Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room ...Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room temperature in CFCl2-CF2Cl.展开更多
Racemic 2-n-butylbutanedioic acid 4-t-butyl esters were synthesized from methyl hexanoate and t-butyl α-iodoacetate via alkylation and subsequently selective hydrolyzation. The （R）-and （S）-2-n-butylbutanedioic ac...Racemic 2-n-butylbutanedioic acid 4-t-butyl esters were synthesized from methyl hexanoate and t-butyl α-iodoacetate via alkylation and subsequently selective hydrolyzation. The （R）-and （S）-2-n-butylbutanedioic acid 4-t-butyl esters were obtained by the resolution of the above-mentioned racemic compounds with（S）-（ - ） or（R）-（ ＋ ）-α- methylbenzylamine, respectively. The e.e. values of the two optical active products were determined to be above 99% by HPLC after the formation of two pairs of diastereoisomers with（R）-（ ＋ ）-α-methylbenzylamine and（S）- phenylalanine methyl ester.展开更多
tert-Butylation of toluene with tert-butanol used as the alkylating agent was investigated over the activated bentonite and HY zeolite used as the catalyst.The influences of various butylation reaction parameters,incl...tert-Butylation of toluene with tert-butanol used as the alkylating agent was investigated over the activated bentonite and HY zeolite used as the catalyst.The influences of various butylation reaction parameters,including the toluene/tert-butanol ratio,the reaction temperature,and the space velocity were discussed.The optimal results were obtained at a reaction temperature of 180 ℃,a space velocity of 4 h-1,and a mole ratio of toluene to tert-butanol equating to 2.The structure and acidic properties of catalyst were characterized by the BET method and the Fourier transform infrared (FTIR) spectroscopy.Compared with the HY zeolite,the activated bentonite possessed high activity for toluene conversion and high para-selectivity because it had larger pore diameter,smaller micropore surface area and higher ratio of total Lewis acids to total Br nsted acids.展开更多
Three Ce 4+ complexes Ce(p tert butylcalixarene)·(dmf) 4·H 2O (complex A), Ce(p tert butylcalixarene) 2·(dmf) 10 (complex B) and Ce(p tert butylcalixarene)·(dmf) 4 (complex C) w...Three Ce 4+ complexes Ce(p tert butylcalixarene)·(dmf) 4·H 2O (complex A), Ce(p tert butylcalixarene) 2·(dmf) 10 (complex B) and Ce(p tert butylcalixarene)·(dmf) 4 (complex C) were prepared from N,N dimethylforamide (dmf) solution of Ce(NO 3) 3. Their thermal stability, optical properties and coordination features were investigated with thermogravimetric and differential thermal analysis, ultraviolet and visible spectrophotometer, fluorescence spectrophotometer, infrared spectroscopy, and 1H NMR spectrometer. In the solvents of C 6H 6, 1,2 dichloroethane and dmf, complexes A and B can exhibit a ligand to metal charge transfer transition lying in ca. 20000 cm -1 in the electronic spectra. Complex A displays a dimeric structure in C 6D 6 solution. Ce 4+ ions in the complexes are coordinated by phenolic groups of the ligands, oxygen atoms of dmf molecules, and / or OH - ions.展开更多
In the interest of driving down the cost of DCM-type light emitting materials, we have found a new approach to prepare 2-（t-butyl）-6-methy1-4H-pyrone, which is cost effective and more amenable to large scale product...In the interest of driving down the cost of DCM-type light emitting materials, we have found a new approach to prepare 2-（t-butyl）-6-methy1-4H-pyrone, which is cost effective and more amenable to large scale production than the reported method. Furthermore, three new DCM-type dyes, N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H- pyran-2-yl）-vinyl）-phenyl]-4-t-butyl-aniline （BDCM-BA）, N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H-pyran- 2-yl）-vinyl）-phenyl]aniline （BDCM-A） and N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H-pyran-2-yl）-vinyl）- phenyl]-4-methoxyl-aniline （BDCM-MA） were synthesized in good yields using 2-（t-butyl）-6-methyl-4H-pyrone as starting material. They can be utilized in OLEDs as nondoped red emitting materials as the result of the restricted concentration quenching effect.展开更多
The solubilities of benzene and diphenyl in mixed solvents of t-butyl alcohol(TBA) and water with different salts have been determined at T = 298.15, 303.15, 308.15 and 313.15K. The molar fraction of TBA [x(TBA)] in m...The solubilities of benzene and diphenyl in mixed solvents of t-butyl alcohol(TBA) and water with different salts have been determined at T = 298.15, 303.15, 308.15 and 313.15K. The molar fraction of TBA [x(TBA)] in mixed solvent is 0.045, and the molality of the salts (m_s)in mixed solvents are 0.000, 0.250, 0.500, 0.750 and 1.000 mol/kg, respectively. The standard Gibbsenergies of solution of benzene and diphenyl in the mixed solvents have also been calculated basedon the solubility data. The effects of different salts on the hydrophobic interaction (HI) forbenzene-benzene pair in the systems were discussed.展开更多
A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = B...A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.展开更多
The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TB...The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100, respectively. The standard Gibbs energies of solution of benzene, toluene and diphenyl in the mixed solvent have also been calculated based on the solubility data. The hydrophobic interactions (HI) for the pairs of benzene-benzene, methane-benzene and methane-methane in the mixed solvent were calculated and discussed.展开更多
A series of novel 3-（（4-（t-buty-）-2-（2-benzylidenehydrazinyl）thiazol-5-yl）methyl）quinolin-2（1H）-ones （7a--7z） were designed, synthesized and evaluated for their ability of inhibiting neuraminidase （NA） o...A series of novel 3-（（4-（t-buty-）-2-（2-benzylidenehydrazinyl）thiazol-5-yl）methyl）quinolin-2（1H）-ones （7a--7z） were designed, synthesized and evaluated for their ability of inhibiting neuraminidase （NA） of influenza H1N1 virus. Some compounds displayed moderate influenza NA inhibitory activity. Compound 71 with the scaffold of 2-（2-（2-methoxybenzylidene）hydrazinyl）thiazole was the best one, exhibiting moderate NA inhibitory activity with ICs0 of 44.66 ~tmol/L. Structure-activity relationship showed that compounds with methoxy or hydroxy groups at the ortho position, fluorine and nitro groups at the meta position and chlorine and bromine groups at the para posi- tion of phenyl ring were more active. Docking study indicated that compound 71 has important interactions with some key residues （including Asp151, Glu119, Arg292, Tyr406, and Asn347） and binds to 430-cavity adjacent to NA active site.展开更多
Three substituted α,β,β-trifluorostyrenes(TFS's),i.e.,p-thiomethyltrifluorostyrene(4), p-cyclopropyltrifluorostyrene(5)and p-t-butyltrifluorostyrene(6),have been synthesized.The rate constants(k_2)of the therma...Three substituted α,β,β-trifluorostyrenes(TFS's),i.e.,p-thiomethyltrifluorostyrene(4), p-cyclopropyltrifluorostyrene(5)and p-t-butyltrifluorostyrene(6),have been synthesized.The rate constants(k_2)of the thermal cyclodimerization of these compounds have been measured in the tem- perature range 120—160℃.The polar parameters σ_(mb) of these TFS's calculated from ^(19)F NMR chemi- cal shifts are:for p-thiomethyl,-0.18;p-cyclopropyl,-0.31 and p-t-butyl,-0.22.The spin delo- calization substituent parameters σ'_T(140°)of p-thiomethyl,cyclopropyl and t-butyl groups are 0.59, 0.27 and 0.30 respectively.Thus all of these groups act as electron-donating groups which can also effectively stabilize a spin.展开更多
文摘Electron transfer reactions between O-benzoyl t-butylhydroxyl- amine,t-BuNHOCOPh(1)and perfluorodiacyl peroxides(RfCO_2)_2(2)may serve as a novel method for generating useful t-hutyl perfluoroalkyl nitroxldes at room temperature in CFCl2-CF2Cl.
基金Supported by the National Basic Research Priority Program(No. 2003CCA027).
文摘Racemic 2-n-butylbutanedioic acid 4-t-butyl esters were synthesized from methyl hexanoate and t-butyl α-iodoacetate via alkylation and subsequently selective hydrolyzation. The （R）-and （S）-2-n-butylbutanedioic acid 4-t-butyl esters were obtained by the resolution of the above-mentioned racemic compounds with（S）-（ - ） or（R）-（ ＋ ）-α- methylbenzylamine, respectively. The e.e. values of the two optical active products were determined to be above 99% by HPLC after the formation of two pairs of diastereoisomers with（R）-（ ＋ ）-α-methylbenzylamine and（S）- phenylalanine methyl ester.
文摘tert-Butylation of toluene with tert-butanol used as the alkylating agent was investigated over the activated bentonite and HY zeolite used as the catalyst.The influences of various butylation reaction parameters,including the toluene/tert-butanol ratio,the reaction temperature,and the space velocity were discussed.The optimal results were obtained at a reaction temperature of 180 ℃,a space velocity of 4 h-1,and a mole ratio of toluene to tert-butanol equating to 2.The structure and acidic properties of catalyst were characterized by the BET method and the Fourier transform infrared (FTIR) spectroscopy.Compared with the HY zeolite,the activated bentonite possessed high activity for toluene conversion and high para-selectivity because it had larger pore diameter,smaller micropore surface area and higher ratio of total Lewis acids to total Br nsted acids.
文摘Three Ce 4+ complexes Ce(p tert butylcalixarene)·(dmf) 4·H 2O (complex A), Ce(p tert butylcalixarene) 2·(dmf) 10 (complex B) and Ce(p tert butylcalixarene)·(dmf) 4 (complex C) were prepared from N,N dimethylforamide (dmf) solution of Ce(NO 3) 3. Their thermal stability, optical properties and coordination features were investigated with thermogravimetric and differential thermal analysis, ultraviolet and visible spectrophotometer, fluorescence spectrophotometer, infrared spectroscopy, and 1H NMR spectrometer. In the solvents of C 6H 6, 1,2 dichloroethane and dmf, complexes A and B can exhibit a ligand to metal charge transfer transition lying in ca. 20000 cm -1 in the electronic spectra. Complex A displays a dimeric structure in C 6D 6 solution. Ce 4+ ions in the complexes are coordinated by phenolic groups of the ligands, oxygen atoms of dmf molecules, and / or OH - ions.
基金Project supported by the National Natural Science Foundation of China （Nos. 20272065 and 50125310）, 863 （No. 90101013）, 973 （Nos. 2002AA324080 and 2002CB613405） Program of China. Dedicated to Professor Xikui Jiang on the occasion of his 80th birthday.
文摘In the interest of driving down the cost of DCM-type light emitting materials, we have found a new approach to prepare 2-（t-butyl）-6-methy1-4H-pyrone, which is cost effective and more amenable to large scale production than the reported method. Furthermore, three new DCM-type dyes, N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H- pyran-2-yl）-vinyl）-phenyl]-4-t-butyl-aniline （BDCM-BA）, N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H-pyran- 2-yl）-vinyl）-phenyl]aniline （BDCM-A） and N,N-bis-[p-（2-（4-dicyanomethylene-6-t-butyl-4H-pyran-2-yl）-vinyl）- phenyl]-4-methoxyl-aniline （BDCM-MA） were synthesized in good yields using 2-（t-butyl）-6-methyl-4H-pyrone as starting material. They can be utilized in OLEDs as nondoped red emitting materials as the result of the restricted concentration quenching effect.
文摘The solubilities of benzene and diphenyl in mixed solvents of t-butyl alcohol(TBA) and water with different salts have been determined at T = 298.15, 303.15, 308.15 and 313.15K. The molar fraction of TBA [x(TBA)] in mixed solvent is 0.045, and the molality of the salts (m_s)in mixed solvents are 0.000, 0.250, 0.500, 0.750 and 1.000 mol/kg, respectively. The standard Gibbsenergies of solution of benzene and diphenyl in the mixed solvents have also been calculated basedon the solubility data. The effects of different salts on the hydrophobic interaction (HI) forbenzene-benzene pair in the systems were discussed.
文摘A series of nickel halides bearing 2,4-di-t-butyl-6-（quinolin-8-yliminomethyl） phenolate ligands was synthesized and characterized by IR spectroscopy and elemental analysis. Molecular structures of C1 （R = H, X = Br） and C2 （R = H, X = C1） were further confirmed by single-crystal X-ray crystallographic studies, and revealed a distorted square planar geometry at nickel. Upon activation with diethylaluminum chloride （Et2AlCl）, all nickel pre-catalysts displayed good catalytic activity [up to 9.3 × 10^5 g mol-1（Ni） h-1] for ethylene oligomerization with major dimerization. In the presence of methylaluminoxane （MAO）, the nickel complex C1 was capable of ethylene polymerization under 3 MPa, and produced polyethylene products with narrow polydispersity （1.16-1.73） and molecular weights in the range of 2.6-4.95 kg/mol.
基金Project supported by the National Natural Science Foundation of China (Grant No. 29573144)
文摘The solubilitices of benzene, toluene and diphenyl in mixed solvents of t-butyl alcohol (TBA) and water at 283.15, 288.15, 293.15 and 298.15 K have been determined by spectrophotometry. The mole fraction of TBA [x (TBA)] in the mixed solvent are 0.000, 0.010, 0.020, 0.030, 0.040, 0.045, 0.050, 0.060, 0.080 and 0.100, respectively. The standard Gibbs energies of solution of benzene, toluene and diphenyl in the mixed solvent have also been calculated based on the solubility data. The hydrophobic interactions (HI) for the pairs of benzene-benzene, methane-benzene and methane-methane in the mixed solvent were calculated and discussed.
文摘A series of novel 3-（（4-（t-buty-）-2-（2-benzylidenehydrazinyl）thiazol-5-yl）methyl）quinolin-2（1H）-ones （7a--7z） were designed, synthesized and evaluated for their ability of inhibiting neuraminidase （NA） of influenza H1N1 virus. Some compounds displayed moderate influenza NA inhibitory activity. Compound 71 with the scaffold of 2-（2-（2-methoxybenzylidene）hydrazinyl）thiazole was the best one, exhibiting moderate NA inhibitory activity with ICs0 of 44.66 ~tmol/L. Structure-activity relationship showed that compounds with methoxy or hydroxy groups at the ortho position, fluorine and nitro groups at the meta position and chlorine and bromine groups at the para posi- tion of phenyl ring were more active. Docking study indicated that compound 71 has important interactions with some key residues （including Asp151, Glu119, Arg292, Tyr406, and Asn347） and binds to 430-cavity adjacent to NA active site.
基金This work was financially supported by the National Natural Science Foundation of China.
文摘Three substituted α,β,β-trifluorostyrenes(TFS's),i.e.,p-thiomethyltrifluorostyrene(4), p-cyclopropyltrifluorostyrene(5)and p-t-butyltrifluorostyrene(6),have been synthesized.The rate constants(k_2)of the thermal cyclodimerization of these compounds have been measured in the tem- perature range 120—160℃.The polar parameters σ_(mb) of these TFS's calculated from ^(19)F NMR chemi- cal shifts are:for p-thiomethyl,-0.18;p-cyclopropyl,-0.31 and p-t-butyl,-0.22.The spin delo- calization substituent parameters σ'_T(140°)of p-thiomethyl,cyclopropyl and t-butyl groups are 0.59, 0.27 and 0.30 respectively.Thus all of these groups act as electron-donating groups which can also effectively stabilize a spin.
