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).

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 1-(4-Fluorophenyl)-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H)-one

The crystal structure of the title compound 1-（4-fluorophenyl） -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H） -one（C23H21FN4O2S,Mr = 436.5） has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854（3） ,b = 17.2678（4） ,c = 18.1828（5）A,β = 99.364（2） °,V = 4332.58（18） A^3,Z = 4,Dc = 1.338,F（000） =1824,μ = 0.185 mm^-1,MoKa radiation（λ = 0.71073） ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I 〉 2σ（I） . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5（1H） -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.

Enzymatic Synthesis and Characterization of Novel Polycarbonates Derived from 5-Allyloxy-1, 3-dioxan-2-one and 5, 5-Dimethvl-1.3-dioxan-2-one

Novel polycarbonates from 5-allyloxy-1, 3-dioxan-2-one （ATMC） with 5, 5-dimethyl- 1, 3-dioxan-2-one （DTC） were successfully synthesized for the first time using immobilized porcine pancreas lipase （IPPL） as catalyst. The resulting copolymers were characterized by IR, ^1H NMR, ^13C NMR and GPC. The molecular weight （Mn） of the copolymer with molar feed ratio of 10：90 （ATMC：DTC） was 9300 and the polydispersity was 1.31, while the Mn increased to 14300 and polydispersity of 1.25 with the feed ratio of 50：50. Moreover, the composition of the copolymers agreed well with the monomer feed.

A NOVEL METHOD FOR SYNTHESIZING α,α-DISUBSTITUTED α-AMINO ACID——DIALKYLATION OF 2-OXAZOLIN-5-ONE

4,4-Dialkyl-2-oxazolin-5-ones are prepared by one step reaction of 2-oxazolin-5-one with the magnesium methyl carbonate(MMC)and alkyIhalides.It is a novel and convenient method for synthesis of α, Υ-disubstitutcd α-amino acid by hydrolysis of 4,4-dialkyl-2-oxazolin-5-ones.

SINGLE LANTHANUM TRIS(N-PHENYLETHYL-3,5-DI-t-BUTYLSALICYLALDIMINATO)S INITIATOR FOR RING-OPENING POLYMERIZATION OF 1,4-DIOXAN-2-ONE IN BULK

A rare earth Schiff base complex:lanthanum tris(N-phenylethyl-3,5-di-t-butylsalicylaldiminato)s [La(OPEBS)_3] was successfully applied as single component initiator for the ring-opening polymerization of 1,4-dioxan-2-one (PDO) in bulk.The influence of reaction conditions,such as polymerization temperature,the molar ratio of the monomer to initiator (M/I) on the monomer conversion and molecular weight of the polymer has been investigated.Poly(1,4-dioxan-2-one) with a viscosity-average molecular weight (My) o...

Synthetic Approach for Novel Fluorine Substituted <i>α</i>-Aminophosphonic Acids Containing 1,2,4-Triazin-5-One Moiety as Antioxidant Agents

Novel fluorine substituted α-amino phosphonic acids containing 1,2,4-triazin- 5-one (6a-f) have been obtained from fluoroacylation of 6-(2&prime;-amino-5&prime;-nitrophenyl)-3-thioxo-1,2,4-triazin-5(4H)-one (1) followed by ammonilysis to give the corresponding 3-amino-derivative 3. Condensation of compound 3 with nitro/halogenated aromatic aldehydes yielded the Schiff bases 4. The simple addition of diethyl phosphonate to compound 4 produced the α-amino phosphonates 5. Acidic hydrolysis of compound 5 produced the fluorine substituted α-amino acids derivatives 6. Structures of the new compounds have been established with the help of elemental analysis and spectral measurements. Also, the products evaluated as antioxidants, where the fluorinated α-amino phosphonic acids 6 are more active than the other synthesized systems.

Various Routes to Synthesise 3-Thioxo-1,2,4-Triazine-5-One Derivatives as Antimicrobial Agents

A simple condensation afforded some new 3-thioxo-1,2,4-triazin-5-one derivatives (4, 6 and 8). Utilizing a facile condensation of (E)-4-(4’-bromo styryl)-2-oxo-3-buteneoic acid with thiosemicarbazide, dithioic formic acid hydrazide, and thiocarbahydrazide in different conditions. Structures of these compounds were confirmed by elemental and spectral analysis. The preliminary biocidal activity of these products were evaluated against some microbial and compared to Mycostatine and piperacillin as antibiotics were most of derivatives exhibited good activity.

One-Pot Three Component Domino Reaction for the Synthesis of Novel Isoxazolo[2,3-<i>c</i>][1,3,5]Thiadiazepin-2-Ones Catalyzed by <i>PTSA</i>—A Green Chemistry Approach

The synthesis of novel isoxazolo[2,3-c][1,3,5]thiadiazepin-2-ones has been achieved in excellent yields by one-pot three-component Domino reaction without the production of toxic waste products by using p-toluene sulfonic acid (PTSA) as a Lewis acid catalyst. PTSA plays a crucial role in the success of the reaction, as well as for increasing reaction rate.

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.

Spontaneous Changes of Solid 5,7-di-<i>tert</i>-butylspiro(2,5)octa-4,7-diene-6-one in Storage Conditions at Room Temperature

On an example of spontaneous changes 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one at room temperature, a new example of condensations in a solid station is opened. The single crystal of 2-(3’, 5'-di-tert-butyl-4'-hydroxy-phenyl)-ethyloxy-p-cresole is produced as result of a structure transformation 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one in a solid phase at room temperature except a single crystal at transformation 5,7-di-tert-butylspiro (2,5) octa-4,7-diene-6-one a new substance is formed too. Spectrums 1Н and 13С NMR differ from similar spectrums of initial compound and the single crystal. New substance represents an admixture of isomeric compounds, capable reversible to be transformed in initial 5,7-di-tert-butylspiro(2,5) octa-4,7-diene-6-one and 2-(3’, 5'-di-tert-butyl-4'-hydroxyphenyl)-ethyloxy-p-cresole.

Synthesis and Crystal Structure of 2-Ethoxy-3-n-butyl-benzofuro [2,3-d]pyrimidin-4(3H)-one

The crystal structure of the new title compound 2-ethoxy-3-n-butyl- benzofuro[2,3d]pyrimidin-4（3H）-one （C16H18N2O3, Mr = 286.32） has been prepared and determined by singlecrystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 13.7167（14）, b = 13.113（1）, c = 8.378（1） A, β = 98.992（2）^o, V = 1488.4（3） A^3, Z = 4, Dc = 1.278, F（000） = 608, μ = 0.089 mm^-1, MoKa radiation （2 = 0.71073）, R = 0.0498, wR = 0.1238 for 2336 observed reflections with I 〉 2σ（I）. X-ray diffraction analysis reveals that all ring atoms in the benzo[4, 5]furo [2,3-d] pyrimi- dinone moieties are almost coplanar.

Synthesis and Crystal Structure of N-[(2S)-4-bromo-2-(L-menthyloxy)-5-oxo-2,5-dihydro-3-furyl]-L-leucine

Starting from（5S）-（L-menthyloxy）-3,4-dibromo-5H-furan-2-one and L-leucine,the title compound N-[（2S）-4-bromo-2-（L-menthyloxy）-5-oxo-2,5-dihydro-3-furyl]-L-leucine 5（C20H32BrNO5,Mr = 446.37） was obtained in one-pot process via the tandem Michael addition-elimination reaction in the presence of potassium hydroxide.The chemical structure and absolute configuration of the title compound were confirmed via rotation,UV-Vis,FT-IR,1H NMR,13C NMR,MS and elemental analysis,especially by the X-ray single-crystal diffraction.The crystal crystallizes in an orthorhombic system,space group P212121 with a = 12.5249（16）,b = 19.005（3）,c = 19.719（3） ,V = 4693.7（10） 3,Z = 8,Dc = 1.263 g/m3,μ = 1.778 mm-1,F（000） = 1872,the final R = 0.0617 and wR = 0.1576 for 3967 observed reflections（I 2σ（I））.X-ray analysis reveals that the title compound has two independent molecules in the asymmetric part of the unit cell with the two five-membered furanones being almost planar.The essential part of the electron delocalization is concentrated in the N（1）,C（3）,C（1）,C（37） and O（7） region and N（2）,C（28）,C（27）,C（30） and O（4） region in the other molecule respectively,but does not take place at the expense of delocalization within the ester function.

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.

Possible Mechanism of Therapeutic Effect of 3-Methyl-l-phenyl-2-pyrazolin-5-one and Bone Marrow Stromal Cells Combination Treatment in Rat Ischemic Stroke Model

Background： The functional improvement following bone marrow stromal cells （BMSCs） transplantation after stroke is directly related to the number of engrafted cells and neurogenesis in the injured brain. Here, we tried to evaluate whether 3-methyl-1-phenyl-2-pyrazolin-5-one （MCI-186）, a free radical scavenger, might influence BMSCs migration to ischemic brain, which could promote neurogenesis and thereby enhance treatment effects after stroke. Methods： Rat transient middle cerebral artery occlusion （MCAO） model was established. Two separate MCAO groups were administered with either MC1-186 or phosphate-buffered saline （PBS） solution to evaluate the expression of stromal cell-derived factor-1 （SDF-1） in ischemic brain, and compared to that in sham group （n 5/group/time point[at 1,3, and 7 days after operation]）. The content ofchemokine receptor-4 （CXCR4, a main receptor of SDF-I） at 7 days after operation was also observed on cultured BMSCs. Another four MCAO groups were intravenously administered with either PBS, MCI-186, BMSCs （2 ×106）, or a combination of MCI-186 and BMSCs （n = 10/ group）. 5-bromo-2-deoxyuridine （BrdU） and Nestin double-immunofluorescence staining was performed to identity the engrafted BMSCs and neuronal differentiation. Adhesive-removal test and foot-fault evaluation were used to test the neurological outcome. Results： MC1-186 upregulated the expression ofSDF- 1 in ischemic brain and CXCR4 content in BMSCs was enhanced after hypoxic stimulation. When MCAO rats were treated with either MCI- 186, BMSCs, or a combination ofMCI- 186 and BMSCs, the neurologic function was obviously recovered as compared to PBS control group （P 〈 0.01 or 0.05, respectively）. Combination therapy represented a further restoration, increased the number of BMSCs and Nestin- cells in ischemic brain as compared with BMSCs monotherapy （P 〈 0.01）. The number ofengrafted-BMSCs was correlated with the density of neuronal cells in ischemic brain （r = 0.72, P 〈 0.01 ） and the improvement of foot-thult （r = 0.70, P 〈 0.0 t ）. Conclusion： MCI- 186 might promote BMSCs migration to the ischemic brain, amplify the neurogenesis, and improve the effects of cell therapy.

Vitamin B12: An efficient type catalyst for the one-pot synthesis of 3,4,5-trisubstituted furan-2(5H)-ones and N-aryl-3-aminodihydropyrrol-2-one-4-carboxylates

Vitamin B12 was applied as catalyst for the one-pot three-component synthesis of 3,4,5-trisubstituted furan-2（5H）-ones from the condensation between aldehydes, amines and dialkylacetylendicarboxylates at ambient temperature in Et OH. In addition, N-aryl-3-aminodihydropyrrol-2-one-4-carboxylates were synthesised using mentioned catalyst at ambient temperature in Et OH from condensation between formaldehyde, amines, and dialkylacetylenedicarboxylates. This methodology has number of advantages such as： use of green and nonhazardous catalyst, clean work up, short reaction times,high yields and no need to column chromatography.

An effcient one-pot multi-component synthesis of 3,4,5-substituted furan-2(5H)-ones catalyzed by tetra-n-butylammonium bisulfate

A facile one-pot synthesis of 3,4,5-substituted furan-2（5H）-one derivatives from a three-component reaction of aniline derivatives, dialkylacetylenedicarboxylates and aromatic aldehydes under mild conditions using tetra-n-butylammonium bisulfate as a catalyst has been developed.