The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as differen...The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.展开更多
The crystal of the title compound (C36H29N3O,Mr = 519.62) has been prepared and structurally determined by X-ray single-crystal diffraction. It crystallizes in triclinic P space group with the crystal cell parameters:...The crystal of the title compound (C36H29N3O,Mr = 519.62) has been prepared and structurally determined by X-ray single-crystal diffraction. It crystallizes in triclinic P space group with the crystal cell parameters: a = 12.544(4), b = 14.112(4), c = 17.770(5)? = 96.150(6), = 106.112(5), = 107.156(5)? V = 2825.7(14) 3, Z = 4, Dc = 1.221g/cm3, (MoK? = 0.074 mm-1 , F(000) = 1096,the final R = 0.0747 and wR = 0.1632 for 4713 observed reflections with I >2(I). The E-stereochemistry of the title compound can be confirmed by the result of the X-ray diffraction analysis.展开更多
A new aromatic diamine,3,5-diaminobenzoylpiperazine （3,5-DABP）,was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3...A new aromatic diamine,3,5-diaminobenzoylpiperazine （3,5-DABP）,was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride （TMC） as organic monomer,thin film composite （TFC） nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4MgSO4MgCl2NaCl.This sequence indicates that the membranes are negatively charged.展开更多
Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic com...Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.展开更多
A novel series of diaryl urea derivatives bearing sulfonamide moiety have been designed and synthesized. Their in vitro antitumor effect against human cancer cell lines MX-1, A375, HepG2, Ketr3 and HT-29 was screened ...A novel series of diaryl urea derivatives bearing sulfonamide moiety have been designed and synthesized. Their in vitro antitumor effect against human cancer cell lines MX-1, A375, HepG2, Ketr3 and HT-29 was screened and evaluated by the standard MTT assay with sorafenib as the positive control. Some of the compounds showed significant inhibitory activity against multiple cell lines compared to sorafenib. In particular, 2,6-dimethyl-4-{6-[3-（4-chloro-3-（trifluoromethyl）phenyl）urealnaphthalen- 2-yllsulfonyl morpholine （10d） was found to be the most potent against A375, HepG2 and Ketr3 with ICs0 values of 0.65-0.97 μmol/L, which were 5-20-fold more potent than sorafenib. Compound 10d emerged as a valuable lead for further optimization.展开更多
An efficient approach for the synthesis of N-arylated amides was developed via copper(Ⅱ) triflate-catalyzed direct oxidation of(aryl)methylamines to primary arylamides by air and subsequent N-arylation by diaryliodon...An efficient approach for the synthesis of N-arylated amides was developed via copper(Ⅱ) triflate-catalyzed direct oxidation of(aryl)methylamines to primary arylamides by air and subsequent N-arylation by diaryliodonium salts. Various substituted benzylamines could be applied in the reaction, providing a series of N-arylated amides in moderate to good yields. This method showed convenient, practical, and environment friendly advantages.展开更多
Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1....Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1.54 to 1.66 dL/g. The precipitated PSA copolymers with feed content of p-phenylene diamine （PPD） being less than 50% （mole fraction） can be redissolved in N-methyl-2-pryrrolidone （NMP） or N, N-dimethylacetamide （DMAc） with lithium chloride of WLiC1 ： 0.02. All of the PSA copolymers exhibit enhanced tensile strength in comparison with PSA and still maintain excellent thermal stability in either air or nitrogen atmosphere展开更多
文摘The rate constants of the nucleophilic reactions between amines and benzhydrylium ions were calculated using first-principles theoretical methods. Solvation models including PCM, CPCM, and COSMORS, as well as different types of atomic radii including UA0, UAKS, UAHF, Bondi, and UFF, and several single-point energy calculation methods （B3LYP, B3P86, B3PW91, BHANDH, PBEPBE, BMK, M06, MP2, and ONIOM method） were examined. By comparing the correlation between experimental rate constants and the calculated values, the ONIOM（CCSD（T）/6-311＋＋G（2df,2p）：B3LYP/6-311＋＋G（2df,2p））//B3LYP/6- 31G（d）/PCM/UFF） method was found to perform the best. This method was then employed to calculate the rate constants of the reactions between diverse amines and diarylcarbenium ions. The calculated rate constants for 65 reactions of amines with diarylcarbenium ions are in agreement with the experimental values, indicating that it is feasible to predict the rate constant of a reaction between an amine and a diarylcarbenium ion through ab initio calculation.
基金This work was supported by the NNSFC (No. 29832030 and 20072018)
文摘The crystal of the title compound (C36H29N3O,Mr = 519.62) has been prepared and structurally determined by X-ray single-crystal diffraction. It crystallizes in triclinic P space group with the crystal cell parameters: a = 12.544(4), b = 14.112(4), c = 17.770(5)? = 96.150(6), = 106.112(5), = 107.156(5)? V = 2825.7(14) 3, Z = 4, Dc = 1.221g/cm3, (MoK? = 0.074 mm-1 , F(000) = 1096,the final R = 0.0747 and wR = 0.1632 for 4713 observed reflections with I >2(I). The E-stereochemistry of the title compound can be confirmed by the result of the X-ray diffraction analysis.
基金Supported by the National Natural Science Foundation of China（21076176） the Research and Development Project of Tangshan（10140201C-3）+1 种基金 the Research and Development Project of Hebei Province（07275113） the Research Fund of Tangshan Normal College
文摘A new aromatic diamine,3,5-diaminobenzoylpiperazine （3,5-DABP）,was synthesized from 3,5-diaminobenzoic acid and 1-formyl piperazine.The structure of 3,5-DABP was identified by FT-IR spectra and 1H NMR spectra.With 3,5-DABP as aqueous monomer and trimesoyl chloride （TMC） as organic monomer,thin film composite （TFC） nanofiltration membranes were prepared by interfacial polymerization technology.The salt rejection order of these TFC membranes is Na2SO4MgSO4MgCl2NaCl.This sequence indicates that the membranes are negatively charged.
文摘Peculiarities of a liquid phase hydrogenation, namely lower diffusivity of components influencing the reaction rate and deactivation of catalysts by leaching, are discussed. A focus is on hydrogenation of aromatic compounds, whereas the following processes are evaluated： （l） partial hydrogenation of benzene to cyclohexene; （2） hydrogenation of aniline; （3） hydrogenation of diphenylamine; （4） preparation of aniline from nitrobenzene; （5） hydrogenation of chloronitrobenzenes; （6） hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture. Processes （1） and （6） are typically carried out in the water-oil system. Generally, this type of system allows reaching a higher selectivity to desired products. In the case of hydrogenation of 4-nitrosodiphenylamine and 4-nitrodiphenylamine mixture, the water phase extracts a water soluble catalyst; which is recycled and used for condensation of aniline and nitrobenzene. Problems of reaction kinetics, as well as catalysts deactivation are here discussed.
基金financially supported by the National Science&Technology Major Project(2009ZX09301-003-9-1)
文摘A novel series of diaryl urea derivatives bearing sulfonamide moiety have been designed and synthesized. Their in vitro antitumor effect against human cancer cell lines MX-1, A375, HepG2, Ketr3 and HT-29 was screened and evaluated by the standard MTT assay with sorafenib as the positive control. Some of the compounds showed significant inhibitory activity against multiple cell lines compared to sorafenib. In particular, 2,6-dimethyl-4-{6-[3-（4-chloro-3-（trifluoromethyl）phenyl）urealnaphthalen- 2-yllsulfonyl morpholine （10d） was found to be the most potent against A375, HepG2 and Ketr3 with ICs0 values of 0.65-0.97 μmol/L, which were 5-20-fold more potent than sorafenib. Compound 10d emerged as a valuable lead for further optimization.
基金This work was financially supported by the National Nature Science Foundation of China(21272069,20672035)the Fundamental Reearch Funds for the Central Universities and Key Laboratory of Organofluorine Chemistry,Shanghai Institute of Organic Chemistry,Chinese Academy of Sciences.
文摘An efficient approach for the synthesis of N-arylated amides was developed via copper(Ⅱ) triflate-catalyzed direct oxidation of(aryl)methylamines to primary arylamides by air and subsequent N-arylation by diaryliodonium salts. Various substituted benzylamines could be applied in the reaction, providing a series of N-arylated amides in moderate to good yields. This method showed convenient, practical, and environment friendly advantages.
基金the National Natural Science Foundation of China (No. 50973059)the Scientific Research Foundation of 2009 Graduate School of Shanghai University
文摘Various polysulfonamide （PSA） statistical copolymers were synthesized by polycondensation of three aromatic diamines and terephthaloyl chloride. The inherent viscosities of the resulting PSA copolymers range from 1.54 to 1.66 dL/g. The precipitated PSA copolymers with feed content of p-phenylene diamine （PPD） being less than 50% （mole fraction） can be redissolved in N-methyl-2-pryrrolidone （NMP） or N, N-dimethylacetamide （DMAc） with lithium chloride of WLiC1 ： 0.02. All of the PSA copolymers exhibit enhanced tensile strength in comparison with PSA and still maintain excellent thermal stability in either air or nitrogen atmosphere
