A series of novel -aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified ...A series of novel -aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, 1H NMR, 13 C NMR and elemental analysis. The crystal structure of diethyl[(4-cyano-1H-pyrazol-3-ylamino)(3,5-difluorophenyl)methyl]phosphonate(4a, C15H17F2N4O3P) was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1 with a = 8.381(3), b = 10.103(5), c = 11.268(3) , = 83.772(19), = 74.726(19), = 70.964(18), V = 869.9(6) 3, Mr = 370.30, Dc = 1.414 g/cm3, Z = 2, F(000) = 384, = 0.200 mm-1, Mo Ka radiation( = 0.71073 ), the final R = 0.0487 and w R = 0.0823 for 1582 observed reflections with I > 2(I). X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51. Two intermolecular hydrogen bonds and a face-to-face ··· stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/m L, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/m L. Unfortunately, all of the compounds showed weak antitumor activities.展开更多
The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline(1) and 3-(4-fluoro-3-methylphenyl)quinoline(2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic aci...The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline(1) and 3-(4-fluoro-3-methylphenyl)quinoline(2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids.The title compounds were characterized by single-crystal X-ray diffraction,1H NMR,13C NMR,EI-MS,elemental analysis and IR.The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline(C17H9F6N,Mr = 341.25) belongs to the monoclinic system,space group P21n,a = 12.3072(13),b = 4.9378(6),c = 24.493(2) ,V = 1473.1(3) 3,Z = 4,Dc = 1.539 Mg m-3,λ = 0.71073 ,μ = 0.144 mm-1,F(000) = 688,the final R = 0.0715 and wR = 0.1873 for 1875 observed reflections with I > 2σ(I) and the crystal of 3-(4-fluoro-3-methylphenyl)quinoline(C16H12FN,Mr = 237.27) belongs to the orthorhombic system,space group Pca21,a = 23.794(2),b = 3.9094(3),c = 25.669(2) ,V = 2387.7(4) 3,Z = 8,Dc = 1.320 Mg m-3,λ = 0.71073 ,μ = 0.088 mm-1,F(000) = 992,the final R = 0.0534 and wR = 0.1188 for 2270 observed reflections with I > 2σ(I).展开更多
A new copper(Ⅱ)-2,2-biimidazole metal-organic POMs-supported compound[Cu(H2biim)2]{[Cu(H2biim)2]2[H10W12O44]}·8H2O(H2biim=2,2-biimidazole)has been successfully synthesized under hydrothermal conditions and chara...A new copper(Ⅱ)-2,2-biimidazole metal-organic POMs-supported compound[Cu(H2biim)2]{[Cu(H2biim)2]2[H10W12O44]}·8H2O(H2biim=2,2-biimidazole)has been successfully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and TG.The crystal adopts space group P1 with a=11.800(2),b=13.437(3),c=13.685(3),V=1922.5(7)3,Dc=3.507 g/cm3,C36H62Cu3N24W12O52,Mr=4059.92,F(000)=1837,μ=18.796 mm-1,Z=1,R=0.0579 and wR=0.1465 for 8734 observed reflections(I>2(I)).X-ray crystallography analysis exhibits that the title compound consists of one[H10W12O44]6-polyanion and three[Cu(H2biim)2]units.And significantπ-πstacking interactions and intermolecular O–H···O or N–H···O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.Thermal stability and magnetic property of the complex have also been investigated.展开更多
The title compound N-4-methyl-1,2,3-thiadiazole-5-carbonyl-N?-3,5-dichloro-4- (1,1,2,2- tetrafluoroethoxyl)phenyl urea (C13H8Cl2F4N4O3S, Mr = 447.19) has been synthesized from 4-methyl- 1,2,3-thiadiazole-5-carbonyl ch...The title compound N-4-methyl-1,2,3-thiadiazole-5-carbonyl-N?-3,5-dichloro-4- (1,1,2,2- tetrafluoroethoxyl)phenyl urea (C13H8Cl2F4N4O3S, Mr = 447.19) has been synthesized from 4-methyl- 1,2,3-thiadiazole-5-carbonyl chloride as the starting material, and its structure was characterized by proton Nuclear Magnetic Resonance (1H NMR), Infra Red Spectroscopy (IR), high-resolution mass spectroscopy (HRMS), and single-crystal X-ray diffraction. The crystal of the title compound belongs to triclinic, space group P with a = 6.0780(8), b = 11.3760(14), c = 12.1440(18) , α = 96.887(7), β = 91.027(12), γ = 104.252(13)°, Z = 2, V = 806.98(19) ·3, Dc = 1.840 g/cm3, μ = 0.601 mm-1, F(000) = 448, R = 0.0450 and wR = 0.0869. X-ray analysis indicates that the 1,2,3-thiadiazole ring is not coplanar with the phenyl ring, and the dihedral angle is 33.57°. Two intermolecular hydrogen bonds N(2)-H…O(1), S(1)…H-C(11), and three weak intermolecular interactions, C(11)…O(1), N(1)…O(2) and S…O(1), are observed. The bioassay results indicate that the title compound has good insecticidal activity against Culex pipiens pallens and good induction activity for tobacco against tobacco mosaic virus which is equal to that of TDL.展开更多
The title compound (E)-ethyl 2-fluoro-2-(3-oxoisobenzofuran-1(3H)-ylidene) acetate was synthesized as an unexpected product by the reaction of phthalyl dichloride with bis-silylenol ether, which is not in accordance w...The title compound (E)-ethyl 2-fluoro-2-(3-oxoisobenzofuran-1(3H)-ylidene) acetate was synthesized as an unexpected product by the reaction of phthalyl dichloride with bis-silylenol ether, which is not in accordance with our previous studies. The title compound was characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, 19F NMR, GCMS, HRMS and IR. The crystal (C12H9FO4, Mr = 236.19) belongs to the monoclinic system, space group P21/c, a = 19.1609(8), b = 7.9831(3), c = 13.7715(6) , V = 2106.13(15) 3, Z = 8, Dx = 1.490 Mg m-3, MoKα radiation, λ = 0.71073, μ = 0.12 mm-1, F(000) = 976, the final R = 0.025 and wR = 0.1300 for 4505 observed reflections with I > 2σ(I).展开更多
A new crystal of(E)-2-(2,4-dichlorophenoxy)-1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)vinyl 2-(2,4-dichlorophenoxy)acetate has been determined by single-crystal X-ray diffraction. The compound crystallizes in...A new crystal of(E)-2-(2,4-dichlorophenoxy)-1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)vinyl 2-(2,4-dichlorophenoxy)acetate has been determined by single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1 with a = 7.9393(17), b = 11.974(3) ?, c = 13.532(3) ?, α = 90.937(4), β = 101.998(3), γ = 101.363(4)°, V = 1231.5(5) ?3, Dc = 1.500 Mg/m3, Z = 2, F(000) = 568 and μ = 0.585 mm^(-1). The molecular packing in the crystal is the result of C(10)–H(10)···O(5) hydrogen bond, as well as weak π-π stacking interactions. The herbicidal activity results indicated that the title compound 3 showed 80~100% inhibitory activities against all of the tested weeds at a dosage of 150 g×ai/ha.展开更多
2-Benzyl-7-butoxyl-9-isobutyl-1-methyl-β-carboline bromide(H-2-65) was synthesized by the reaction of Harmine with 1-iodobutane via N9-alkylation, demethyl and N2-quaternarization to obtain the new compound. The resu...2-Benzyl-7-butoxyl-9-isobutyl-1-methyl-β-carboline bromide(H-2-65) was synthesized by the reaction of Harmine with 1-iodobutane via N9-alkylation, demethyl and N2-quaternarization to obtain the new compound. The results demonstrate that H-2-65 has more remarkable anticancer activities in vitro. The results of 1H NMR, 13 C NMR, DEPT, g COSY, g HSQC, g HMBC, MS, single-crystal X-ray diffraction and elemental analysis showed that the title compound crystallizes in the triclinic system, space group P1 with a = 9.545(5), b = 11.724(5), c = 11.839(6) , α = 77.530(6), β = 87.169(6), γ = 72.823(5)o, Z = 2, V = 1235.8(10)3, Dc = 1.294 g·cm-3, F(000) = 504, the final R = 0.0453, wR = 0.1262 and S = 1.044.展开更多
The title compound, 1-(naphthalene-2-yl)-2-(1H-pyrazol-1-yl)ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-...The title compound, 1-(naphthalene-2-yl)-2-(1H-pyrazol-1-yl)ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-ray single crystal diffraction. Molecular geometry from X-ray experiment of I in the ground state was compared using the Density Functional Theory (DFT) with B3LYP/6-311G(d,p) basis set. In addition, DFT calculation, molecular electrostatic potentials (MEP) and frontier molecular orbitals of I were performed at the B3LYP/6-311G(d,p) level of the theory.展开更多
The structure of(E)-N-[(E)-3-[(1R,2R)-2-(3,4-dibromo-phenyl)-1-fluro-cyclopropyl]-allylidene]-2-θ-tolyl-acetamide(C_(21)H_(18)ONFBr_2,M_r=479.18)has been determined by X-ray singlecrystal diffraction and theoretical ...The structure of(E)-N-[(E)-3-[(1R,2R)-2-(3,4-dibromo-phenyl)-1-fluro-cyclopropyl]-allylidene]-2-θ-tolyl-acetamide(C_(21)H_(18)ONFBr_2,M_r=479.18)has been determined by X-ray singlecrystal diffraction and theoretical calculations to establish the configuration,stereochemistry and a stable conformation of the molecule.The compound crystallizes in the monoclinic space group P2_1/c,a=28.3452(10),b=4.9311(10),c=14.257(2)A,β=102.7654(10)°,V=1943.5(5)A^3 and Z=4.The structure has been refined to the final R=0.05 for the observed structure factors with I>3σ(I).Theoretical calculations in the ground state have been carried out for the compound studied using the Hartree-Fock(HF)and density functional theory(DFT)(B3LYP)with 6-31G(d,p)basis sets.The results show that the studied compound prefers the keto form.The compound involves intra-and intermolecular hydrogen bonding of C-H…O and C-H…F types,which further stabilize the structure and display a trans configuration for the C=N and C=C double bonds.The calculated results show that the predicted geometry can well reproduce the structural parameters.展开更多
基金supported by the Future Talent Project of JXAU(No.09003444)the Doctoral Research Foundation of JXAU(No.09004065)
文摘A series of novel -aminophosphonates containing pyrazole and fluorine moieties was designed and synthesized through ultrasonic-assisted condensation and solvent-free addition reactions. Their structures were verified by IR, 1H NMR, 13 C NMR and elemental analysis. The crystal structure of diethyl[(4-cyano-1H-pyrazol-3-ylamino)(3,5-difluorophenyl)methyl]phosphonate(4a, C15H17F2N4O3P) was determined by single-crystal X-ray diffraction. Compound 4a crystallizes in the triclinic system, space group P1 with a = 8.381(3), b = 10.103(5), c = 11.268(3) , = 83.772(19), = 74.726(19), = 70.964(18), V = 869.9(6) 3, Mr = 370.30, Dc = 1.414 g/cm3, Z = 2, F(000) = 384, = 0.200 mm-1, Mo Ka radiation( = 0.71073 ), the final R = 0.0487 and w R = 0.0823 for 1582 observed reflections with I > 2(I). X-ray diffraction analysis reveals that there are two planes in 4a, and the dihedral angle is 71.51. Two intermolecular hydrogen bonds and a face-to-face ··· stacking interaction are observed in the crystal structure. The compounds were evaluated for their antifungal, antiviral and antitumor activities, respectively. Among them, 4b, 4c, 4g and 4h exhibit good activities on Sclerotium rolfsii Sacc at 200 μg/m L, while 4b, 4c, 4f and 4g possess good anti-TMV activities at 500 μg/m L. Unfortunately, all of the compounds showed weak antitumor activities.
文摘The title compounds 3-(3,5-bis(trifluoromethyl)phenyl)quinoline(1) and 3-(4-fluoro-3-methylphenyl)quinoline(2) were synthesized through Suzuki-Miyaura Cross coupling reaction of 3-bromoquinoloine with aryl boronic acids.The title compounds were characterized by single-crystal X-ray diffraction,1H NMR,13C NMR,EI-MS,elemental analysis and IR.The crystals of 3-(3,5-bis(trifluoromethyl)phenyl)quinoline(C17H9F6N,Mr = 341.25) belongs to the monoclinic system,space group P21n,a = 12.3072(13),b = 4.9378(6),c = 24.493(2) ,V = 1473.1(3) 3,Z = 4,Dc = 1.539 Mg m-3,λ = 0.71073 ,μ = 0.144 mm-1,F(000) = 688,the final R = 0.0715 and wR = 0.1873 for 1875 observed reflections with I > 2σ(I) and the crystal of 3-(4-fluoro-3-methylphenyl)quinoline(C16H12FN,Mr = 237.27) belongs to the orthorhombic system,space group Pca21,a = 23.794(2),b = 3.9094(3),c = 25.669(2) ,V = 2387.7(4) 3,Z = 8,Dc = 1.320 Mg m-3,λ = 0.71073 ,μ = 0.088 mm-1,F(000) = 992,the final R = 0.0534 and wR = 0.1188 for 2270 observed reflections with I > 2σ(I).
基金supported by the Knowledge Innovation Program(No.KJCX2-EW-H01)of Chinese Academy of SciencesNational Natural Science Foundation of China(No.21003125,21073190)Natural Science Foundation of Fujian Province(2010J05040,2010J01057)
文摘A new copper(Ⅱ)-2,2-biimidazole metal-organic POMs-supported compound[Cu(H2biim)2]{[Cu(H2biim)2]2[H10W12O44]}·8H2O(H2biim=2,2-biimidazole)has been successfully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and TG.The crystal adopts space group P1 with a=11.800(2),b=13.437(3),c=13.685(3),V=1922.5(7)3,Dc=3.507 g/cm3,C36H62Cu3N24W12O52,Mr=4059.92,F(000)=1837,μ=18.796 mm-1,Z=1,R=0.0579 and wR=0.1465 for 8734 observed reflections(I>2(I)).X-ray crystallography analysis exhibits that the title compound consists of one[H10W12O44]6-polyanion and three[Cu(H2biim)2]units.And significantπ-πstacking interactions and intermolecular O–H···O or N–H···O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework.Thermal stability and magnetic property of the complex have also been investigated.
基金funded in part by grants from the National Natural Science Foundation of China (20872071)the Natural Science Foundation of Tianjin (10JCZDJC17500)+3 种基金the National Key Project for Basic Research (2010CB126105)the National Key Technology Research and Development Program (2011BAE06B02)the Foundation of Achievements Transformation and Spreading of Tianjin Agricultural Science and Technology(201002250)Tianjin Key Technology Research and Development Program (11ZCGYNC00100)
文摘The title compound N-4-methyl-1,2,3-thiadiazole-5-carbonyl-N?-3,5-dichloro-4- (1,1,2,2- tetrafluoroethoxyl)phenyl urea (C13H8Cl2F4N4O3S, Mr = 447.19) has been synthesized from 4-methyl- 1,2,3-thiadiazole-5-carbonyl chloride as the starting material, and its structure was characterized by proton Nuclear Magnetic Resonance (1H NMR), Infra Red Spectroscopy (IR), high-resolution mass spectroscopy (HRMS), and single-crystal X-ray diffraction. The crystal of the title compound belongs to triclinic, space group P with a = 6.0780(8), b = 11.3760(14), c = 12.1440(18) , α = 96.887(7), β = 91.027(12), γ = 104.252(13)°, Z = 2, V = 806.98(19) ·3, Dc = 1.840 g/cm3, μ = 0.601 mm-1, F(000) = 448, R = 0.0450 and wR = 0.0869. X-ray analysis indicates that the 1,2,3-thiadiazole ring is not coplanar with the phenyl ring, and the dihedral angle is 33.57°. Two intermolecular hydrogen bonds N(2)-H…O(1), S(1)…H-C(11), and three weak intermolecular interactions, C(11)…O(1), N(1)…O(2) and S…O(1), are observed. The bioassay results indicate that the title compound has good insecticidal activity against Culex pipiens pallens and good induction activity for tobacco against tobacco mosaic virus which is equal to that of TDL.
文摘The title compound (E)-ethyl 2-fluoro-2-(3-oxoisobenzofuran-1(3H)-ylidene) acetate was synthesized as an unexpected product by the reaction of phthalyl dichloride with bis-silylenol ether, which is not in accordance with our previous studies. The title compound was characterized by single-crystal X-ray diffraction, 1H NMR, 13C NMR, 19F NMR, GCMS, HRMS and IR. The crystal (C12H9FO4, Mr = 236.19) belongs to the monoclinic system, space group P21/c, a = 19.1609(8), b = 7.9831(3), c = 13.7715(6) , V = 2106.13(15) 3, Z = 8, Dx = 1.490 Mg m-3, MoKα radiation, λ = 0.71073, μ = 0.12 mm-1, F(000) = 976, the final R = 0.025 and wR = 0.1300 for 4505 observed reflections with I > 2σ(I).
基金supported in part by the National Natural Science Foundation of China(No.21172090 and 21472062)the Natural Science Foundation of Hubei Province(No.2014CFA111)excellent doctorial dissertation cultivation grant from Central China Normal University(No.2015YBYB116)
文摘A new crystal of(E)-2-(2,4-dichlorophenoxy)-1-(5,5-dimethyl-2-oxido-1,3,2-dioxaphosphinan-2-yl)vinyl 2-(2,4-dichlorophenoxy)acetate has been determined by single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1 with a = 7.9393(17), b = 11.974(3) ?, c = 13.532(3) ?, α = 90.937(4), β = 101.998(3), γ = 101.363(4)°, V = 1231.5(5) ?3, Dc = 1.500 Mg/m3, Z = 2, F(000) = 568 and μ = 0.585 mm^(-1). The molecular packing in the crystal is the result of C(10)–H(10)···O(5) hydrogen bond, as well as weak π-π stacking interactions. The herbicidal activity results indicated that the title compound 3 showed 80~100% inhibitory activities against all of the tested weeds at a dosage of 150 g×ai/ha.
基金Supported by the National Key Technology Research and Development Program of the Ministry of Science and Technology of China(No.2012BAI30B00)
文摘2-Benzyl-7-butoxyl-9-isobutyl-1-methyl-β-carboline bromide(H-2-65) was synthesized by the reaction of Harmine with 1-iodobutane via N9-alkylation, demethyl and N2-quaternarization to obtain the new compound. The results demonstrate that H-2-65 has more remarkable anticancer activities in vitro. The results of 1H NMR, 13 C NMR, DEPT, g COSY, g HSQC, g HMBC, MS, single-crystal X-ray diffraction and elemental analysis showed that the title compound crystallizes in the triclinic system, space group P1 with a = 9.545(5), b = 11.724(5), c = 11.839(6) , α = 77.530(6), β = 87.169(6), γ = 72.823(5)o, Z = 2, V = 1235.8(10)3, Dc = 1.294 g·cm-3, F(000) = 504, the final R = 0.0453, wR = 0.1262 and S = 1.044.
基金the Faculty of Arts and Sciences, Ondokuz Mayιs University, Turkey, for the use of the Stoe IPDSII diffractometer (purchased under grant No. F279 of the University Research Fund)
文摘The title compound, 1-(naphthalene-2-yl)-2-(1H-pyrazol-1-yl)ethanone O-butyl oxime, I, was synthesized. The crystal and molecular structures of I were determined by IR, 1H-NMR, mass spectrum, elemental analysis and X-ray single crystal diffraction. Molecular geometry from X-ray experiment of I in the ground state was compared using the Density Functional Theory (DFT) with B3LYP/6-311G(d,p) basis set. In addition, DFT calculation, molecular electrostatic potentials (MEP) and frontier molecular orbitals of I were performed at the B3LYP/6-311G(d,p) level of the theory.
文摘The structure of(E)-N-[(E)-3-[(1R,2R)-2-(3,4-dibromo-phenyl)-1-fluro-cyclopropyl]-allylidene]-2-θ-tolyl-acetamide(C_(21)H_(18)ONFBr_2,M_r=479.18)has been determined by X-ray singlecrystal diffraction and theoretical calculations to establish the configuration,stereochemistry and a stable conformation of the molecule.The compound crystallizes in the monoclinic space group P2_1/c,a=28.3452(10),b=4.9311(10),c=14.257(2)A,β=102.7654(10)°,V=1943.5(5)A^3 and Z=4.The structure has been refined to the final R=0.05 for the observed structure factors with I>3σ(I).Theoretical calculations in the ground state have been carried out for the compound studied using the Hartree-Fock(HF)and density functional theory(DFT)(B3LYP)with 6-31G(d,p)basis sets.The results show that the studied compound prefers the keto form.The compound involves intra-and intermolecular hydrogen bonding of C-H…O and C-H…F types,which further stabilize the structure and display a trans configuration for the C=N and C=C double bonds.The calculated results show that the predicted geometry can well reproduce the structural parameters.
