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 ...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.展开更多
A one-pot three component condensation synthesis of imidazo[1,5-a]pyridines using of various aromatic aldehydes and dipyridil ketone with ammonium acetate in the presence of Lithium chloride as catalyst in good yields...A one-pot three component condensation synthesis of imidazo[1,5-a]pyridines using of various aromatic aldehydes and dipyridil ketone with ammonium acetate in the presence of Lithium chloride as catalyst in good yields under microwave irradiation has been described.展开更多
One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characte...One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860(5), b = 13.8246(6), c = 19.0140(8) A, β = 104.3870(1)°, V = 3128.2(2) A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F(000) = 1444 and μ(Mo Kα) = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ(I) and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni(OTP)]n chain and the 2D [Ni2(bib)3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.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
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
The title compound (C20H15ClN4O, Mr = 362.81) was synthesized by the reaction of ethyl 2-cyano-3-(2-chlorophenyl)-1-acylate with 5-amino-3-methyl-1-phenylpyrazole under microwave irradiation and its structure was dete...The title compound (C20H15ClN4O, Mr = 362.81) was synthesized by the reaction of ethyl 2-cyano-3-(2-chlorophenyl)-1-acylate with 5-amino-3-methyl-1-phenylpyrazole under microwave irradiation and its structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.8192(19), b = 15.976(3), c = 13.094(3) ? = 103.074(4), V = 1797.1(7) ?, Z = 4, Dc = 1.341 g/cm3, = 0.229 mm-1, F(000) = 752, R = 0.0632 and wR = 0.1278. X-ray analysis reveals that the pyridine ring adopts an envelope conformation. The dihedral angle between the pyrazole and pyridine planes is 2.19, and inter- molecular hydrogen bonds are also observed in the molecule.展开更多
The synthesis process of 2-mercapto-5-methoxyimidazo[4,5-b]pyridine, a crucial intermediate of tenatoprazole which is a new proton pump inhibitor, was studied.2,6-Dichloropyridine as raw material was nitrated by nitri...The synthesis process of 2-mercapto-5-methoxyimidazo[4,5-b]pyridine, a crucial intermediate of tenatoprazole which is a new proton pump inhibitor, was studied.2,6-Dichloropyridine as raw material was nitrated by nitric acid/sulfuric acid, and after amination 2-amino-3-nitro-6-chloropyridine was obtained.It then reacted with sodium methoxide to give 2-amino-3-nitro-6-methoxypyridine and the intermediate was reduced by H2 with Raney Ni as catalyst to give 2,3-diamino-6-methoxypyridine.Finally cyclization was finished with carbon bisulfide to give the title compound.The optimal reaction conditions and yield(temperature, time, molar yield) were as follows: nitration,110℃, 8 h, 79.3%; amination, room temperature, 10 h, 87.6%; methoxylation,65℃, 30min, 98.7%; reduction,70℃, 3 h; cyclization, reflux, 4 h, 72.4% (two steps).The melting point of the title compound was the same as that reported in literature, and its structure was confirmed by 1H NMR.展开更多
基金Supported by the Scientific Research Foundation of Higher Education Institutions of Ningxia(No.NGY2017004)the National Natural Science Foundation of China(Nos.21763022 and 50564043)the Major Innovation Projects for Building First-class Universities in China’s Western Region(No.ZKZD2017003)
文摘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.
文摘A one-pot three component condensation synthesis of imidazo[1,5-a]pyridines using of various aromatic aldehydes and dipyridil ketone with ammonium acetate in the presence of Lithium chloride as catalyst in good yields under microwave irradiation has been described.
基金supported by the Natural Science Foundation of Shandong Province(ZR2011BL020,ZR2012CM019)National Natural Science Foundation of China(21451001)Key Discipline and Innovation Team of Qilu Normal University
文摘One novel nickel coordination polymer, {[Ni(OTP)(bib)1.5(H2O)]·2H2O}n(1, H2 OTP = 2-hydroxy-5-(3',5'-terephthalic acid) pyridine, bib = 1,4-bis(1-imdazoly)benzene), has been synthesized and characterized by elemental analysis(EA), IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. The crystal of 1 crystallizes in monoclinic, space group P21/n with a = 12.2860(5), b = 13.8246(6), c = 19.0140(8) A, β = 104.3870(1)°, V = 3128.2(2) A3, Z = 4, C32H28N7 Ni O8, Mr = 697.32, Dc = 1.481 g/cm^3, F(000) = 1444 and μ(Mo Kα) = 0.684 mm-1. The final R = 0.0704 and w R = 0.1764 for 5485 observed reflections with I 2σ(I) and R = 0.1087 and wR = 0.2010 for all data. Topology analysis reveals that complex 1 is a 3D 2-fold interpenetrated {4^4·6^6}-nov net based on the 1D [Ni(OTP)]n chain and the 2D [Ni2(bib)3]n sql sheet. And the variable-temperature magnetic susceptibility measurements exhibit weak antiferromagnetic coupling interaction.
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.
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.
基金This work was supported by the NNSFC (No. 20372057) the NSF of Jiangsu Province (No. BK2001142)+2 种基金 the Open Foundation of Key Laboratory of Organic Synthesis of Jiangsu Province College of Chemistry and Chemical Engineering Suzhou University (No. S
文摘The title compound (C20H15ClN4O, Mr = 362.81) was synthesized by the reaction of ethyl 2-cyano-3-(2-chlorophenyl)-1-acylate with 5-amino-3-methyl-1-phenylpyrazole under microwave irradiation and its structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 8.8192(19), b = 15.976(3), c = 13.094(3) ? = 103.074(4), V = 1797.1(7) ?, Z = 4, Dc = 1.341 g/cm3, = 0.229 mm-1, F(000) = 752, R = 0.0632 and wR = 0.1278. X-ray analysis reveals that the pyridine ring adopts an envelope conformation. The dihedral angle between the pyrazole and pyridine planes is 2.19, and inter- molecular hydrogen bonds are also observed in the molecule.
文摘The synthesis process of 2-mercapto-5-methoxyimidazo[4,5-b]pyridine, a crucial intermediate of tenatoprazole which is a new proton pump inhibitor, was studied.2,6-Dichloropyridine as raw material was nitrated by nitric acid/sulfuric acid, and after amination 2-amino-3-nitro-6-chloropyridine was obtained.It then reacted with sodium methoxide to give 2-amino-3-nitro-6-methoxypyridine and the intermediate was reduced by H2 with Raney Ni as catalyst to give 2,3-diamino-6-methoxypyridine.Finally cyclization was finished with carbon bisulfide to give the title compound.The optimal reaction conditions and yield(temperature, time, molar yield) were as follows: nitration,110℃, 8 h, 79.3%; amination, room temperature, 10 h, 87.6%; methoxylation,65℃, 30min, 98.7%; reduction,70℃, 3 h; cyclization, reflux, 4 h, 72.4% (two steps).The melting point of the title compound was the same as that reported in literature, and its structure was confirmed by 1H NMR.