A new trinuclear nickel complex,[Ni3（pdc）3（2,2＇-bipy）3（H2O）2]·2H2O（H2pdc = pyridine 2,6-dicarboxylic acid,2,2＇-bipy = 2,2＇-bipyridine） has been hydrothermally synthesized and characterized by IR,elemen...A new trinuclear nickel complex,[Ni3（pdc）3（2,2＇-bipy）3（H2O）2]·2H2O（H2pdc = pyridine 2,6-dicarboxylic acid,2,2＇-bipy = 2,2＇-bipyridine） has been hydrothermally synthesized and characterized by IR,elemental analysis and X-ray diffraction methods.Crystal data for this complex：monoclinic,space group P21/n,a = 21.206（4）,b = 10.002（2）,c = 28.066（6）,β = 108.18（3）°,C51H41N9Ni3O16,Mr = 1212.06,V = 5.656（2） nm3,Dc = 1.423 g·cm-3,μ（MoKα） = 1.062 mm-1,Z = 4,F（000） = 2488,GOOF = 1.034,the final R = 0.0543 and wR = 0.1237 for 6149 observed reflections with Ⅰ 〉 2σ（Ⅰ）.In the complex,three nickel（Ⅱ） ions are bridged by the pyridine 2,6-dicarboxylic acid groups,and all nickel（Ⅱ） ions are seven-coordinated by nitrogen atoms of 2,2＇-bipyridine and pyridine 2,6-dicarboxylic acid and oxygen atoms from pyridine 2,6-dicarboxylic and water to adopt a severely distorted pentagonal bipyramidal geometry.The emission and excitation peaks of the complex in ethanol solutions are located at 336 and 316 nm,respectively.展开更多
Some spectral properties and luminescence intensities of Tb 3+ chelates of substituted pyridine 2, 6 dicarboxylic acids and 4 phenyl pyridine 2, 6 dicarboxylic acid analogues were measured in some solutions...Some spectral properties and luminescence intensities of Tb 3+ chelates of substituted pyridine 2, 6 dicarboxylic acids and 4 phenyl pyridine 2, 6 dicarboxylic acid analogues were measured in some solutions (H 2O and EtOH etc.) by synergistic effect of EDTA. The substitution at the aromatic ring has a significant effect upon the observed luminescence intensities, excitation wavelengths, and lifetime of the complexes. Moreover, the changes in the environment cause great variation in those properties of certain Tb 3+ chelates. The results show that some of hte chelates (4 acetaminopoxypyridine 2, 6 dicarboxylic acid, 4 ethoxypyridine 2, 6 dicarboxylic acid and 4 methoxypyridine 2, 6 dicarboxylic acid etc.) have a stronger emission and longer lifetime at room temperature and may thus be used as perfectly sensitizers in fluorescence analysis.展开更多
Reducing 2, 6-pyridinedicaboxylic acid diethyl ester to 2,6-di(hydroxymethyl)pyridine was carried out by using NaBH4/CaCl2 as reducing agent. It is an improved and efficient method. The yield is up to 91%.
We have described herein a catalyst-free preparation method of pyridine-2,6-bis(N-alkylthiazoline-2-thiones) (4a-i) by the reaction of primary amines, CS2, and pyridine-2,6-bis(2-bromo-1,3- dicarbonyl) derivatives (2a...We have described herein a catalyst-free preparation method of pyridine-2,6-bis(N-alkylthiazoline-2-thiones) (4a-i) by the reaction of primary amines, CS2, and pyridine-2,6-bis(2-bromo-1,3- dicarbonyl) derivatives (2a-c) in water. Also, we have described a catalyst free, green chemistry protocols to monobromination of pyridine-2,6-bis(2-bromo-1,3-dicarbonyl) derivatives with high yield, using NBS as a brominating agent, that led to eco-friendly isolation and purification proce-dures. Furthermore, we have studied the reactivity of pyridine-2,6-bis(2-bromo-1-methyl-pro- pane-1,3-dione) (2a) towards thiourea to afford 2,6-bis(5-benzoyl-2-aminothiazol-4-yl)pyridine (9).展开更多
Sixteen new 1,6-disubstituted fulvenes have been prepared by acylation of cyclopentadienyl sodium and the result of preliminary pharmacological tests showed that several of them have antineoplastic activity.
A method of synthesis of 4,6-disubstituted 5-thioxo-1,2,4-triazin- 3-ones from benzothioformanilides and semicarbazide is described.And six new compounds were synthesized by this method.
The reaction of CoCl2·6H2O with 2,6-bis（N,N＇-bis（2,6-diisopropyl-4-（2,3-dimethy-oxyl-benzoylamide）phenylimino））pyridine（L） afforded the complex [CoCl2L],which was fully characterized by elemental analysi...The reaction of CoCl2·6H2O with 2,6-bis（N,N＇-bis（2,6-diisopropyl-4-（2,3-dimethy-oxyl-benzoylamide）phenylimino））pyridine（L） afforded the complex [CoCl2L],which was fully characterized by elemental analysis,UV-vis,IR spectroscopy,fluorescence,and X-ray diffraction analysis.The compound is of triclinic system,space group P1 with a = 13.058（3）,b = 13.798（3）,c = 16.695（3） ,α = 98.191（3）,β = 102.792（3）,γ = 101.820（3）°,V = 2815.0（9） 3,Z = 2,F（000） = 1122,μ = 0.45 mm-1,R = 0.061 and wR = 0.1349 for 9842 observed reflections（Ⅰ 〉 2σ（Ⅰ））.The Co（Ⅱ） center adopts a distorted square-pyramidal coordination geometry.The extended structure shows a one-dimensional zigzag double chain linked by hydrogen bonds and π-π stacking interactions.展开更多
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 densit...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.展开更多
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). Th...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.展开更多
基金Supported by the Science and Technology Fund of Hengyang Science and Technology Bureau (No. 2008KS035)the Construct Program of the Key Discipline in Hunan Province
文摘A new trinuclear nickel complex,[Ni3（pdc）3（2,2＇-bipy）3（H2O）2]·2H2O（H2pdc = pyridine 2,6-dicarboxylic acid,2,2＇-bipy = 2,2＇-bipyridine） has been hydrothermally synthesized and characterized by IR,elemental analysis and X-ray diffraction methods.Crystal data for this complex：monoclinic,space group P21/n,a = 21.206（4）,b = 10.002（2）,c = 28.066（6）,β = 108.18（3）°,C51H41N9Ni3O16,Mr = 1212.06,V = 5.656（2） nm3,Dc = 1.423 g·cm-3,μ（MoKα） = 1.062 mm-1,Z = 4,F（000） = 2488,GOOF = 1.034,the final R = 0.0543 and wR = 0.1237 for 6149 observed reflections with Ⅰ 〉 2σ（Ⅰ）.In the complex,three nickel（Ⅱ） ions are bridged by the pyridine 2,6-dicarboxylic acid groups,and all nickel（Ⅱ） ions are seven-coordinated by nitrogen atoms of 2,2＇-bipyridine and pyridine 2,6-dicarboxylic acid and oxygen atoms from pyridine 2,6-dicarboxylic and water to adopt a severely distorted pentagonal bipyramidal geometry.The emission and excitation peaks of the complex in ethanol solutions are located at 336 and 316 nm,respectively.
文摘Some spectral properties and luminescence intensities of Tb 3+ chelates of substituted pyridine 2, 6 dicarboxylic acids and 4 phenyl pyridine 2, 6 dicarboxylic acid analogues were measured in some solutions (H 2O and EtOH etc.) by synergistic effect of EDTA. The substitution at the aromatic ring has a significant effect upon the observed luminescence intensities, excitation wavelengths, and lifetime of the complexes. Moreover, the changes in the environment cause great variation in those properties of certain Tb 3+ chelates. The results show that some of hte chelates (4 acetaminopoxypyridine 2, 6 dicarboxylic acid, 4 ethoxypyridine 2, 6 dicarboxylic acid and 4 methoxypyridine 2, 6 dicarboxylic acid etc.) have a stronger emission and longer lifetime at room temperature and may thus be used as perfectly sensitizers in fluorescence analysis.
文摘Reducing 2, 6-pyridinedicaboxylic acid diethyl ester to 2,6-di(hydroxymethyl)pyridine was carried out by using NaBH4/CaCl2 as reducing agent. It is an improved and efficient method. The yield is up to 91%.
文摘We have described herein a catalyst-free preparation method of pyridine-2,6-bis(N-alkylthiazoline-2-thiones) (4a-i) by the reaction of primary amines, CS2, and pyridine-2,6-bis(2-bromo-1,3- dicarbonyl) derivatives (2a-c) in water. Also, we have described a catalyst free, green chemistry protocols to monobromination of pyridine-2,6-bis(2-bromo-1,3-dicarbonyl) derivatives with high yield, using NBS as a brominating agent, that led to eco-friendly isolation and purification proce-dures. Furthermore, we have studied the reactivity of pyridine-2,6-bis(2-bromo-1-methyl-pro- pane-1,3-dione) (2a) towards thiourea to afford 2,6-bis(5-benzoyl-2-aminothiazol-4-yl)pyridine (9).
文摘Sixteen new 1,6-disubstituted fulvenes have been prepared by acylation of cyclopentadienyl sodium and the result of preliminary pharmacological tests showed that several of them have antineoplastic activity.
文摘A method of synthesis of 4,6-disubstituted 5-thioxo-1,2,4-triazin- 3-ones from benzothioformanilides and semicarbazide is described.And six new compounds were synthesized by this method.
基金Project supported by the Scientific and Technological Research Program of Chongqing Municipal Education Commission(KJ1601215,KJ15012002)the Ministry of Education “Chunhui Plan”(Z2016177)
文摘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.
文摘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.
