Crystal Structures of Schiff Base from 4-Aminoantipyrine and Pyridine-2-carboxaldehyde and Its Perchlorate

The Schiff base pyridine-2-carboxaldehyde-4-aminoantipyrine （CI7H16N4O 1） and its perchlorate （C17H17N4O·ClO4 2） have been prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray crystallography analysis. Both 1 and 2 crystallize in the monoclinic system, space group P21/c. For 1, a = 8.6820（12）, b = 24.934（3）, c = 7.0064（10） A,, β= 97.942（3）°, V = 1502.2（4） A^3, Z = 4, Dc = 1.293 g/cm^3, F（000） = 616,μ = 0.084 mm^-1, the final R = 0.0592 and wR = 0.1244. For 2, a = 5.9302（2）, b = 20.347（7）, c = 14.663（6） A, β= 90.200（9）°, V= 1769.201） A^3, Z = 4, Dc = 1.475 g/cm^3, F（000） = 816, μ = 0.254 mm^-1, the final R = 0.0533 and wR = 0.0819. As expected, both molecular structures of 1 and 2 adopt a trans configuration about the central C=N double bond. 2 is an ionic compound with the protonation at N（1） of pyridine-2-carboxaldehyde-4- aminoantipyrine.

Synthesis, Characterization and Crystal Structure of Cobalt(II) Complex of a Schiff Base Derived from Isoniazid and Pyridine-4-Carboxaldehyde

A new hydrogen bonded Cobalt(II) Schiff base complex,?N’-(pyridine-4-carboxaldehyde) isonicotinoylhydrazone Cobalt(II), has been synthesized from isoniazid and pyridine-4-carboxaldehyde and characterized by IR spectroscopy, 1H-NMR, elemental analysis, TGA and single crystal X-ray structure determination. X-ray crystal structure analysis shows an octahedral complex with a metal centre coordinated to two ligand molecules through the pyridine nitrogen atoms and four water molecules and containing two nitrate groups as counter ions. The complex crystallizes in the monoclinic crystal system and P2(1)/n space group. The unit cell dimensions are: a = 7.2108(4) Å, b = 16.6020(9) Å, c = 13.0389(6) Å,α = 90°, β = 103.972(4)°, γ = 90°. The molecule is symmetrical about the cobalt centre as observed from the 1H-NMR and 13C-NMR and confirmed by the single crystal X-ray structure of the complex. Thermogravimetric analysis shows two steps decomposition of the complex to leave a metal oxide residue. The title compound is expected to be biologically active as one of the precursors (isoniazid) is a therapeutic agent with well-established clinical applications.

Synthesis, Crystal Structure and DNA-Binding Property of a Mn(Ⅱ) Complex Based on 5-(Tri-fluoromethyl)pyridine-2-carboxylic Acid

A new complex Mn(Htpc)2(H2O)2(1, Htpc = 5-(trifluoromethyl)pyridine-2-carboxylic acid) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. 1 belongs to triclinic system, space group P■ with a = 5.0885(10), b = 6.5574(13), c = 14.016(3) ?, β = 90.67(3)o, V = 436.34(17) ?3, Z = 1, Dc = 1.793 g·cm-3, μ = 0.855 mm-1, Mr = 471.18, F(000) = 235, the final R = 0.0454 and wR = 0.1134 for 1998 observed reflections with I > 2σ(I). The Mn(Ⅱ) ion is coordinated by two N and two O atoms from two Htpc as well as two O atoms from two coordinated water molecules, forming a 0D motif with distorted octahedral coordinate geometry. The adjacent 0D units are linked into 1D chains through hydrogen bond O(1W)–H(1 WB)···O(2), and via the O(1 W)–H(1 WA)···O(1) hydrogen bond the neighboring 1D chains are connected into a 2D supramolecular layer. Moreover, the interactions between the ligand and its complex with CT-DNA were studied by EtBr fluorescence probe, which suggested that these compounds bind to CT-DNA through an intercalation mode. The binding constants were 0.41 and 0.64 for Htpc and complex 1, respectively. It indicates that the interaction between complex 1 and CT-DNA is stronger than Htpc.

Theoretical Study on the Reaction Mechanism of 2-Methoxybenzaldehyde,4-Bromo-indanone,Malononitrile and Ammonium Acetate One-pot to Form 6-(2-Methoxyphenyl)-2-amino-6-bromo-5H-indeno[1,2-b]pyridine-3-carbonitrile

The reaction mechanism of 2-methoxybenzaldehyde, 4-bromo-indanone, malononitrile and ammonium acetate one-pot to form 6-（2-methoxyphenyl）-2-amino-6-bromo-5 Hindeno[1,2-b]pyridine-3-carbonitrile was studied by density functional theory. The geometries of the reactants, transition states, intermediates and products were optimized at the PW91/DNP level. Vibration analysis was carried out to confirm the transition state structure. Reaction pathways were investigated in this study. The result indicates that the reaction Re→ TSB1→IMB1→ TSB2→ IMB2→TSB3→IMB3→TSB4→IMB4→TSB5→IMB5→TSB6→IMB6→TSB7→IMB7→ TSB8→IMB8→TSB9→IMB9→P2 is the main pathway, the activation energy of which is the lowest. The dominant product predicted theoretically is in agreement with the experiment results.

Green Chemistry Approach to Fast and Highly Efficient One-Pot Synthesis of Bis-Isoxazolyl-1,2,5,6-Tetrahydro Pyridine-3-Carboxylates

The synthesis of the bis-isoxazolyl-1,2,5,6-tetrahydro pyridine-3-carboxylates is achieved in high yield without the production of toxic waste products by using room temperature ionic liquid (RTILs) triethyl ammonium acetate (TEAA). The RTIL TEAA played the dual role of efficient green solvent as well as recyclable catalyst.

THE FIRST BINUCLEAR MOLYBDENUM AND TUNGSTEN COMPLEXES WITH DOUBLY-BRIDGING PYRIDINE-2-THIOLATO LIGANDS.X-RAY CRYSTAL STRUCTURE OF THE COMPLEX[Mo_2(CO)_4(μ-pyS)_2(PPh_3)_2].2C_7H_8

The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.

Synthesis of Some New Pyridine-2-yl-Benzylidene-Imines

A series of new Schiff bases derived from 2-aminopyridenes and various aromatic aldehydes have been synthesized and thoroughly investigated by 1H and 13C NMR spectroscopy. The imines were found to exist as only a single E-isomer at ambient temperature. Interestingly, 1H- and 13C-NMR chemical shifts of the (CH=N) amino group are affected by the type of substituent group (X) on the aryl ring. Furthermore UV and IR Spectra of some of the title compounds are also reported.

Synthesis and Crystal Structure of (Z)-1- (3-Fluorobenzyl)-5-((3-fluorobenzylimino)(2-hydroxy-4-methoxyphenyl)methyl)pyridin-2(1H)-one

The title compound （Z）-1-（3-fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4- methoxyphenyl）methyl）pyridin-2（1H）-one （C27H22F2N2O3,Mr = 460.47） was synthesized and crystallized. The crystal belongs to the triclinic system,space group P1 with a = 9.951（6）,b = 10.059（6）,c = 12.927（7）A,α = 109.828（7）,β = 102.304（7）,γ = 104.898（7）°,Z = 2,V = 1110.2（11）A^3,Dc =1.377 Mg/m^3,μ（MoKα） = 0.102 mm^-1,F（000） = 480,the final R = 0.0449 and Rw = 0.1250 for 4595 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that both m-fluorobenzyl groups are diorientationally disordered because of the rotation of C–C single bond which was represented as F（1）,F（2） and F（1＇）,F（2＇）. The diorientational disorder was refined and gave the occupancies of 0.665（4） and 0.335（4） for F（1） and F（1＇）,0.631（3） and 0.369（3） for F（2） and F（2＇）. Hydrogen bonds existing in the cell link different components to stabilize the crystal structure. The active data proved that the title compound has good anti-HBV activity.

5-Alkylpyrrole-2-carboxaldehyde derivatives from the Chinese sponge Mycale lissochela and their PTP1B inhibitory activities

Two new 5-alkylpyrrole-2-carboxaldehyde derivatives,mycalenitrile-15（1） and mycalenitrile-16（2）,along with five known related ones（3-7）,were isolated from the South China Sea sponge Mycale lissochela.The structures of the new compounds were elucidated on the basis of extensive spectroscopic analysis and by comparison of their NMR data with those reported in the literature.In bioassay,compounds 1 and 7 exhibited significant PTPIB（Protein-tyrosine phosphatase 1B,a recognized target for diabetes and obesity） inhibitory activities with IC（50） values of 8.6 and 3.1 μmoI/L,respectively.A preliminary SAR analysis of the isolated compounds with their PTP1 B inhibitory effects was described.

Polymerization of 1,3-Butadiene Catalyzed by Cobalt(Ⅱ) and Nickel(Ⅱ) Complexes Bearing Pyridine-2-imidate Ligands

Cobalt and nickel complexes （la-ld and 2a-2d, respectively） supported by 2-imidate-pyridine ligands were synthesized and used for 1,3-butadiene polymerization. The complexes were characterized by IR and element analysis, and complex la was further characterized by single-crystal X-ray diffraction. The solid state structure of complex la displayed a distorted tetrahedral geometry. Upon activation with ethylaluminum sesquichloride （EASC）, all the complexes showed high activities toward 1,3-butadiene polymerization. The cobalt complexes produced polymers with high cis-1,4 contents and high molecular weights, while the nickel complexes displayed low cis-l,4 selectivity and the resulting polymers had low molecular weights. The catalytic activities of the complexes highly depended on the ligand structure. With the increment of polymerization temperature, the cis-1,4 content and the molecular weight of the resulting polymer decreased.

Relationship between Coordination Structure and Biological Activity of Copper(II) Nicotinate

The copper（Ⅱ） complexes of pyridine-3-carboxylic acid （nicotinic acid） and pyridine-2-carboxylic acid （isonicotinic acid） were synthesized, and their structures were characterized by elemental analysis, infrared spectrum, powder X-ray diffraction and so on. The results show that under experimental conditions, the ligands of synthesized copper nicotinate and copper isonicotinate are coordinated simultaneity with copper（Ⅱ） via the nitrogen of pyridine group and an oxygen of carboxylic acid group to form bidentate chelates. The crystal of copper nicotinate with two six-membered chelate rings belongs to monoclinic system, while that of copper isonicotinate having two five-membered chelate rings is of triclinic system. The tests show that the biological activities, such as the improvement of feed utilization, growth, anti-oxidation ability of organism and disease-resistant power, are different when copper nicotinate, copper inicotinate, copper-lysine chelate, copper-methionine chelate and copper sulphate are added in pig＇s feed, respectively. Due to its higher biological activity, less pollution and lower toxicity, copper nicotinate has wide potential applications as a feed additive.

Three-component reaction of alkyl isocyanides with acetylenic esters and pyridine-2-carboxaldoxime or α-furildioxime:Synthesis and dynamic NMR study of ketenimines and bis(ketenimines)

The addition of pyridine-2-carboxaldoxime or α-furildioxime to dialkyl acety lenedicarboxy lates under neutral conditions in the presence of alkyl isocyanides leads to ketenimines and bis（ketenimines） in good yields.

A New Thioamide Derivative for Separation and Preconcentration of Multi Elements in Aquatic Environment by Cloud Point Extraction

2-(pyridine-2-yl)-N-p-chlorohydrazinecarbothioamide (HCPTS) was synthesized, characterized and successfully applied for the preconcentration of Cu(II), Ni(II), Zn(II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II) in water, blood, and urine samples prior to graphite furnace atomic absorption determination (GFAAS);Hg was determined by cold vapor technique. Under the optimum experimental conditions (i.e. pH = 8, 10–4 M of HCPTS, 0.05% w/v of Triton X-114), calibration graphs were linear in the range of 0.02 to 200 ng?mL–1 for Co(II), Cd(II), Pb(II) and Ni(II);0.03 to 200 ng?mL–1 for Cu(II);0.07 to 200 ng?mL–1 for Fe(II) and Zn(II) and 0.02 to 150 ng?mL–1 for Hg(II). The enrichment factors were 43, 51, 41, 46, 54, 40, 45 and 52 for Cu(II), Ni(II),Zn (II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II), respectively. The limit of detection were found to be 0.019, 0.094, 0.0514, 0.052, 0.0165, 0.047, 0.068 and 0.041 ng?mL–1 for Cu(II), Ni(II), Zn(II), Cd(II), Co(II), Pb(II), Fe(II), and Hg(II), respectively. The developed method was applied to the determination of these metal ions in water, blood and urine samples with satisfactory results.

PdCl_2-catalyzed heterocyclotrimerization in MeOH/scCO_2:A versatile approach to dimethyl pyridine-3,5-dicarboxylate from methyl acrylate and urea

A novel and green method for the synthesis of dimethyl pyridine-3,5-dicarboxylate has been developed. It is PdCl2-catalyzed heterocyclotrimerization of methyl acrylate with urea in methanol/supercritical carbon dioxide. The target compound was obtained with a 75% isolated yield under the optimized con-ditions.

Synthesis, Crystal Structure and Luminescence of a New Europium(Ⅲ) Coordination Polymer with Imidazole Carboxylic Ligand

A new luminescent compound,{[Eu3(L)4(H2O)8]·(NO3)·4H2O}n(1,H2L=2-(pyridine-3-yl)-imidazole-4,5-dicarboxylic acid)has been solvothermally synthesized and structurally characterized by elemental analyses,IR and single-crystal X-ray diffraction.1 crystallizes in monoclinic,space group C2/c with a=21.0183(19),b=9.5227(6),c=28.227(3)A,β=106.885(5)°,V=5406.1(8)A3,Dc=2.038 g/cm3,μ=3.358 mm1,Mr=1658.76,F(000)=3247,Z=4,the final R=0.0488,wR=0.1195 and S=1.075.The deprotonated L ligand employs aμ4-bridge to coordinate with three Eu(Ⅲ)ion,forming a wave-like(3,4)-connected 2D structure.The existence of π…πinteraction between the pyridine rings of L ligands leads to an infinite 3D network.Furthermore,the thermal analysis,powder diffraction and solid-state photoluminescent properties of compound 1 have also been investigated.

Synthesis and characterization of poly(2,5-diyl pyrrole-2-pyrrolyl methine)semiconductor copolymer

The proposed technique to synthesise poly {（2,5-diyl pyrrole）（2-pyrrolyl methine）}（PPPM） copolymer by condensation of pyrrole and pyrrole-2-carboxaldehyde monomers catalyzed by Maghnite-H＋ is introduced.The protons are exchanged with Maghnite-H＋, which is available in the form of a montmorillonite silicate clay sheet. The effect of several parameters such as time and temperature of copolymerization, [pyrrole]/[pyrrole-2-carboxaldehyde] molar ratio, amount of Maghnite-H＋, and solvent on the produced poly（2,5-diyl pyrrole-2-pyrrolyl methine） semiconductor copolymer material（yield%） was investigated. The synthesized PPPM copolymer was characterized using nuclear magnetic resonance, Fourier transform infrared, and ultraviolet-visible spectroscopy.The results show that the synthesized copolymer using the copolymerization technique is a real organic copolymer consisting of two monomers units（i.e, pyrrole and pyrrole-2-carboxaldehyde）. Also, the synthesized copolymer is more soluble than polypyrrole in most of the commonly used organic solvents. Hence, copolymerization of pyrrole with pyrrole-2-carboxaldehyde will overcome the insolubility of polypyrrole. In addition, the resultant copolymer exhibits good film formability. The produced copolymer has several potential applications in the field of rechargeable batteries, sensors, capacitors, light emitting diodes, optical displays, and solar cells.