719-721Mixed ligand schiff base complexes of Cu(II) and Ni(II) derived from 7-formyl-8-hydroxyquinoline and 2-hydroxy-4-metho benzophenone, 2-hydroxy-4-methoxyacetophenone, 2-hydroxy-1-acetophenone or l-hydroxy-2-acetophenone and ethylenediamine have been synthesised an their spectral, magnetic and anti-fungal studies carried out

Jejurkar, C R

Patel, V K

Vasanwala, (Mis) AM

English

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Indian Journal of Che istryVol. 28A, August 198 ,pp. 719-721Synthesis of . ed schiff base complexes ofCu(II) and i(II) and their spectral,magnetic and antifungal studiesV K Patel, (Mis) AM VasanwaIa & C R Jejurkar*Applied ChemistryEngineering,epartment, FacuIty of Technology andS University, Baroda 390 001Received 19May 19 8; revised 29 August 1988; accepted 17October 1988Mixed ligand sc iff base complexes of Cu(U) andNi(U) derived fro 7-formyl-8-hydroxyquinoline and2-hydroxy-4-metho benzophenone, 2-hydroxy-4-methoxyacetophe one, 2-hydroxy-l-acetophenone orl-hydroxy-Z-acetop enone and ethylenediamine havebeen synthesised an their spectral, magnetic and anti-fungalstudies carrie out.Some binary and mixed ligand schiff base com-plexes of hydroxy ketones and hydroxy aldehydeshave been report by Bhattacharya and cowork-ers I - 4. The schi base complexes are known toshow antifungal ac ivity" -7, which is increased by thepresence of hydro y group in the ligand. So, it wasthought worthwhi e to synthesise complexes ofschiff bases with h droxy substitutents on the phe-nyl and heterocy he rings. We report here newmixed ligand schi base complexes derived from7-formyl-8-hydrox quinoline and 2-hydroxy-4-methoxybenzop enone, 2-hydroxy-4-methoxy-acetophenone, 2-h droxy-Lacetophenone or I-hy-droxy-2-acetophe one and ethylendiamine. Workon complexes of -formyl-8-hydroxyquinoline orits mixed schiff b e has not been reported in theliterature.As schiff base complexes are known to havefungicidal activitie , such isolated complexes havebeen tested agains Alternaria triticina and Puccinarecondita as test 0 ganisms, which are found to af-fect the growth f potatoes, maize and wheatcrops.All the chemi als were AR grade reagents.7-Formyl-8-hydro quinoline was prepared by themodified form of e rlier reported method".ExperimentalPreparation of l-fo myl-s-hydraxyquinolineA solution of 8 hydroxyquinoline (8g) in 20mlof chloroform was mixed with a solution of sodi-urn hydroxide (16.5g) in 30 ml water and 60ml ofethanol were added. The contents were refluxed at100°C for 12hr. Then the solution was acidified(pH 6.5-6.8) with dilute HCl when a brick-red sol-id was precipitated. On TLC analysis it was foundto be a mixture of 5-formyl-8-hydroxyquiqoline,7-formyl-8-hydroxyquinoline and unreacted 8-hy-droxyquinoline. The unreacted 8-hydroxyqui'nolinewas removed by washing the brick-red solid withether and then 7-formyl-8-hydroxyquinoline wasextracted by chloroform. The residue left was5-formyl-8-hydroxyquinoline which was discarded.7-Formyl-8-hydroxyquinoline was recovered fromchloroform by evaporation of chloroform. Theyield was found to be 3.0g. The substance wascrystallized repeatedly from chloroform (m.p.263°C, lit. 264°C).Preparation of ligands (schiff bases)Schiff base ligands (I) were prepared by usingthe method reported by Dharkaray and Saxena').Preparation of complexesA solution of metal acetate in 95% ethanol(20 mmol) was mixed with the schiff base ligand in95% ethanol (20 mmol) in 1:1 (M:L) ratio andcontents were refluxed in 150 ml ethanol on a wa-ter-bath for 2-3hr. The refluxed solution was thenpoured into ice cold water when a coloured solidseparated out which was isolated by filtration andwashed with ether, recrystallised from chloroformand dried in vacuo at room temperature. The719Complexes ftdt(8.M.)INDIAN J CHEM, SEe. A, AUGUST 1989complexes were analysed for metal contents usingcomplexometric titration with EDTA. Carbon, hy-drogen and nitrogen were determined by micro-an-alysis (Table 1) at the Chemistry Department, Fa-culty of Science, M.S. University of Baroda. Purityof the complexes was checked by TLC technique,using silica gel G (Si-Chem) with chloro-form + ether (5:3) mixture as adsorbant and ultra-violet light as visualisation agent.The IR spectral data were recorded in KEr ona Perkin-Elmer 427 grating spectrophotometerand electronic spectra in chlorofrom on a Beck-man spectrophotometer. The magnetic measure-ments were carried out by Gouy's method. Thefungicidal activity was studied by the Agar platetechnique''"!' using Alternaria truicinia found inpotatoes and Puccina recondita found in wheatand maize as test organisms (Table 2).Results and DiscussionThe analytical data (Table 1) show that thecomposition of the complexes is ML (H20hwhere M = Cu(II) or Ni(ll) and L= schiff bases.The chloroform solutions of the complexesshowed very poor molar conductivity(5.8-8.2 ohm -lcm2mol-l) indicating the com-plexes to be neutral. The electronic spectra ofCutll) complexes showed a broad absorption max-imum at 17000 em - 1 corresponding to 2Big ...• 2A1gtransition, characteristic of distorted octahedralgeometry".The electronic spectra of Ni(II) complexes inchloroform showed three bands at 8500, 14500and 25500 cm-I which are assigned to3A2g...• 3 T2!\vJ, 3A2g...• 3 T1,/( v2) and 3A2g...• P( v3)transitions respectively, indicating a pseudo-oc-tahedral environment around the Ni(II) ions!'.The structures of the complexes (II) are sup-ported by magnetic measurements. The magneticmoment values at 300K for Cuill) complexes werefound to be in the range 1.82-1.92 B.M. and forNirll) complexes in the range 3.20-3.98 B.M.corresponding to the octahedral geometry of themolecules 14 15. The slightly higher values for Ni(U)complexes than the spin-only value may be due toorbital contribution. The IR spectra of the freeschiff base ligands exhibited two bands at - 1600and - 1690 em - 1 due to vC = Nand vC = C fre-quencies respectively", These bands show shifts tolower wavenumbers in the IR spectra of the metalcomplexes indicating the involvement of nitrogenof azomethine group in the metal complex forma-tion 171 K. The coordinated nature of water moleculewas confirmed by a broad band in the region3300- 3400 ern - 1 due to stretching mode and a720Table l=-Analyrical and structural data of mixed schiff basecomplexesFound (C Ie)%,Metal N C H(CuC2fiNP3H2t'2HP) 11.60 8.16 0.21 4.11(12.15) (8.03) ( 9.11) (4.01)(CuC2,N303H'~'2H20) 15.11 9.08 4.01 5.21(14.09) (9.32) ( 5.93) (5.10)(CuC2oNP2H,7'2H20) 16.02 11.01 8.50 4.98I (15.73) (10.48) ( 9.47) (5.20)(CuC2oN,02HI7'2H20) 16.52 11.08 9.03 5.72(15.73) (10.48) ( 9.47) (5.20)(NiCu,N303H2,'2H20) 11.52 8.20 1.02 4.90(11.33) rs.u: ( 0.26) (4.82)(Ni.C2'N,01H'~'2H201) 13.01 9.10 5.80 5.13(12.88) (9.22) ( 5.24) (5.04)(NIC20NP3HI7'2H20) 14.02 9.82 9.20 5.51(14.36) (10.27) ( 8.73) (5.13)(NiC20N,03H'7'2HP) 13.85 10.35 57.8 5.40(14.36) (10.27) ( 8.73) (5.13)1.851.821.921.853.903.283.203.80OQ:.'-':~jCH2)~ ~ HS, \ C=NHON=~N -: \;/ \I 0----t-OH20O<~JCH2~22 I C = N Hfl N =~'.J ~ ",./o--r--OH200<':::::H {CH2)2 H33 I ~=N/H O'N=--, h \+2/O-M_OtH;~ICH2)2-N=(WHERE M = Cu (II),(II)band at - 800 cm - 1 due to ro king mode in theCu(I!) and Ni(I!) complexes. T e new bands ob-served in the far IR spectra f the metal corn-piexes at 450 and 380 cm-I • e due to vM - °and vN - M respectively.Table 2 - Fungicidal act vity data of mixed schiff base complexesn PDA mediumComplexes Concentrationof complexes% inhibitionAc triticina P. recondita(CuC2"N,O,H" ·2HP) lO~g/ml (70-90) (60.70)(CuC2IN,O,H",2H2O) 10 ~g/ml (75-90) (50-75)(CuC2uN,01HI7'2HP) lO~g/ml (75-115) (70-90)(CuC 2UN,02H ,7'2H20) lO~g/ml (70-90) (70-90)(NiC2I,N,O,H" '2H2O) lO~g/ml (60.70) (65-75)(NiC2,N,O,H,"'2H2O) lO~g/ml (65-70) (60-70)(NiC2UN.1°2H,7·2HP) l Ou g zml (60-70) (60-70)( .c., .102HI7·2H20) lO~g/ml (60-70) (60-75)NOTESAcknowledgementThe authors are thankful to Prof J M Trivedi,Head, Applied Chemistry Department for provid-ing necessary laboratory facilities. The authors arealso thankful to Prof P K Bhattacharya, Head,Chemistry Department for permission to work inhis laboratory.ReferencesI Thaker B T & Bhattacharya P K, J inorg nucl Chern, 37(1975)615.2 Thaker B T & Bhattacharya P K. Indian J Chern. 14(1976)619.3 Mohankurriar V B & Bhattacharya P K, J inorg nuclChern. 52(1975) 1041.4 Doraswami Uma & Bhattacharya P K. J inorg nucl Chern.97(1975) 1665.5 Cyba H A, US PAT 3-398-17011968; Chern Abstr, 69(1968) 6363.6 Snamt T & Umezari S, Bull chem Soc (Japall. 29 (1(56)975.7 Theiss H, Schomberger H & Borach K, Arch Pharma,299 (1966) 1031.X Sen R N & RayS K,JchemSoc. 9{1(32) 173.9 Dharkarey R & Saxena G, J chem Soc, 32 (19115) 35.10 Srivastav U, Khan R H & Bahel S C, J Antibact AntifungAgents Japan. 7 ( 1979) 8.II Harrigan W F & Margaret E. Laboratory methods ill mic-robiology (Academic Press, Agriculture College Ayr Scot-land) 1966, p 236.12 Lever A B P. Inorganic electronic speclroscoP.l{ElsevierNew York) 1968. p 236.13 Yamada S, Coord Chern Rev, I (1(63) 141.14 Figgis B N & Lewis, J Progr inorg Chern. 12 (1964) 1954.15 Flipen R B & FridbergS A. Phys Rev. 121 (1961) 1541.16 Nakamota K, Infrared spectra of inorganic and coordina-lion compounds, 2nd edn (Wiley lnterscience, New York)1970, 163.17 Daasch L M & Haninem U E. J Am chern Soc. 72{ 1950)3673.III Cox M, Clark R J H & Hilledge M J, Nature London,212.19 Cifferi R & Baldacci E, lnst Bull Plant Project, 19 (1945)33.Fungicidal activityThe antifungal of the compounds waschecked by Agar late technique III-II. Seven-dayold cultures of A lte '/wria triticinia and Puccina re-condita were used as test organisms which weregrown on potato a ar medium prepared by dis-solvin.g 79g of drie potato powder, 20g of dex-trose and 1.0g of gar in 1SOml of water. Themix! ure was then hated till it became a jelly-likesub ..stance; it was! n poured in a petri dish andcooled and then use as PDA medium.'For test solution a concentration of 10 u g/ mlwas used. The perc ntage inhibition was calculat-e.d as 100X (C - T) C where C is the diameter of'fungus colony in te t plate. All the complexes andligands were found 0 be highly active against boththe organisms teste . The metal complexes weremore active than th corresponding ligands whichis in accordance wit the fact that chelation of me-tal to ligands incr ases the fungitoxicity of themolecule I".721

Synthesis of mixed schiff base complexes of Cu(II) and Ni(II) and their spectral, magnetic and antifungal studies

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Synthesis of mixed schiff base complexes of Cu(II) and Ni(II) and their spectral, magnetic and antifungal studies

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