The title compound N1-（2-（4-bromo-2-nitrophenoxy）-2-dimethyl acyloxymethyl）-5-fluorouracil（C15H13BrFN3O7, Mr = 446.19） was synthesized and structurally characterized by ^1H-NMR, -（13）C-NMR, ESI-MS and single-c...The title compound N1-（2-（4-bromo-2-nitrophenoxy）-2-dimethyl acyloxymethyl）-5-fluorouracil（C15H13BrFN3O7, Mr = 446.19） was synthesized and structurally characterized by ^1H-NMR, -（13）C-NMR, ESI-MS and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a = 8.3325（6）, b = 10.1808（13）, c = 11.8194（16） A, α = 73.194（12）, β= 72.351（9）, γ = 89.509（8）o, V = 911.2（2） A^3, Z = 2, T = 300.79（10） K, μ（Cu Kα） = 3.578 mm^-1, Dc = 1.626 g/cm3, F（000） = 448.0, GOF = 1.060, 5723 reflections measured（8.232≤2θ≤139.592°）, 3339 unique（Rint = 0.0184, Rsigma = 0.0254） which were used in all calculations. The final R = 0.0517（I 〉 2s（I）） and wR = 0.1494（all data）. Hydrogen bonds and π-π interactions together stabilize the structure of the molecule. The preliminary biological test shows that the title compound has good antitumor activity against A549 in vitro and lower toxicity to normal cells.展开更多
The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geomet...The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geometries of the reactants,transition states, intermediates and products were optimized at the B3LYP/6-31+G* level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-311+G* level was individually investigated. Polarizable continuum models(PCM)were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3,does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the ratelimiting step is reduced by 56.53 kJ mol-1 in gas and 44.84 kJ mol 1in solvent, demonstrating a high catalytic efficiency of CuI.展开更多
The title compound has been synthesized and characterized crystallographicaUy. It is a co-crystal consisting of two different neutral zinc（H） complexes with Hbpbm （Hbpbm = 4- bromo-2-（benzimidazol-2-yl）phenol） a...The title compound has been synthesized and characterized crystallographicaUy. It is a co-crystal consisting of two different neutral zinc（H） complexes with Hbpbm （Hbpbm = 4- bromo-2-（benzimidazol-2-yl）phenol） and Hnpbm （Hnpbm = 2-（1-butylbenzimidazol-2-yl）phenol）. One is a monomeric mixed-ligand complex of [Zn（bpbm）（npbm）] 1 and the other a dimer of [Zn2（npbm）4] 2 with their ratio of 2：1. Thus the overall formula for the title compound is 21.2. Adjacent 1 and 2 are connected to each other by intermolecular hydrogen bonding interactions in the lattice. The crystal data： monoclinic, space group P21/c, a = 15.0141（12）, b = 20.9941（17）, c = 18.4686（15） A, β = 97.445（2）°, V = 5772.4（8） A^3, Mr= 2429.68, Z = 2, Dc = 1.398 g/cm^3,μ = 1.579 -1 mm , F（000） = 2504, R = 0.0637 and wR = 0.1771 for 6464 observed reflections （I 〉 2σ（I））. The geometrical structure for 1 has also been theoretically optimized and compared with the experimental one.展开更多
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 d...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.展开更多
苯胺或取代苯胺、二硫化碳与水合肼在氢氧化钾催化下经加成与取代反应合成了10种N(4)-取代氨基硫脲,随后在浓盐酸催化下分别与2-羟基-1-萘甲醛加成合成了10种未见报道的2-羟基-1-萘甲醛缩-N(4)-取代氨基硫脲.通过IR、1 H NMR与13 C NMR...苯胺或取代苯胺、二硫化碳与水合肼在氢氧化钾催化下经加成与取代反应合成了10种N(4)-取代氨基硫脲,随后在浓盐酸催化下分别与2-羟基-1-萘甲醛加成合成了10种未见报道的2-羟基-1-萘甲醛缩-N(4)-取代氨基硫脲.通过IR、1 H NMR与13 C NMR对标题化合物进行了结构表征;采用离体法初步测试了标题化合物对6种常见农作物真菌病源菌的抑菌活性,并推测其可能的构效关系.结果表明,标题化合物对水稻纹枯病菌、小麦赤霉病菌、番茄早疫病菌、黄瓜枯萎病菌、马铃薯晚疫病菌及辣椒疫霉病菌均表现出一定的抑菌活性,其抑菌活性大小与标题化合物N(4)-取代基中苯环所连取代基的类型与位置有关.展开更多
Remarkable progress was made in the development of white-light-emitting diodes （LEDs）. White LEDs provided a light element having a semiconductor InGaN light-emitting chip （blue or UV LEDs） and luminescent phospho...Remarkable progress was made in the development of white-light-emitting diodes （LEDs）. White LEDs provided a light element having a semiconductor InGaN light-emitting chip （blue or UV LEDs） and luminescent phosphors. Here we reported the sialon s-phase of （Sr,Eu）2A12Si10N14O4. Eu^2＋ activator ions that were substituted for the strontium site represented a new type of yeUow-green phosphor that could be excited by blue LEDs used for application in the fabrication of white LEDs.展开更多
The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the ...The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the “flux”method,where the st arting materials are solved in a melt,which is usually formed by excess CuO and BaO or a KCl/NaCl mixture.The crystals are produced by slow cooling of the heate d solvent.This method,however,suffers from several disadvantages: (1) the crystals are contaminated with the crucible material, (2) the crystals are difficult to remove from the crucible, (3) the crystals contain flux inclusions.展开更多
The crystal structure of 1-(1-t-butyl-5-methyl-4-pyrazolylcarbonyl)-3,5-dimeth- yl-1H-yl-pyrazole ([C14H20N4O]2, Mr = 520.68) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to tr...The crystal structure of 1-(1-t-butyl-5-methyl-4-pyrazolylcarbonyl)-3,5-dimeth- yl-1H-yl-pyrazole ([C14H20N4O]2, Mr = 520.68) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group P with a = 11.049(4), b = 11.313(4), c = 13.964(5) , ?= 69.085(6), b = 75.962(6), = 62.245(6), V = 1436.7(9) 3, Z = 2, Dc = 1.204 g/cm3, m = 0.079 mm-1, F(000) = 560, R = 0.0790 and wR = 0.1416 for 4729 unique reflections with 2635 observed ones (I > 2(I)). The results indicate that the pyrazole rings display aromaticity. The four pyrazole moieties are approximately coplanar in each case. The dihedral angles between planes 1 and 2, 3 and 4 are 40.99 and 10.77? respectively.展开更多
基金Gansu Province Science and Technology Bureau Program Funds(144FKCA065)
文摘The title compound N1-（2-（4-bromo-2-nitrophenoxy）-2-dimethyl acyloxymethyl）-5-fluorouracil（C15H13BrFN3O7, Mr = 446.19） was synthesized and structurally characterized by ^1H-NMR, -（13）C-NMR, ESI-MS and single-crystal X-ray diffraction. The compound crystallizes in triclinic, space group P1, with a = 8.3325（6）, b = 10.1808（13）, c = 11.8194（16） A, α = 73.194（12）, β= 72.351（9）, γ = 89.509（8）o, V = 911.2（2） A^3, Z = 2, T = 300.79（10） K, μ（Cu Kα） = 3.578 mm^-1, Dc = 1.626 g/cm3, F（000） = 448.0, GOF = 1.060, 5723 reflections measured（8.232≤2θ≤139.592°）, 3339 unique（Rint = 0.0184, Rsigma = 0.0254） which were used in all calculations. The final R = 0.0517（I 〉 2s（I）） and wR = 0.1494（all data）. Hydrogen bonds and π-π interactions together stabilize the structure of the molecule. The preliminary biological test shows that the title compound has good antitumor activity against A549 in vitro and lower toxicity to normal cells.
文摘The detailed mechanism of CuI-catalyzed C-O intramolecular coupling reaction of 2-(2-bromo-4-fluoro-phenyl)-1-cyclohexen-1-yl trifluoromethane–sulfonate was studied with the density functional theory(DFT). The geometries of the reactants,transition states, intermediates and products were optimized at the B3LYP/6-31+G* level. Meanwhile, the single point energy of species involved in gas and solvent at B3LYP/6-311+G* level was individually investigated. Polarizable continuum models(PCM)were applied to the dioxane and water solutions at the same level, respectively. Results show that the rate-limiting step, M3→TS3,does not change in different solutions. However, the activation energy in a dioxane solution is lower than that in water, which explains the previous experimental results. Compared with the non-catalyzed reaction process, the activation energy of the ratelimiting step is reduced by 56.53 kJ mol-1 in gas and 44.84 kJ mol 1in solvent, demonstrating a high catalytic efficiency of CuI.
基金This work was supported by the Natural Science Foundation of Guangdong Province (No. 06301028)
文摘The title compound has been synthesized and characterized crystallographicaUy. It is a co-crystal consisting of two different neutral zinc（H） complexes with Hbpbm （Hbpbm = 4- bromo-2-（benzimidazol-2-yl）phenol） and Hnpbm （Hnpbm = 2-（1-butylbenzimidazol-2-yl）phenol）. One is a monomeric mixed-ligand complex of [Zn（bpbm）（npbm）] 1 and the other a dimer of [Zn2（npbm）4] 2 with their ratio of 2：1. Thus the overall formula for the title compound is 21.2. Adjacent 1 and 2 are connected to each other by intermolecular hydrogen bonding interactions in the lattice. The crystal data： monoclinic, space group P21/c, a = 15.0141（12）, b = 20.9941（17）, c = 18.4686（15） A, β = 97.445（2）°, V = 5772.4（8） A^3, Mr= 2429.68, Z = 2, Dc = 1.398 g/cm^3,μ = 1.579 -1 mm , F（000） = 2504, R = 0.0637 and wR = 0.1771 for 6464 observed reflections （I 〉 2σ（I））. The geometrical structure for 1 has also been theoretically optimized and compared with the experimental one.
基金This work was supported by the National Natural Science Foundation of China (No. 20472072 and 20332060)the CAS Academician Foundation of Zhejiang Province
文摘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.
文摘苯胺或取代苯胺、二硫化碳与水合肼在氢氧化钾催化下经加成与取代反应合成了10种N(4)-取代氨基硫脲,随后在浓盐酸催化下分别与2-羟基-1-萘甲醛加成合成了10种未见报道的2-羟基-1-萘甲醛缩-N(4)-取代氨基硫脲.通过IR、1 H NMR与13 C NMR对标题化合物进行了结构表征;采用离体法初步测试了标题化合物对6种常见农作物真菌病源菌的抑菌活性,并推测其可能的构效关系.结果表明,标题化合物对水稻纹枯病菌、小麦赤霉病菌、番茄早疫病菌、黄瓜枯萎病菌、马铃薯晚疫病菌及辣椒疫霉病菌均表现出一定的抑菌活性,其抑菌活性大小与标题化合物N(4)-取代基中苯环所连取代基的类型与位置有关.
基金Project supported by the Economic Affair (95-EC-17-A-07-S1-043)the National Science Council (94-2113-M-002-030)
文摘Remarkable progress was made in the development of white-light-emitting diodes （LEDs）. White LEDs provided a light element having a semiconductor InGaN light-emitting chip （blue or UV LEDs） and luminescent phosphors. Here we reported the sialon s-phase of （Sr,Eu）2A12Si10N14O4. Eu^2＋ activator ions that were substituted for the strontium site represented a new type of yeUow-green phosphor that could be excited by blue LEDs used for application in the fabrication of white LEDs.
文摘The growth of crystals of the high T c oxide superconductors has been hampe red by the complexities of the materials and their phase diagrams.The most common crys tal growth technique adopted for these oxides is the “flux”method,where the st arting materials are solved in a melt,which is usually formed by excess CuO and BaO or a KCl/NaCl mixture.The crystals are produced by slow cooling of the heate d solvent.This method,however,suffers from several disadvantages: (1) the crystals are contaminated with the crucible material, (2) the crystals are difficult to remove from the crucible, (3) the crystals contain flux inclusions.
基金the Natural Science Foundation of Shandong Province (No. Y2003B01) and NNSFC (No. 20172031)
文摘The crystal structure of 1-(1-t-butyl-5-methyl-4-pyrazolylcarbonyl)-3,5-dimeth- yl-1H-yl-pyrazole ([C14H20N4O]2, Mr = 520.68) has been determined by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group P with a = 11.049(4), b = 11.313(4), c = 13.964(5) , ?= 69.085(6), b = 75.962(6), = 62.245(6), V = 1436.7(9) 3, Z = 2, Dc = 1.204 g/cm3, m = 0.079 mm-1, F(000) = 560, R = 0.0790 and wR = 0.1416 for 4729 unique reflections with 2635 observed ones (I > 2(I)). The results indicate that the pyrazole rings display aromaticity. The four pyrazole moieties are approximately coplanar in each case. The dihedral angles between planes 1 and 2, 3 and 4 are 40.99 and 10.77? respectively.
