• Journal of the Korean Chemical Society
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• v.55 no.2
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• pp.230-234
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• 2011

The present study describes the synthesis of 4,5-dihydro-6-(4-methoxy-3-methylphenyl)-3(2H)-pyridazinone derivatives. The synthesis of the first target compound, 4,5-dihydro-6-(4-methoxy-3-methylphenyl)-3(2H)-pyridazinone (1), was achieved by Friedel-Crafts acylation of o-cresyl methyl ether with succinic anhydride and subsequent cyclization of the intermediary g-keto acid with hydrazine hydrate. Condensation of compound 1 with aromatic aldehydes in the presence of sodium ethoxide affords the corresponding 4-substituted benzyl pyridazinones (3a-d). The dihydropyridazinone 1 underwent dehydrogenation upon treatment with bromine/acetic acid mixture to give (4). Pyridazine (5) has been synthesized upon the reaction of pyridazinone (1) with 1,3-diphenyl-2-propen-1-one under the Michael addition reaction. N-dialkylaminomethyl derivatives 6a-b have been obtained from the reaction of pyridazinone 1 with formaldehyde and secondary amine, whereas reaction of 1 with formaldehyde gives N-hydroxymethyl derivative (7). This study also includes the synthesis of the 3-chloropyridazine derivative 8 in excellent yield by heating pyridazinone 3b in phosphorus oxychloride. The behaviour of the chloro derivative toward sodium azide, benzyl amine and anthranilic acid was also studied. The proposed structures of the products were confirmed by elemental analysis, spectral data and chemical evidence.

• Journal of the Korean Chemical Society
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• v.53 no.6
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• pp.683-692
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• 2009

The synthesis of a novel series of nickel(II) complexes with new ligands derived from hydrazones of isoniazid have been reported in present work. The complexes have general compositions [$Ni(L)_2X_2$] or $[Ni(L)_3](ClO_4)_2$ {L = N-isonicotinamido-furfuraldimine (INH-FFL), N-isonicotinamido-3',4',5'-trimethoxybenzaldimine (INH-TMB) or N-isonicotinamido-cinnamalidene (INH-CIN) and X = $Cl^-$, ${NO_3}^-$, $ NCS^-$ or $CH_3COO^-$}. The ligands hydrazones behave as neutral bidentates (N and O donor) through the carbonyl oxygen and azomethine nitrogen. The new complexes with octahedral geometry have been characterized by elemental analysis, molecular weight determinations, magnetic susceptibility/moment, thermogravimetric, electrochemical and spectroscopic studies viz. infrared and electronic spectra. On the basis of conductivity measurements in nitrobenzene ($PhNO_2$) solution the [$Ni(L)_2X_2$] and $[Ni(L)_3](ClO_4)_2$ complexes have been found to be non-electrolytes and 1:2 electrolytes, respectively. Thermal properties have also been investigated, which support the geometry of the complexes. Antibacterial and antifungal properties of nickel(II) complexes and few standard drugs have also been examined and it has been observed that the complexes have moderate antibacterial activities.

• Journal of the Korean Chemical Society
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• v.55 no.1
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• pp.70-80
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• 2011

Two new palladium (II) complexes, [Pd (phen)(pip-dtc)]$NO_3$ and [Pd(phen)(mor-dtc)]$NO_3$, (where phen is 1,10-Phenantroline, pip-dtc is piperidinedithiocarbamate anion and mor-dtc is morpholinedithiocarbamate anion) have been synthesized and characterized by elemental analysis, spectroscopic studies (FT-IR, $^1H$ NMR, UV-Vis) and conductance measurement. In these complexes, the dithiocarbamate ligands coordinate with Pd (II) center as bidentate with two sulfur atoms. These two complexes have been tested against chronic myelogenous leukemia cell line, K562. They show $IC_{50}$ values less than cisplatin and thus the mode of binding of the complexes to calf thymus DNA (CT-DNA) were investigated by ultraviolet difference and fluorescence spectroscopy. They can denature DNA, exhibit cooperative binding and intercalate into DNA. Several binding and thermodynamic parameters are also described.

• Journal of the Korean Chemical Society
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• v.55 no.4
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• pp.594-602
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• 2011

The effect of ${\alpha}$-, ${\beta}$- and ${\gamma}$-picolines on the stereochemistry of the coordination compounds of lanthanide(III) nitrates derived from 4[N-(furfural)amino]antipyrine semicarbazone (FFAAPS) has been studied. The general composition of the present coordination compounds is [Ln(FFAAPS)$(NO_3)_3$Pic] (Ln=La, Pr, Nd, Sm, Gd, Tb, Dy or Ho and Pic=${\alpha}$-, ${\beta}$- or ${\gamma}$-picolines). All these coordination compounds have been characterized by elemental analyses, molecular weight, molar conductance, magnetic susceptibility, infrared and electronic spectra. The infrared studies suggest that the FFAAPS behaves as a neutral tridentate ligand with N, N, O donor while ${\alpha}$-, ${\beta}$- or ${\gamma}$-picoline is coordinated to the lanthanide(III) ions via heterocyclic N-atom. Nitrates are bicovalently bonded in these compounds. From the electronic spectral data, nephelauxetic effect (${\beta}$), covalence factor ($b^{1/2}$), Sinha parameter (${\delta}%$) and the covalence angular overlap parameter (${\eta}$) have been calculated. Thermal stabilities of these complexes have been studied by thermogravimetric analysis. The coordination number of lanthanide(III) ions in the present compound is found to be ten. The antibacterial studies screening of the primary ligand FFAAPS and the complexes showed that the present complexes have moderate antibacterial activities.

• Journal of the Korean Chemical Society
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• v.55 no.4
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• pp.612-619
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• 2011

Lanthanide(III) complexes of 1,2-diphenyl-4-butyl-3,5-pyrazolidinedione(phenylbutazone, PB) have been synthesized and characterized by elemental analyses, molar conductance measurements, IR, UV-Vis. and NMR spectra. The spectral data reveal that the PB acts as a bidentate and mono-ionic ligand coordinating through both the carbonyl oxygens of the pyrazolidinedione ring. The molar conductance data suggest that the complexes are non-electrolytes. The thermal behaviour of the complexes was studied by TG and DTG in air atmosphere and the results provide information about dehydration, thermal stability and thermal decomposition. The final products are found to be the corresponding metal oxides. The thermodynamic parameters and kinetic parameters were evaluated for the dehydration and decomposition stages. The negative entropy values of the decomposition stages indicate that the activated complexes have a more ordered structure than the reactants and that the reactions are slower than normal. Based on these studies, the complexes have been formulated as $[Ln(PB)_3]{\cdot}5H_2O$(Ln=La and Ce) and $[Ln(PB)_3(H_2O)_2]{\cdot}2H_2O$(Ln=Pr, Nd and Sm).

• Journal of the Korean Chemical Society
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• v.34 no.1
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• pp.51-62
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• 1990

Pentadentate Schiff base cobalt(II) complexes; Co(II)(Sal-DET) and Co(II)(Sal-DPT) were synthesized and these complexes were allowed to react with dry to form oxygen adducts of cobalt(II) complexes such as [Co(III)(Sal-DET)]$_2O_2$ and [Co(III)(DPT)]$_2O_2$ in aprotic solvents. These complexes have been identified by IR spectra, TGA, DSC, magnetic susceptibility measurements, and elemental analysis. It has been found that the oxygen adadduct complexes of $\mu$-peroxo type have hexaccordinated octahedral configuration with pentadentate schiff base cobalt(II) and oxygen, but the mole ratio of oxygen to cobalt(III) complexes of first step for oxygen adduct formation reaction of cobalt(II) complexes in aprotic solvents are 1:1. The redox reaction processes of Co(II)(Sal-DET), Co(II)(Sal-DPT), and oxygen adduct of cobalt(II) complexes were investigated by cyclic voltammetry and DPP method with glassy carbon electrode in 0.1M TEAP-DMSO and 0.1M TEAP-pyridine. As a result the reduction reaction processes of Co(III)/Co(II) and Co(II)/Co(I) for cobalt(II) complexes and oxygen adducts of cobalt(II) complexes are two irreversible steps of one eletron process, and reaction processes of oxygen for oxygen adducts complexes were quasireversible and redox range of potential was $E_{pc}$ = -0.97V∼-0.86V and $E_{pa}$ = -0.87V ∼ 0.64V.

• Journal of the Korean Chemical Society
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• v.31 no.6
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• pp.542-554
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• 1987

Tetradentate schiff base cobalt(II) complexes; Co(SED), Co(SND) and Co(SOPD) have been prepared, these complexes have react with dry oxygen in DMSO to form oxygen adducts cobalt(III) complexes; $[Co(SED)(DMSO)]_2O_2,\;[Co(SND)(DMSO)]_2O_2$ and $[Co(SOPD)(DMSO)]_2O_2$. It seems to be that the oxygen adducts cobalt(Ⅲ) complexes have heexa coordinated octahedral configration with tetradentate schiff base cobalt (III), DMSO and oxygen, and the mole ratio of oxygen to cobalt(II) complexes are 1 : 2, these complexes have been identified by IR-Spectra, T.G.A., magnetic susceptibilitis and elemental analysis of C.H.N. and Cobalt. The redox reaction process of Co(SED), Co(SND) and Co(SOPD) complexes was investigated by cyclic voltammetry with glassy carbon electrode in 0.1M TEAP-DMSO. The results of redox reaction process of Co(II) / Co(III) and Co(II) / Co(I) for cobalt(SED) and cobalt(SOPD) complexes and Co(II) / Co(III) process for cobalt(SND) complex are reversible process but Co(II) / Co(I) process of Cobalt(SND) complex is irreversible, and oxygen adduct complexes to quasi reversibly with oxygen should be very closed related to the redox potentials of range, $E_{pc}$ = -0.80~-0.89V and $E_{pa}$ = -0.70~-0.76V.

• Journal of the Korean Chemical Society
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• v.35 no.1
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• pp.24-37
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• 1991

We synthesized the binuclear Tetradentate Schiff base nickel(II) and copper(II) complexes ; [Ni(II)$_2$(SMPO)$_2$(L)$_2$], [Ni(II)$_2$(SPPD)$_2$(L)$_2$] and [Cu(II)$_2$(SMPD)$_2$] and [Cu(II)$_2$(SPPD)$_2$] (where, L : Py, DMSO and DMF). We identified the structure of these complexes by elemental analysis, IR-spectrum, T.G.A, D.S.C and ESR measurements. According to the results of cyclic voltammetry and DPP measurements in aprotic solvent included 0.1M TEAP as supporting electrolyte, we knew that diffusional controlled redox process of one step with one electron was irreversible process in 0.1M TEAP-Py solution. Also it was reversible or quasi reversible process in 0.1M TEAP-DMSO solution and reversible or E.C reaction mechanism in 0.1M TEAP-DMF solution at mononuclear complexes ; [Cu(II)(SOPD)] and [Ni(II)(SOPD)(L)$_2$]. But, we knew that diffusional controlled redox process of two step for one electron of binuclear complexes was as follows. The values of redox potential for dimeric complexes in 0.1M TEAP-L solution (where, L ; Py, DMSO and DMF) with scan rate 100mV/sec.

• Journal of the Korean Chemical Society
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• v.37 no.6
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• pp.612-617
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• 1993

Some vanadium(III) complexes have been prepared from the reaction of VC$l_3$ with N, P, O-donating ligands and characterized by elemental analysis, $^1$H-NMR infrared and UV-Visible spectroscopy. 3,5-Lutidine, 1,2-phenylenediamine, 8-hydroxyquinoline, 9,10-phenanthrenequinone, triphenylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane and 1,1'-bis(diphenylphosphino)ferrocene were chosen as coordinating ligands. Stretching frequency ${\nu}g$(V-Cl) of complexes appears) at 298∼367 cm-1, which show octahedral geometries. Stretching frequency of ${\nu}g$(V-X) (X = N, P, O) indicates that ligands are coordinated to vanadium(III). Stretching frequency ${\nu}g(C{\equiv}N)$ of acetonitrile in these complexes are characteristically shifted to about 70 c$m^{-1}$ higher compared with that of a free ligand (2260 c$m^{-1}$). Bending frequency of $\delta(C{\equiv}N)$ is also shifted to about 60 c$m^{-1}$ higher compared with that of a free ligand (377 c$m^{-1}$). Finally each vanadium(III) complex showed the following formulation; [VC$l_3$(L)$_2$MeCN] or [VC$l_3$(L-L)MeCN].

• Journal of the Korean Chemical Society
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• v.39 no.11
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• pp.856-862
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• 1995

The tungsten oxo-nitrosyl complexes (n-Bu4N)2[W5O12(NO)2{RC(NH2)NHO}2{RC(NH)NO}2] (R=(CH3)2CH, CH3CH2CH2, CH3SCH2) have been synthesized by the reactions of polyoxotungsten complex (n-Bu4N)2[W6O19] and tungsten dinitrosyl monomeric complex [W(NO)2(acac)(CH3CN)2](BF4) with butylamidoxime derivatives. The prepared complexes have been characterized by elemental analysis, infrared, UV-visible, 1H NMR and 13C NMR spectroscopy. The pentanuclear species was formed by the interaction of the electron-withdrawing {W(NO)2}2+ unit between the two dinuclear tungsten {W2O5}2+ cores. We can estimate to exist large proton interactions viewed from the four doublet in 1H NMR spectrum of (n-Bu4N)2[W5O12(NO)2{(CH3)2CHC(NH2)NHO}2{(CH3)2CHC(NH)NO}2]. We also drew informations of the two different coordination mode and symmetry of the complexes because two ligands appear in 13C NMR spectra instead of four. The {W(NO)2}2+ unit has been cis-form and C2v symmetry in geometric structure.