The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic proc...The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic procedures were confirmed. Dichloronitrobenzene was obtained in 78.9% yield based on 2,6 dichloroaniline. The reaction of 2,6 dichloronitrobenzene and methyl cyanoacetate with potassium carbonate catalyst in N,N dimethyl formamide gave methyl 2 cyano 2 (3′ chloro 2′ nitrophenyl) acetate in 80.2% yield. The third procedure product 3 chloro 2 nitrophenylacetic acid was obtained by hydrolysis in 82.6% yield. Decarboxylation reaction of 3 chloro 2 nitrophenylacetic acid produced 3 chloro 2 nitrotoluene in 72.9% yield.The structure of products was identified by IR and NMR.展开更多
Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base...Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.展开更多
A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（...A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（trichloromethyl） carbonate（BTC, triphosgene） and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.展开更多
The title compound （R）-N′-[2-（4-methoxy-6-chloro）-pyrimidyl]-N-[3-methyl-2-（4- chlorophenyl）butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic ...The title compound （R）-N′-[2-（4-methoxy-6-chloro）-pyrimidyl]-N-[3-methyl-2-（4- chlorophenyl）butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic data： C17H18C12N4O3, Mr = 397.25, monoclinic, space group P21/c, a = 12.331（2）, b = 14.025（3）, c = 23.085（5） A, β = 99.607（4）°, Z = 8, V = 3936.2（13） A3, Dc = 1.341 g/cm^3, F（000） = 1648, R = 0.0718, wR = 0.1585 and/t（MoKα） = 0.353 mm^-1. The preliminary biological tests showed that the title compound has definite insecticidal and fungicidal activities.展开更多
Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic a...Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic and elemental analysis and single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1 with unit cell dime sions a = 8.7137(10), b = 10.2010(14), c = 10.6593(13), α = 62.671(9), β = 82.701(10), γ = 79.762(10), V = 827.21(8) ?3, Z = 2.展开更多
Objective 1-Bromo-3-chloro-5,5-dimethylhydantoin （BCDMH） is a solid oxidizing biocide for water disinfection.The objective of this study was to investigate the toxic effect of BCDMH on zebrafish.Methods The developm...Objective 1-Bromo-3-chloro-5,5-dimethylhydantoin （BCDMH） is a solid oxidizing biocide for water disinfection.The objective of this study was to investigate the toxic effect of BCDMH on zebrafish.Methods The developmental toxicity of BCDMH on zebrafish embryos and the dose-effect relationship was determined.The effect of BCDMH exposure on histopathology and tissue antioxidant activity of adult zebrafish were observed over time.Results Exposure to 4 mg/L BCDMH post-fertilization was sufficient to induce a number of developmental malformations,such as edema,axial malformations,and reductions in heart rate and hatching rate.The no observable effects concentration of BCDMH on zebrafish embryo was 0.5 mg/L.After 96 h exposure,the 50% lethal concentration （95% confidence interval （CI）） of BCDMH on zebrafish embryo was 8.10 mg/L （6.15-11.16 mg/L）.The 50% inhibitory concentration （95% CI） of BCDMH on hatching rate was 7.37 mg/L （6.33-8.35 mg/L）.Histopathology showed two types of responses induced by BCDMH,defensive and compensatory.The extreme responses were marked hyperplasia of the gill epithelium with lamellar fusion and epidermal peeling.The histopathologic changes in the gills after 10 days exposure were accompanied by significantly higher catalase activity and lipid peroxidation.Conclusion These results have important implications for studies on the toxicity and use of BCDMH and its analogs.展开更多
Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-d...Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-dichlorophenylacetic acid （2,4-DCPA）, 4-chlorophenylacetic acid （4-DCPA）, 4,4＂-dipyridyl （4,4＂-bipy）, 1,3-bis（4-pyridyl）propane（bpp） and AgNO3. Compound 1 crystallizes in monoclinic, space group P21/c with a = 10.035（2）, b = 17.796（3）, c = 16.448（2） A, fl = 104.086（2）°, V= 2705.9（2） A3, Dc = 1.893 g/cm-3, C28H23C12NsO6Ag2, Mr = 812.15, F（000） = 1608,μ（MoKot） = 1.615 mm-1, Z = 4, R = 0.0310, wR = 0.0832 for 4357 observed reflections （I 〉 20（/））, and R = 0.0362, wR = 0.0873 for all data. Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.840（2）, b = 24.971（5）, c = 9.3301（2）°, fl = 117.504（2）°, V= 2033.5（7） A3, Dc = 1.666 g/cm3, C2tH19C12N202Ag, Mr = 510.15, F（000） = 1024,/I（MoKa） = 1.273 mml, Z= 4, R = 0.0315 and wR = 0.0680 for 2853 observed reflections （1 〉 20（/）） and R = 0.0454, wR = 0.0736 for all data. Compound 3 crystallizes in monoclinic, space group P21/n with a = 15.472（4）, b = 9.000（2）, c = 16.262（4） A, fl = 112.049（4）°, V = 2099.0（8） A3, Dc = 1.562 g/cm-3, C2H22C1N203Ag, Mr = 493.73, F（000） = 1000, μ（MoKa） = 1.111 mm-1, Z = 4, R = 0.0296, wR = 0.0821 for 3059 observed reflections （I 〉 2δ-（I））, and R = 0.0398, wR = 0.0986 for all data. The complexes were characterized by elemental analysis, FT-IR, thermogravimetrie analysis （TGA） and X-ray single-crystal structure analysis. Fluorescence properties of complex 3 and PXRD of 1 and 2 have been studied. As a result, in complex 1, the Ag（I） ion is surrounded by two nitrogen atoms from two bipy ligands to form an infinite chain, and adjacent Ag-bipy chains produce ＂＇rungs＂ of a ladder by silver ions contact. And in complexes 2 and 3, the two-dimensional ,β-sheet like layers are obtained by Ag……Ag interactions.展开更多
A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has bee...A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650（2）, b = 12.240（2）, c = 19.760（4） A, α = 72.01（3）, β = 77.11（3）, γ = 83.48（3）°, V = 2609.4（9） A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F（000） = 1466, μ（MoKa） = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.展开更多
A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitri...A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%. The key step including the reaction of compound 5 with POCl3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.展开更多
A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structur...A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.展开更多
Structural and thermodynamic parameters of 16 chloro-phenol compounds in water solution were calculated and fully optimized by using Onsager model in self-consistent reaction field（SCRF） based on the B3LYP/6-311G＊...Structural and thermodynamic parameters of 16 chloro-phenol compounds in water solution were calculated and fully optimized by using Onsager model in self-consistent reaction field（SCRF） based on the B3LYP/6-311G＊＊ level.These quantum chemical parameters were used as theoretical descriptors to correlate with the experimental biodegradation rate constant（Kb） of 16 compounds by stepwise multiple linear regression.As a result,a three-parameter model including molecular average polarizability（α）,entropy（Sθ）,and molar heat capacity at constant volume（CVθ） were established for Kb prediction,which was proposed with correlation coefficient R2 = 0.894.α exhibits the most significant effect on Kb.Variance analysis and standard t-value test were applied to validate the model.As expected,this model exhibits good robustness and prediction ability,which can be used in Kb prediction of analogs.展开更多
Introduction It seems to be realized that a number of special reactions would occur owing to the three electron-withdrawing groups in the title compound 1(4-chloro-3,5-dinitrobenzotrifluoride（1;） and 2-chloro-3, 5-d...Introduction It seems to be realized that a number of special reactions would occur owing to the three electron-withdrawing groups in the title compound 1(4-chloro-3,5-dinitrobenzotrifluoride（1;） and 2-chloro-3, 5-dinitrobenzotrifluoride （1;）). Some of展开更多
（R）-2-Chloro-l-（m-chlorophenyl）ethanol,a precursor of（R）-3-chlorostyrene oxide which is the key chiral intermediate for the preparation of severalβ3-adrenergic receptor agonists was prepared in 40%yield and 99%...（R）-2-Chloro-l-（m-chlorophenyl）ethanol,a precursor of（R）-3-chlorostyrene oxide which is the key chiral intermediate for the preparation of severalβ3-adrenergic receptor agonists was prepared in 40%yield and 99%ee by the Lipozyme TL IM-catalyzed second resolution of the corresponding racemate in the presence of vinyl acetate.展开更多
Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by...Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.展开更多
The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- ...The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess展开更多
The total synthesis of the labeled componed from immediacetic acid through esterifying, reducing with LiAID: as a labeling agent, chlerinating and phosphory, lating reactions was first, reported in this paper.
A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl ...A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.展开更多
Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent...Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent molar absorption coefficient at 434 nm is 5.20×10 5 L·mol -1 ·cm -1 . The method has been applied to the determination of 5.0×10 -9 (content by weight) Cadmium(Ⅱ) in honey.展开更多
The title compound bis[-chloro-(o-chloro-benzylidene) hydrazine] (C14H8Cl4N2, Mr = 346.02) has been prepared, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic,...The title compound bis[-chloro-(o-chloro-benzylidene) hydrazine] (C14H8Cl4N2, Mr = 346.02) has been prepared, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 10.777(2), b = 6.456(2), c = 10.988(3) , b = 90.48(2), V = 764.5(3) 3, Z = 2, Dc = 1.503 g/cm3, F(000) = 348 and ?MoK? = 0.763 mm-1 (l = 0.71073 ?. The structure was refined to R = 0.0793 and wR = 0.2398 for 1694 observed reflections with I > 2s(I). The results of crystal structure determination show that both C(7) and C(7)a are of sp2 hybridization and there exists electronic conjugation in the aza-diene of -C=NN=C.展开更多
Three new compounds, including one chloro-furoeremophilanoid （1）, one eremophiladiolide （2）, a rare dimer of nor- furoeremophilanoid, ligulatrovine A （3）, and a known furoeremophilanolide （4）, were isolated fr...Three new compounds, including one chloro-furoeremophilanoid （1）, one eremophiladiolide （2）, a rare dimer of nor- furoeremophilanoid, ligulatrovine A （3）, and a known furoeremophilanolide （4）, were isolated from Ligularia atroviolacea. The structures of compounds 1-4 were elucidated by spectroscopic methods including 1D and 2D NMR experiments as well as X- ray diffraction study.展开更多
文摘The synthesis of 3 chloro 2 nitrotoluene using 2,6 dichloroaniline as starting material by diazotization, substitution, condensation, decarboxylic reaction was studied and the best conditions of the synthetic procedures were confirmed. Dichloronitrobenzene was obtained in 78.9% yield based on 2,6 dichloroaniline. The reaction of 2,6 dichloronitrobenzene and methyl cyanoacetate with potassium carbonate catalyst in N,N dimethyl formamide gave methyl 2 cyano 2 (3′ chloro 2′ nitrophenyl) acetate in 80.2% yield. The third procedure product 3 chloro 2 nitrophenylacetic acid was obtained by hydrolysis in 82.6% yield. Decarboxylation reaction of 3 chloro 2 nitrophenylacetic acid produced 3 chloro 2 nitrotoluene in 72.9% yield.The structure of products was identified by IR and NMR.
基金This work was supported by the National Natural Science Foundation of China.
文摘Coupling reaction of 4-chloro-7-H-pyrrolo[2,3-d]pyrimidine with 2,3,5-tri-O-acetyl -β-D-ribofuranosyl chloride under the basic condition was investigated. An abnormal coupling reaction, in which the heterocyclic base attacked at the carbon of 1,2-O-methylidene moiety instead of anomeric carbon of ribose was observed and the structure of products 5a, 5b were identified by NMR and X-Ray diffraction.
基金the National Natural Science Foundation of China(Nos.20806073 and 20876147)the National Key Technology Research and Development Program(No.2007BAI34B06) for financial support
文摘A series of（Z）-2-chloro-1,3-diarylpropen-1-ones were unexpectedly synthesized in moderate yields by treatment of easily available 2,3-epoxy-1,3-diarylpropan-1-ones with Vilsmeier reagent,which was derived from bis（trichloromethyl） carbonate（BTC, triphosgene） and DMF.A possible mechanism was also proposed,where sequential ring-opening,halogenation and elimination reactions were involved.
基金This work was sponsored by the National Key Technologies R & D Programs (No. 2004BA308A22-8)
文摘The title compound （R）-N′-[2-（4-methoxy-6-chloro）-pyrimidyl]-N-[3-methyl-2-（4- chlorophenyl）butyryl]-urea has been synthesized, and its crystal structure and biological behaviors were studied. Crystallographic data： C17H18C12N4O3, Mr = 397.25, monoclinic, space group P21/c, a = 12.331（2）, b = 14.025（3）, c = 23.085（5） A, β = 99.607（4）°, Z = 8, V = 3936.2（13） A3, Dc = 1.341 g/cm^3, F（000） = 1648, R = 0.0718, wR = 0.1585 and/t（MoKα） = 0.353 mm^-1. The preliminary biological tests showed that the title compound has definite insecticidal and fungicidal activities.
文摘Synthesis of the title compound was carried out by base-catalyzed cyclization of 1-pivaloyl-3-(2-chloro-4-nitrophenyl) thiourea with α-bromoacetone produced in situ. The structure was confirmed by the spectroscopic and elemental analysis and single crystal X-ray diffraction data. It crystallizes in the triclinic space group P-1 with unit cell dime sions a = 8.7137(10), b = 10.2010(14), c = 10.6593(13), α = 62.671(9), β = 82.701(10), γ = 79.762(10), V = 827.21(8) ?3, Z = 2.
基金supported by the National Science and Technology Major Project "Creation of Major New Drugs", 2008ZX09305-001
文摘Objective 1-Bromo-3-chloro-5,5-dimethylhydantoin （BCDMH） is a solid oxidizing biocide for water disinfection.The objective of this study was to investigate the toxic effect of BCDMH on zebrafish.Methods The developmental toxicity of BCDMH on zebrafish embryos and the dose-effect relationship was determined.The effect of BCDMH exposure on histopathology and tissue antioxidant activity of adult zebrafish were observed over time.Results Exposure to 4 mg/L BCDMH post-fertilization was sufficient to induce a number of developmental malformations,such as edema,axial malformations,and reductions in heart rate and hatching rate.The no observable effects concentration of BCDMH on zebrafish embryo was 0.5 mg/L.After 96 h exposure,the 50% lethal concentration （95% confidence interval （CI）） of BCDMH on zebrafish embryo was 8.10 mg/L （6.15-11.16 mg/L）.The 50% inhibitory concentration （95% CI） of BCDMH on hatching rate was 7.37 mg/L （6.33-8.35 mg/L）.Histopathology showed two types of responses induced by BCDMH,defensive and compensatory.The extreme responses were marked hyperplasia of the gill epithelium with lamellar fusion and epidermal peeling.The histopathologic changes in the gills after 10 days exposure were accompanied by significantly higher catalase activity and lipid peroxidation.Conclusion These results have important implications for studies on the toxicity and use of BCDMH and its analogs.
基金supported by the Guangdong Science and Technology Department(No.S2012020011054 and 2011B090400415)the Zhanjiang Municipality(No.2011C3108001)projects
文摘Three new coordination polymers {[Ag2（2,4-DCPA）（4,4＂-bipy）2（NO3）].（H20）}, （1）, [Ag（2,4-DCPA）（bpp）], （2） and {[Ag（4-DCPA）（bpp）]＇（H20）}, （3）, were synthesized by evaporation methods using 2,4-dichlorophenylacetic acid （2,4-DCPA）, 4-chlorophenylacetic acid （4-DCPA）, 4,4＂-dipyridyl （4,4＂-bipy）, 1,3-bis（4-pyridyl）propane（bpp） and AgNO3. Compound 1 crystallizes in monoclinic, space group P21/c with a = 10.035（2）, b = 17.796（3）, c = 16.448（2） A, fl = 104.086（2）°, V= 2705.9（2） A3, Dc = 1.893 g/cm-3, C28H23C12NsO6Ag2, Mr = 812.15, F（000） = 1608,μ（MoKot） = 1.615 mm-1, Z = 4, R = 0.0310, wR = 0.0832 for 4357 observed reflections （I 〉 20（/））, and R = 0.0362, wR = 0.0873 for all data. Compound 2 crystallizes in monoclinic, space group P21/c with a = 9.840（2）, b = 24.971（5）, c = 9.3301（2）°, fl = 117.504（2）°, V= 2033.5（7） A3, Dc = 1.666 g/cm3, C2tH19C12N202Ag, Mr = 510.15, F（000） = 1024,/I（MoKa） = 1.273 mml, Z= 4, R = 0.0315 and wR = 0.0680 for 2853 observed reflections （1 〉 20（/）） and R = 0.0454, wR = 0.0736 for all data. Compound 3 crystallizes in monoclinic, space group P21/n with a = 15.472（4）, b = 9.000（2）, c = 16.262（4） A, fl = 112.049（4）°, V = 2099.0（8） A3, Dc = 1.562 g/cm-3, C2H22C1N203Ag, Mr = 493.73, F（000） = 1000, μ（MoKa） = 1.111 mm-1, Z = 4, R = 0.0296, wR = 0.0821 for 3059 observed reflections （I 〉 2δ-（I））, and R = 0.0398, wR = 0.0986 for all data. The complexes were characterized by elemental analysis, FT-IR, thermogravimetrie analysis （TGA） and X-ray single-crystal structure analysis. Fluorescence properties of complex 3 and PXRD of 1 and 2 have been studied. As a result, in complex 1, the Ag（I） ion is surrounded by two nitrogen atoms from two bipy ligands to form an infinite chain, and adjacent Ag-bipy chains produce ＂＇rungs＂ of a ladder by silver ions contact. And in complexes 2 and 3, the two-dimensional ,β-sheet like layers are obtained by Ag……Ag interactions.
基金Supported by the Science and Technology Research Projects of the Education Committee of Jilin Province(No.2013212)
文摘A new Cd（II） coordination polymer, namely, [Cd3（1,2,3-BTC）2（L）2]·2.25H2O （1, L = 2-（2-chloro-6-fluorophenyl）-1H-imidazo[4,5-A][1,10]phenanthroline and 1,2,3-BTC = 1,2,3-ben- zenetricarboxylate）, has been synthesized under hydrothermal conditions. The compound was characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group Pī with α = 11.650（2）, b = 12.240（2）, c = 19.760（4） A, α = 72.01（3）, β = 77.11（3）, γ = 83.48（3）°, V = 2609.4（9） A3, Z = 2, C56H31Cd3Cl2F2N8O14.25, Mr = 1489.99, Dc = 1.896 g/cm3, F（000） = 1466, μ（MoKa） = 1.401 mm^-1, R = 0.0401 and wR = 0.1104. Compound 1 shows a 1D chain structure, and the neigh- boring 1D chains of 1 are joined together by π···π interactions to result in a 2D supramolecular layer. In addition, the luminescent property of 1 has been studied in the solid state at room temperature.
基金supported by Outstanding Youth Foundation of Heilongjiang Province(No.JC200706)
文摘A novel method for synthesis of 2-butyl-5 -chloro-3H-imidazole-4-carbaldehyde 2, a key intermediate of Losartan was reported. The compound 2 was synthesized from starting material dimethyl malonate 6 and n-valeronitrile 8 by six steps with an overall yield of 40%. The key step including the reaction of compound 5 with POCl3/DMF followed by hydrolysis to give compound 2 with the yield of 68%.
基金Supported by Key Laboratory of Organic Synthesis of Jiangsu Province(KJS1308)
文摘A novel two-dimensional lead（II） coordination polymer 1, [C11H7Cl2NO3Pb]n, has been prepared by solvothermal reaction of new bridging ligand（5-chloro-quinolin-8-yloxy）acetic acid（HL） with PbCl2, and its structure was characterized by IR, elemental analysis, TG-DTA and single-crystal X-ray diffraction analysis. The crystal is of monoclinic system, space group P21/c with a = 16.7603（7）, b = 8.6907（4）, c = 8.4745（3）A, β = 101.1110（11）°, C11H7Cl2NO3 Pb, Mr = 479.27, V = 1211.25（9）A3, Z = 4, Dc = 2.628 g/cm^3, F（000） = 880, μ = 14.367 mm^-1, R = 0.0173 and wR = 0.0508. The asymmetric unit contains one lead（II） cation, one（5-chloro-quinolin-8-yloxy）acetate（L） ligand and a chloride ion. The PbII center is hepta-coordinated in a distorted pentagonal bipyramidal geometry. The coordination sphere of the Pb atom is completed by two oxygen atoms and one nitrogen atom of the same L ligand, two bridging chloride ions and two bridging oxygen atoms of two adjacent L ligands. Two PbII centers are linked by the two L ligands to form a C2-symmetric dimer unit with a planar [Pb2O2] ring. Each dimer unit acts as a secondary building unit（SBU） and links adjacent four dimer units by the chloride atoms and oxygen atoms of carboxylate groups of L, forming a two-dimensional array. Such two-dimensional layers are packed through intermolecular C–H…Cl hydrogen bonds into a three-dimensional supramolecular structure. When the dimer unit is viewed as a 4-connected node, 1 is simplified as a 4-nodal 2-D network with square lattices of the diagonal lengths to be 6.079（1）A. The fluorescence emission peak of complex 1 appears near 407 nm.
基金Supported by the State Key Program of NNSFC (No. 20737001)NNSFC (No. 20977044)
文摘Structural and thermodynamic parameters of 16 chloro-phenol compounds in water solution were calculated and fully optimized by using Onsager model in self-consistent reaction field（SCRF） based on the B3LYP/6-311G＊＊ level.These quantum chemical parameters were used as theoretical descriptors to correlate with the experimental biodegradation rate constant（Kb） of 16 compounds by stepwise multiple linear regression.As a result,a three-parameter model including molecular average polarizability（α）,entropy（Sθ）,and molar heat capacity at constant volume（CVθ） were established for Kb prediction,which was proposed with correlation coefficient R2 = 0.894.α exhibits the most significant effect on Kb.Variance analysis and standard t-value test were applied to validate the model.As expected,this model exhibits good robustness and prediction ability,which can be used in Kb prediction of analogs.
文摘Introduction It seems to be realized that a number of special reactions would occur owing to the three electron-withdrawing groups in the title compound 1(4-chloro-3,5-dinitrobenzotrifluoride（1;） and 2-chloro-3, 5-dinitrobenzotrifluoride （1;）). Some of
基金support from the National Natural Science Foundation of China(No20672110)
文摘（R）-2-Chloro-l-（m-chlorophenyl）ethanol,a precursor of（R）-3-chlorostyrene oxide which is the key chiral intermediate for the preparation of severalβ3-adrenergic receptor agonists was prepared in 40%yield and 99%ee by the Lipozyme TL IM-catalyzed second resolution of the corresponding racemate in the presence of vinyl acetate.
基金Supported by the National Natural Science Foundation of China(No. 2 0 16 2 0 0 5 ) .
文摘Chloro 2 diethylaminoethyl 3(2H) pyridazinone was synthesized by the reaction of 6 chloro 3(2H) pyridazinone and 2 diethylamionethyl chloride reaction in methylbenzene. Then the structure was characterized by means of 1H NMR, IR, UV. By the method of ab initio HF and density functional theory (DFT) B3LYP, the geometric structures of the reagent intermediate, the product and its isomer were optimized and their total energies were calculated. The properties for the frontier molecular orbitals and the rules for energy distribution were analyzed systematically. It was shown that the energy of the nitrogen alkyl compound is lower than that of the oxy alkyl compound and the former is stable than the latter . This result is in accordance with the fact that 6 chloro 2 diethylaminoethyl 3(2H) pyridazinone is synthesized by the reaction of \{6 chloride \}2 diethylaminoethyl 3(2H) pyridazinone and 2 diethylaminoethyl chloride.
文摘The reaction of cis- 2- chloro- 4- phenyl- 5, 5- dimethyl- 1, 3. 2-dioxaghosghor inan-2- thione (Ⅰ) with methoxide or phenoxide at room temperatute takes place with retent ion of configuration. while refluxing cis- (1) and methoxide in methanol, gartial isomerization of cis-thioghosphate (2) to its trans isomer occursand an acyclic intermediate (3) is found to be involved in this grocess
文摘The total synthesis of the labeled componed from immediacetic acid through esterifying, reducing with LiAID: as a labeling agent, chlerinating and phosphory, lating reactions was first, reported in this paper.
文摘A series of new complexes, CpTiCl[S2P(OR)2]2 (where R) Et, n-Pr, i-Pr, Bui, Ph) and CpTiCl [S2POGO]2 (where G) –CH2CMe2CH2-, -CMe2CMe2-) have been prepared by the drop wise addition of the appropriate O, O’-dialkyl or -alkylene dithiophosphoric acid to cyclopentadienyl titanium trichloride in 1:2 molar ratio and refluxed in benzene solution. The new compounds were characterized by molecular weight measurements elemental analyses and spectroscopic studies (1H, 13C, and 31P NMR, and in-frared). We suggest a distorted tetrahedron structure of these new complexes and the dithioligand behaves as bidentate ligand.
文摘Synthesis of a new high sensitive water soluble chromogenic reagent mes o tetra (2 chloro 4 sulfophenyl)prophyrin and the conditions for the reaction of this reagent with cadmiun(Ⅱ) were studied. The apparent molar absorption coefficient at 434 nm is 5.20×10 5 L·mol -1 ·cm -1 . The method has been applied to the determination of 5.0×10 -9 (content by weight) Cadmium(Ⅱ) in honey.
基金This project was supported by the National Natural Science Foundation of China (20272053) and Natural Science Foundation of Zhejiang Province (200016)
文摘The title compound bis[-chloro-(o-chloro-benzylidene) hydrazine] (C14H8Cl4N2, Mr = 346.02) has been prepared, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/n with a = 10.777(2), b = 6.456(2), c = 10.988(3) , b = 90.48(2), V = 764.5(3) 3, Z = 2, Dc = 1.503 g/cm3, F(000) = 348 and ?MoK? = 0.763 mm-1 (l = 0.71073 ?. The structure was refined to R = 0.0793 and wR = 0.2398 for 1694 observed reflections with I > 2s(I). The results of crystal structure determination show that both C(7) and C(7)a are of sp2 hybridization and there exists electronic conjugation in the aza-diene of -C=NN=C.
基金part financially supported by DAAD-CSC PPP project (No.CSC [2004] 3067) and intramural foundation from Wenzhou Medical College.
文摘Three new compounds, including one chloro-furoeremophilanoid （1）, one eremophiladiolide （2）, a rare dimer of nor- furoeremophilanoid, ligulatrovine A （3）, and a known furoeremophilanolide （4）, were isolated from Ligularia atroviolacea. The structures of compounds 1-4 were elucidated by spectroscopic methods including 1D and 2D NMR experiments as well as X- ray diffraction study.
