Herein,a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis fo r aniline N,N-diethylation with ethanol was proposed,and the SO4^2-/Ce0.84Zr0.16O2-WO3-ZrO2 catalyst(SCWZ)with both Lewis...Herein,a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis fo r aniline N,N-diethylation with ethanol was proposed,and the SO4^2-/Ce0.84Zr0.16O2-WO3-ZrO2 catalyst(SCWZ)with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method,which shows better catalytic activity than the reported solid acidic catalysts.Besides,the SO4^2-/ZrO2(SZ)and SO4^2-/WO3-ZrO2(SWZ)catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component.The SO4^2-and WO3 mainly generate Lewis acid by bonding with ZrO2,which is beneficial for the fracture of the N-H bond in aniline.The Ce0.84Zr0.16O2 solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species,which can participate in stripping-OH from ethanol,then the carbocation will also be released,which only needs1.3805 kcal/mol energy,calculated by density functional theory(DFT),to be input.In comparison,the traditional reaction mechanism needs the Br■nsted acidic sites to promote the protonation of ethanol,then dehydration and subsequent formation of carbocation followed,and 108.6846 kcal/mol energy needs to be input,which is far higher than that of the new mechanism.The apparent activation energy(Ea)over SCWZ was measured by experiment to be 34.09 kJ/mol,which is much lower than that of SWZ(47.10 kJ/mol)and SZ(54.37 kJ/mol),illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ.Besides,the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100%and 73%,respectively,The SCWZ can be renewed for 4 times without rapid deactivation,and the longevity of SCWZ is longer than that of SWZ and SZ,as the loaded SO4^2-and tetragonal ZrO2 are stabilized by Ce0.84Zr0.16O2 and WO3,respectively.展开更多
Buxrugulosides A–E,four lignan glycosides(1–4)and a protocatechuate derivative(5)featuring a rare(N,Ndiethyl)methyl amino group at aromatic rings,were obtained from the aerial parts of Buxus rugulosa,which is famous...Buxrugulosides A–E,four lignan glycosides(1–4)and a protocatechuate derivative(5)featuring a rare(N,Ndiethyl)methyl amino group at aromatic rings,were obtained from the aerial parts of Buxus rugulosa,which is famous for treating coronary heart disease.Their structures including absolute configurations were elucidated by HRMS,1 D and 2 D NMR,and by comparing their CD data with previous reports.Compound 1 was a rare sesquilignan,and all of these compounds were the first example of lignans with(N,N-diethyl)methyl amino group.展开更多
The title compound （C40H42N2） has been synthesized by the reaction of l-（l- naphthyl）-l-phenyl-3-chloropropylene and bis（4-（diethylamino） phenyl）methanone, and characterized by IR, ^1H NMR, MS and X-ray diffra...The title compound （C40H42N2） has been synthesized by the reaction of l-（l- naphthyl）-l-phenyl-3-chloropropylene and bis（4-（diethylamino） phenyl）methanone, and characterized by IR, ^1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047（3）, b = 10.807（2）, c = 18.494（4） A, β = 105.727（4）°, V= 3279.4（11） A^3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm^3,μ（MoKa） = 0.085 mm^-1, F（000） = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections （1 〉 2σ（I））. X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4（2）° with the naphthalene ring.展开更多
A new N-diethyl imidazole modified PS resins was synthesized in this paper. The composition, structure, and properties of the resulting resins were studied by means of Fourier transform infrared (FTIR) and elemental a...A new N-diethyl imidazole modified PS resins was synthesized in this paper. The composition, structure, and properties of the resulting resins were studied by means of Fourier transform infrared (FTIR) and elemental analysis methods. The results showed that the resins hold the adsorption function group of quaternary ammonium structure. Meanwhile, the adsorption properties of the resulting resins for iodine were investigated. The results showed that the uptake of iodine found to be higher at natural water than at acidic medium;the adsorption capacity increased with the increasing of temperature, but when the temperature is higher than 30°C, adsorption capacity didn’t increase;the adsorption kinetics of the resins can be modeled by pseudo first-order rate equation and pseudo second-order rate equation wonderfully;Both Freundlich equations and Langmuir equations could well interpret the adsorption of resins for iodine.展开更多
基金Project supported by China Petroleum&Chemical Corporation (J418013-3)。
文摘Herein,a new mechanism involving Lewis acid-oxygen vacancy interfacial synergistic catalysis fo r aniline N,N-diethylation with ethanol was proposed,and the SO4^2-/Ce0.84Zr0.16O2-WO3-ZrO2 catalyst(SCWZ)with both Lewis acid sites and oxygen vacancies was synthesized by the hydrothermal method,which shows better catalytic activity than the reported solid acidic catalysts.Besides,the SO4^2-/ZrO2(SZ)and SO4^2-/WO3-ZrO2(SWZ)catalysts were also prepared and compared with SCWZ to investigate the synergistic effect of each component.The SO4^2-and WO3 mainly generate Lewis acid by bonding with ZrO2,which is beneficial for the fracture of the N-H bond in aniline.The Ce0.84Zr0.16O2 solid solution mainly plays a vital role in generating the oxygen vacancies as the interface active species,which can participate in stripping-OH from ethanol,then the carbocation will also be released,which only needs1.3805 kcal/mol energy,calculated by density functional theory(DFT),to be input.In comparison,the traditional reaction mechanism needs the Br■nsted acidic sites to promote the protonation of ethanol,then dehydration and subsequent formation of carbocation followed,and 108.6846 kcal/mol energy needs to be input,which is far higher than that of the new mechanism.The apparent activation energy(Ea)over SCWZ was measured by experiment to be 34.09 kJ/mol,which is much lower than that of SWZ(47.10 kJ/mol)and SZ(54.37 kJ/mol),illustrating comparatively preferable kinetics for SCWZ than that of SWZ and SZ.Besides,the conversion of aniline and selectivity to N,N-diethylaniline over SCWZ reach almost 100%and 73%,respectively,The SCWZ can be renewed for 4 times without rapid deactivation,and the longevity of SCWZ is longer than that of SWZ and SZ,as the loaded SO4^2-and tetragonal ZrO2 are stabilized by Ce0.84Zr0.16O2 and WO3,respectively.
基金supported by the“Double FirstClass”University Project(No.CPU2018GY08)the Drug Innovation Major Project(No.2018ZX09711-001-007)。
文摘Buxrugulosides A–E,four lignan glycosides(1–4)and a protocatechuate derivative(5)featuring a rare(N,Ndiethyl)methyl amino group at aromatic rings,were obtained from the aerial parts of Buxus rugulosa,which is famous for treating coronary heart disease.Their structures including absolute configurations were elucidated by HRMS,1 D and 2 D NMR,and by comparing their CD data with previous reports.Compound 1 was a rare sesquilignan,and all of these compounds were the first example of lignans with(N,N-diethyl)methyl amino group.
基金The project was supported by the National 863 Program of China (No. 2002AA325050)
文摘The title compound （C40H42N2） has been synthesized by the reaction of l-（l- naphthyl）-l-phenyl-3-chloropropylene and bis（4-（diethylamino） phenyl）methanone, and characterized by IR, ^1H NMR, MS and X-ray diffraction analysis. The crystal belongs to the monoclinic system, space group P21/c with a = 17.047（3）, b = 10.807（2）, c = 18.494（4） A, β = 105.727（4）°, V= 3279.4（11） A^3, Mr = 550.76, Z = 4, Dc = 1.115 g/cm^3,μ（MoKa） = 0.085 mm^-1, F（000） = 1184, the final R = 0.0625 and wR = 0.1384 for 2276 observed reflections （1 〉 2σ（I））. X-ray analysis reveals that the butadiene fragment adopts a planar cisiod conformation and makes a dihedral angel of 69.4（2）° with the naphthalene ring.
文摘A new N-diethyl imidazole modified PS resins was synthesized in this paper. The composition, structure, and properties of the resulting resins were studied by means of Fourier transform infrared (FTIR) and elemental analysis methods. The results showed that the resins hold the adsorption function group of quaternary ammonium structure. Meanwhile, the adsorption properties of the resulting resins for iodine were investigated. The results showed that the uptake of iodine found to be higher at natural water than at acidic medium;the adsorption capacity increased with the increasing of temperature, but when the temperature is higher than 30°C, adsorption capacity didn’t increase;the adsorption kinetics of the resins can be modeled by pseudo first-order rate equation and pseudo second-order rate equation wonderfully;Both Freundlich equations and Langmuir equations could well interpret the adsorption of resins for iodine.
