org. hem.1990, 20, (1990). 19. Oza. k., Jain M., Jain., Verma D.., Synthesis characterization, Antimicrobial, Activities, and structural studies of lanthanide (III) complexes with 1-(4-chloroo phenyl)-3-(4- fluoro/hydroxyl phenyal) prop-2-en-1- All rights reserved

6 thiosemicarbazone: Phosphorus, Sulfur Silicon Relat. Elem.2010, 185, Mishra.., Mohapatra B. B. and Guru S., Mixed ligand complexes of bis (ethylmalonato) cobalt (II), copper (II) and zinc (II) with nitrogen donor ligands: J. Indian hem. Soc.1980, 57, (1980). 21. Joshi K.. and Jauhar A.K., Indian Journal hemistry, 1962, 39, Borkhade K.T. and Marathey M.G., Indian Journal hemistry, 1970, 8, Figgis B.., Introduction of ligands fields Wiley Eastern, ew Delhi, ompaigne E.E. and Archer W.L., J. Am. hem. Soc., 1952,74,5801. Tables and Figures: Table I Analytical and Physical data of substituted chalcone thiosemicarbazones Ar-=- (--S- 2 ) Ar omp. Ar Ar Mol. formula colour Mol. Wt. m.p. Yield % Elemental analysis % (calcd.) S 2a 4-l O l 3 OS Yellow , 4.25, 12.66, 16.59, 4.82, 1 2b 2-l F lf 3 S ream , 3.91, 12.59, c O OS Brown ,5.08,14.13, d F F 3 S ream ,4.71,14.04, e S Brown ,5.37,14.93,11.10 Table II Analytical and Physical data of substituted chalconethiosemicarbazones u (II) complexes [Ar-=- (--S- 2 ) Ar ] 2 u (II) omp. o. Ar Ar Mol. formula colour Mol. Wt. m.p. Yield % Elemental analysis % (calcd.) S 3a 4-l O l 2 6 O 2 S 2 u Yellow ,3.95,11.35,8.66 3b 2-l F l 2 F 2 6 S 2 u ream ,3.66,11.29,8.62 3c O O 2 S 2 u Brown ,4.56,12.52,9.55 3d F F 2 6 S 2 u ream ,4.33,12.44,9.50 3e S 2 u Brown ,4.89,13.15,10.03 All rights reserved

7 Table III haracteristic 1 MR spectral data of substituted chalconethiosemicarbazones and their metal complexes omp. Mol. formula 1 MR spectral data(δ,ppm) o. Ar- (m) -(s,1) 2 - =- -O 2a l 3 OS b lf 3 S c OS d F 3 S e S a l 2 6 O 2 S 2 u b l 2 F 2 6 S 2 u c O 2 S 2 u d F 2 6 S 2 u e S 2 u Table IV haracteristic IR spectral data of substituted chalconethiosemicarbazones and their metal complexes IR (KBr : ν max cm -1 ) omp. o. > 2 > Ar- >= >=< M- >=S -S 2a b c d e a b c d e Figures: Fig: VI Antibacterial specie-streptomyces Fig : VII Antibacterial species-bacillus cereus All rights reserved

8 Fig : VIII Antibacterialspeciees-E.coli Fig : IX Antibacterial spesies-streptococus aureus Fig: X Antifungal species-trichoderma Reesei Fig: XI Antifungal species-a. iger Fig: XII Antifungal Speciees-Penicillum Fig : XIII Antifungal Speciees-Fusarium ow to cite this article: Meena SK., Meenakshi J., Synthesis, haracterization, Antimicrobial Activities, and Spectral Studies of some Transition (II) omplexes with substituted chalconethiosemicarbazones J. Atoms and Molecules, 4(3), 2014: All rights reserved