Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Synthesis, Structural Characterization and Antimicrobial Activity of a Novel Cobalt(II) Complex Based on 3-Methyl-1-Phenyl-4-(2-Thienoyl)-Pyrazol-5-One

New cobalt(II) complex, [Co(O2C15H11N2S)2(OH2)2]∙2H2O (1∙2H2O), has been synthesized upon reaction of cobalt chloride hexahydrate (Co(Cl)2∙6H2O) with 3-methyl-1-Phenyl-4-(2-thienoyl)-pyrazol-5-one (referred as HL) in ethanol at room temperature. Single crystal X-ray diffraction (XRD), spectroscopic methods, and microelemental analyses were used to characterize 1∙2H2O. Compound 1∙2H2O crystallizes in the orthorhombic crystal system with a Pbca space group and with the cobalt atom being pseudo-octahedral coordinated. The broth microdilution technique was used to screen the free ligand (HL) and the complex (1∙2H2O) for antimicrobial activities. HL has a low activity (MIC > 100 μg/mL) on all microorganisms, whereas compound 1∙2H2O displayed moderate activity (10 ∙2H2O exhibited bactericidal and fungicidal activity respectively on all the bacteria and yeasts tested. These findings reveal that the antimicrobial activity of HL was enhanced upon coordination to Co(II) ion against all microorganisms (bacteria and fungus).

Dissolution Properties of 2-(Dinitromethylene)-5-methyl-1,3-diazacyclopentane in Dimethyl Sulfoxide and N-Methyl Pyrrolidone

The molar enthalpies of dissolution for 2-（dinitromethylene）-5-methyl-1,3-diazacyclopentane（DNMDZ） in dimethyl sulfoxide（DMSO） and N-methyl pyrrolidone（NMP） were measured using an RD496-2000 Calvet microcalorimeter at 298.15 K under atmospheric pressure.Empirical formulae for the calculation of the molar enthalpies of dissolution（Δ diss H） were obtained from the experimental data of the dissolution processes of DNMDZ in DMSO or NMP.The relationships between the rate constant（k） and the molality（b） and between the reaction order（n） and the molality（b） were determined.The corresponding kinetic equations describing the two dissolution processes were dα/dt=10^-2.16（1-α） ^1.01 for the dissolution of DNMDZ in DMSO,and dα/dt=10^-2.02（1-α）^ 0.85 for the dissolution of DNMDZ in NMP,respectively.

Synthesis and Crystal Structure of a Co(Ⅱ) Complex with Taurine-5-methyl-2-hydroxyisophthalaldehyde Schiff Bases [Co(C_(13)H_(16)N_2O_7S_2)(H_2O)_3]_2·H_2O

The title complex [CoL（H20）3]2·H2O （C26H46N4O21S4CO2）, where L = taurine-5- methyl-2-hydroxyisophthalaldehydes, has been synthesized and characterized by IR and X-ray diffraction analysis. The crystal of the complex belongs to the triclinic system, space group P1, with a = 11.197（4）, b = 13.309（5）, c = 14.486（5） ]A, a = 78.827（13）,β = 70.547（11）, γ = 81.058（13）°, Mr = 996.77, S = 1.08, V= 1987.2（13） A3, Z = 2, Dc = 1.666 g/cm3, F（000） = 1032,μ = 1.131 mm^-1, R = 0.0633 and wR = 0.1293. According to the structural analysis, the Co（ Ⅱ ） ion adopts a slightly distorted six-coordinated octahedral geometry. One N atom of the Schiff base of each molecule was hydrogenated to form hydrogen bond with O atom. Two coterminous molecules packed in one crystal water molecule are linked by intermolecular hydrogen bonds, thus generating an infinite chain constructed by hydrogen bonds.

Synthesis, Crystal Structure and Antitumor Activity of 2-(3-Methyl-5-(methylthio)-4H-1,2,4-triazol-4-yl)isoindoline-1,3-dione

The title compound 2-（3-methyl-5-（methylthio）-4H-1,2,4-triazol-4-yl）isoindoline- 1,3-dione （C12H10NaO2S, Mr= 274.30） has been synthesized by a three-step procedure including the cyclization, hydrazinolysis and substitution reactions, and its crystal structure was determined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P2/c with a = 12.264（3）, b = 14.646（3）, c = 14.349（4） A,β = 91.69（3）°,μ = 0.255 mm1, Mr = 274.30, V = 2576.2（10） A3, Z =8, Dc = 1.414 g/cm3, F（000） = 1136, R = 0.0487 and wR = 0.1329 for 4048 observed reflections with I 〉 2σ（I）. In addition, the preliminary bioassay suggested that the title compound 6 exhibits relatively good antitumor activity against HT-29 and MCF-7.

Synthesis and Crystal Structure of Trans-4-[(5-(2,4-Dichlorophenoxy)-3-methyl-1-phenyl-1H-pyrazol-4-yl)methyleneamino]-1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.

Synthesis and Crystal Structure of Ethyl 3-(4-Chlorophenyl)-3,4-dihydro-6-methyl-4-oxo-2-(pyrrolidin-1-yl)furo[2,3-d]pyrimidine-5-carboxylate

The crystal structure of the title compound ethyl 3-（4-chlorophenyl）-3,4-dihydro-6- methyl-4-oxo-2-（pyrrolidin-1-yl）furo[2,3-d]pyrimidine-5-carboxylate （C20H20ClN3O4, Mr= 401.84） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 20.6215（9）, b = 8.5311（4）, c = 21.6886（9） A^°, β = 91.607（1）°, V = 3814.0（3）A^°^3, Z = 8, Dc = 1.400 g/cm^3, F（000） = 1680, μ = 0.233 mm^-1, R = 0.0718 and wR = 0.1545 for 6717 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals two crystallographically independent molecules in the asymmetric unit.

Synthesis, Characterization and Crystal Structure of a Dinuclear Silver(I) Complex: [AgL(NO_3)]_2 (L= 2-Acetamido-5-methyl-1,3,4-thiadiazole)

The title complex [AgL（NO3）]2 1, where L = 2-acetamido-5-methyl-1,3,4-thiadiazole, was prepared from the reaction of 2-acetamido-5-methyl-1,3,4-thiadiazole with AgNO3 at room temperature and its structure has been determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P2t/c with a = 12.5454（8）, b = 11.9672（12）, c = 6.8925（6） A, β = 98.468（2）°. V= 1023.51（15） A^3, Mr= 3127.08, Dc = 2.123 g/cm^3, Z= 4, μ（MoKoσ） = 2.174 mm^-1, F（000） = 640, R = 0.0259 and wR = 0.0580 for 1787 observed reflections with I 〉 2σ（I）. Complex 1 self-assembls into a quasi-three-dimensional network consisting of adjacent dimers through intermolecular Ag...O weak interactions.

Dual-parameter Correlation Analysis of the Fluorescence Data of 1-Methyl-2-formyl-5-substituted Pyrrole(4-nitrophenyl)hydrazones

By using 1-methyl-2-formyl-5 -Y-substituted pyrrole (4-nitrophenyl)hydrazones as a model for nitrogen-containing heterocyclic aromatic compounds, the emission wavelength [lambda(max(em))] values df their fluorescence spectra have been measured. Correlation results show that the Delta E-em values are mainly affected by polar effects, but spin-delocalizatin effects also exist.

Thermodynamic Study and Spectroscopic Analysis of a Charge-Transfer Complex between 3,5-Diamino-1,2,4-Triazole and 6-Methyl-1,3,5-Triazine-2,4-Diamine with Chloranilic Acid

Studying of charge-transfer (CT) and proton transfer interactions is essential due to their important role in many biological field and industrial applications. The current work will add more information’s about the nature of interaction between 3,5-diamino-1,2,4-triazole (DAT) and 6-methyl-1,3,5-triazine-2,4-diamine (MTDA) with 3,6-dichloro-2,5-dihydroxy-p-benzoquinone (chloranilic acid CLA) which was studied spectrophotometrically in Ethanol (EtOH) and Methanol (MeOH) solvents at different temperatures. The molecular composition of the formed complexes was studied by applying continuous variation and spectrophotometric titration methods and found to be 1:1 charge transfer complex for both Complex (DAT:CLA) and (MTDA:CLA) which are produced. Minimum-Maximum absorbance’s method has been applied to calculate the formation constant KCT and molecular extinction coefficient (ε);they recorded high values confirming high stability of the produced complexes. Oscillator strength (f), transition dipole moment (μ), ionization potential (IP) and dissociation energy (W) of the formed CT-complexes were also determined and evaluated;they showed solvent dependency. It is concluded that the formation constant (KCT) of the complexes is found to depend on the nature of both electron acceptor and donors and on the polarity of solvents.

Enamine Configuration of 5-Methyl-2-phenyl-4- [(Z)-3-tolylamino-phenylmethylene]pyrazol-3(2H)-one

Compound 5-methyl-2-phenyl-4-[（Z）-3-tolylamino-phenylmethylene]pyrazol-3（2H）-one （C24H21N3O） crystallizes in the triclinic system, space group P1, with a = 9.267（3）, b = 9.904（4）,c = 12.035（4） A°, α = 97.896（6）, β = 103.865（6）, γ = 107.950（6）°, Mr= 367.44, Z = 2, V = 993.2（6）A°^3,Dc = 1.229 g/cm^3,μ（MoKa） = 0.077 mm^-1 and F（000） = 388. The structure was refined to R =0.0444 and wR = 0.1199 for 2903 observed reflections （I 〉 2σ（I））. The results of ^1H NMR and single-crystal X-ray diffraction studies showed the enamine character of the compound. The strong intramolecular hydrogen bonds in the large conjugate system, together with weak intermolecular C-H……π hydrogen bonding and π……π stacking, lead to the formation of a multi-dimensional supramolecular network.

Synthesis and Crystal Structure of 4-Bromo-5-ethoxy-3-methyl-5- (naphthalen-1-yl)-1-tosyl-1H-pyrrol-2(5H)-one

The title compound 4-bromo-5-ethoxy-3-methyl-5-（naphthalen-l-yl）-l-tosyl-lH- pyrrol-2（5H）-one 1 （C24H22BrNO4S, Mr = 500.40） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 8.8562（15）, b = 18.118（3）, c = 14.055（2）A, β = 99.855（3）^o, V= 2221.9（6）A3, Z = 4, Dc = 1.496 g/cm^3,μ= 1.975 mm^-1, 2 = 0.71073A, F（000） = 1024, R = 0.0607 and wR = 0.1371.

Synthesis of (S)-2-(3-Arylacrylamido)-3-{4-[2-(5-methyl-2-phenyl-oxazol-4-yl)ethoxy]phenyl}propanoic Acids

The synthesis of （S）-2-（3-arylacrylamido）-3-{4-[2-（5-methyl-2-phenyloxazol-4-yl）etho- xy]phenyl}propanoic acids is described. Their structures were confirmed by ^1H-NMR.

Crystal and Molecular Structure, and Spectral Characteristics of Sodium 3,5-Bis(Hydroxyimino)-1-Methyl-2,4,6-Trioxocyclohexanide

Sodium 3,5-bis(hydroxyimino)-1-methyl-2,4,6-trioxocyclohexanide C7H5N2NaO5 (I) has been isolated as the only product of the reaction of nitrosation of methylphloroglucinol. The structure of the titled compound has been determined from single crystal X-ray diffraction data. The hydrated C7H5N2NaO52.5H2O crystallizes in the monoclinic space group C2/c, with a(?) 16.408(3);b(?) 12.446(3);c(?) 13.716(3);(o) 126.34(3). The planar organic anion exists in a triketo-dihydroxyimino form with the C–O and C–N distances from 1.220(2) to 1.271(2)?? and from 1.292(2) to 1.293?? respectively. In the IR spectrum of I, the sharp absorption band occurred at 1681 cm-1 due to C=O stretching indicating the strong H-interactions. The correlations of theoretical (DFT-B3LYP/aug-cc-pVDZ) and experimental UV-vis absorption spectra in neutral and alkaline ethanolic solutions showed the existence of hydroxyimino-nitroso tautomerism while ionization of I.

The First Two-dimensional Supramolecular Network Constructed by Na(Ⅰ) with 2-Methylimidazole-4,5-dicarboxylate Building Blocks

The title complex [Na（H2MIA-）（H2O）]（1,H3MIA = 2-methyl-1H-imidazole-4,5-dicarboxylic acid） has been synthesized by hydrothermal synthesis and structurally characterized by X-ray crystallography.Compound 1 crystallizes in orthorhombic,space group ibam with a = 14.4737（19）,b = 17.553（2）,c = 6.5285（9）,V = 1658.6（4） 3,C6H7N2NaO5,Mr = 210.12,Z = 8,Dc = 1.675 g/cm3,F（000） = 864,μ = 0.188 mm-1,λ（MoKα） = 0.071073 ,R = 0.0383 and wR = 0.0987 for 1046 observed reflections（I 2σ（I））.In the structure of 1,each coordination water coordinates with two Na（I） ions at the same time and links the neighboring Na（I） ions to form a one-dimensional Na（I）-water chain.Each H2MIA-ligand links the neighboring Na（I） of Na（I）-water chain to form a novel two-dimensional supramolecular network.The 2-D network is stabilized by O-H…N hydrogen bonds and π-π interaction.The 2D network is further linked via O-H…O hydrogen bonds to yield a three-dimensional framework.

Synthesis, Reactions and Characterization of 1,1’-(1,4-Phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(ethan-1-one)

Reaction of 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-thioxo-1,2-dihydropyridine-3-carbonitrile) (1) with methyl iodide afforded the 4,4’-(1,4-phenylene)bis(5-acetyl-6-methyl-2-(methylthio)nicotinonitrile) (2). The reaction of 2 with hydrazine hydrate followed by diazotization reaction af-forded the 1,1’-(1,4-phenylenebis(3-amino-6-methyl-1H-pyrazolo[3,4-b]pyridine-4,5-diyl))bis(e-than-1-one) (3) and 1,1’-(1,4-phenylenebis(3-(chlorodiazenyl)-6-methyl-1H-pyrazolo[3,4-b]-pyridine-4,5-diyl))bis(ethan-1-one) (4) respectively. On the other hand, reaction of 4 with malononitrile, 2-cyanoethanethioamide, ethyl acetoacetate, acetyl acetone, ethyl benzoylacetate, diethylmalonate, ethyl cyanoacetate and phenacylbromide aiming to build up pyrazolotriazine or pyrazole ring on the ring system of 4. Structures of all newly synthesized heterocyclic compounds in the present study were confirmed by considering the data of IR, 1H NMR, mass spectra as well as that of elemental analyses.

Synthesis and Crystal Structure of Dinuclear Copper(Ⅱ)Complex Cu_2(μ-PhCOO)_4(amet)_2·2CH_3COCH_3

Reaction of copper powder, dibenzoyl peroxide and 2-amino-4methyl-5-ethoxycarbonyl thiazole (amet) by refluxing in acetone yielded the dinuclearcopper(Ⅱ) complex Cu2 (μ-PhCOO)4 (amet)2- 2CH3COCH3. Crystal structure determination showed that each copper atom is coordinated by four bridged benzoxy and oneamet molecule with an M-M bond (Cu-Cu (A) = 2.6899 (7 ) ), therefore the coor-dination environment around the copper center is a distorted square pyramid with N(1)at the apical position. Blocks of Cu2 (μ-PhCOO)4 (amet)2·2CH3COCH3 crystallize inthe triclinic space group Ph, with Mr= 1100.14, a= 9. 631 (1), b=10. 446 (2), c=12. 758(2) ; a=91. 31 (1), β=95. 50(1),γ= 94. 87(1)°, V=1272. 4(3), Z=1, Dc= 1. 436 g/cm3, F(000) = 570, μ=0. 986 mm-1 and R=0.033, Rw=0.049.The IR spectra, which are of great interest since the molecule has ketone, ester andcarboxylate group simultaneously, are also discussed.

Dietary exposure to di-isobutyl phthalate increases urinary 5-methyl-2′-deoxycytidine level and affects reproductive function in adult male mice

Phthalates are a large family of ubiquitous environmental pollutants suspected of being endocrine disruptors. Epidemiological studies have associated phthalate metabolites with decreased reproductive parameters and linked phthalate exposure with the level of urinary 5-methyl-2′-deoxycytidine（5mdC, a product of methylated DNA）. In this study, adult male mice were exposed to 450 mg di-isobutyl phthalate（DiBP）/（kg·day） via dietary exposure for 28 days. Mono-isobutyl phthalate（Mi BP, the urinary metabolite） and reproductive function parameters were determined. The levels of 5mdC and 5-hydroxymethyl-2′-deoxycytidine（5hmdC） were measured in urine to evaluate if their contents were also altered by DiBP exposure in this animal model. Results showed that DiBP exposure led to a significant increase in the urinary 5mdC level and significant decreases in sperm concentration and motility in the epididymis, accompanied with reduced testosterone levels and downregulation of the P450 cholesterol side-chain cleavage enzyme（P450scc） gene in the mice testes. Our findings indicated that exposure to DiBP increased the urinary 5mdC levels,which supported our recent epidemiological study about the associations of urinary 5mdC with phthalate exposure in the male human population. In addition, DiBP exposure impaired male reproductive function, possibly by disturbing testosterone levels; P450scc might be a major steroidogenic enzyme targeted by DiBP or other phthalates.

Synthesis and Antimicrobial Activity of 2-Methyl-5-nitroaniline Derivatives： A Structure-Activity Relationship Study

A series of 2-methyl-5-nitroaniline derivatives, 5a--Sk and 6a--6f, were synthesized in order to determine their in vitro antimicrobial activity. The chemical structures of the synthesized compounds were confirmed by elemental analyses, UV-visible, FT-IR, 1H NMR and 13C NMR spectral studies. The structure-activity relationships of the synthesized compounds were also discussed. Among the synthesized compounds, 5f, 5d, 6b and 6e showed good antimicrobial activity compared to standard drugs.

Cu（OTf）2 Catalyzed Synthesis of Bis（5-methyl-2-furyl）methanes by Condensation of 2-Methylfuran with Carbonyl Compounds under Solvent Free Conditions

A facile and efficient one-pot three-component synthesis of bis（5-methyl-2-furyl）methanes has been achieved via the reaction of 2-methylfuran with a series of aliphatic and aromatic aldehydes and aliphatic ketones in presence of copper（II） triflate under solvent free conditions. The bis（5-methyl-2-furyl）methanes were obtained in 34%--72% yields and the catalyst was recycled up to four successive cycles without much loss in catalytic activity.