An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compoun...An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions.Mechanistic studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition states.The origin of enantioselectivity has also been elucidated based on density functional theory calculations.展开更多
Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by vari...Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170℃,8.0 MPa,and 0.5 h^-1 liquid hourly space velocity of MEA(LHSVMEA)in NH3/H2 atmosphere.The Ni-Re/SiO2 catalyst with the lowest Ni particle size(4.5 nm)exhibited the highest yield(66.4%)of the desired amines(ethylenediamine(EDA)and piperazine(PIP)).The results of the analysis show that the turnover frequency of MEA increased slightly(from 193 to 253 h^-1)as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm.Moreover,the product distribution could be adjusted by varying the Ni particle size.The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm.Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni,which in turn affected the adsorption of MEA and the reaction pathway of MEA amination.Compared to those of small Ni particles,large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density,which favored the amination of MEA and NH3 to form EDA.展开更多
The work is dedicated to develop a one-step eco-friendly method to prepare antibacterial polyethylene terephthalate(PET).We report a one-step eco-friendly method to manufacture antibacterial PET via on-line amination ...The work is dedicated to develop a one-step eco-friendly method to prepare antibacterial polyethylene terephthalate(PET).We report a one-step eco-friendly method to manufacture antibacterial PET via on-line amination reaction by melt coextrusion.Beside evenly mixing of poly(hexamethylene guanidine)(PHMG)and PET in the melt coextrusion procedure,the amination reaction also occurred between PHMG and PET under high temperature(230-270℃).The antibacterial ability of composite PET showed obvious PHMG concentration dependence,and antibacterial activity reached more than 99%when PHMG content was 2.5 wt%.Moreover,LIVE/DEAD fluorescence test further confirmed that the composite PET could kill bacteria quickly and efiectively(within 30 min);while negligible cytotoxicity was observed to HSF and HUVEC cells.Onestep eco-friendly fabrication of composite antibacterial PET was accomplished by on-line melt coextrusion.The composite antibacterial PET has potential use in multiple fields to combat with pathogenic including textiles,packaging materials,decoration materials and biomedical devices,etc.展开更多
基金supported by the National Natural Science Foundation of China(22188101)Sichuan Science and Technology Program(2021YJ0561)。
文摘An efficient catalytic asymmetric dearomatizing amination of 2-naphthols and phenols catalyzed by N,N′-dioxide-copper(I)complex as a chiral catalyst was presented.A variety of optically activeβ-naphthalenone compounds with a nitrogen-containing quaternary carbon stereocenter were obtained with high yield and enantioselectivity under mild reaction conditions.Mechanistic studies indicated that this Csp^(2)–N dearomatizing coupling proceeds via 1,3-reductive elimination of phenolate-Cu~Ⅲ-amino intermediate in five-membered ring transition states.The origin of enantioselectivity has also been elucidated based on density functional theory calculations.
基金supported by the National Natural Science Foundation of China(21273227)Strategic Priority Research Program of Chinese Academy of Sciences(XDB17000000)~~
文摘Ni-Re/SiO2 catalysts with controllable Ni particle sizes(4.5–18.0 nm)were synthesized to investigate the effects of the particle size on the amination of monoethanolamine(MEA).The catalysts were characterized by various techniques and evaluated for the amination reaction in a trickle bed reactor at 170℃,8.0 MPa,and 0.5 h^-1 liquid hourly space velocity of MEA(LHSVMEA)in NH3/H2 atmosphere.The Ni-Re/SiO2 catalyst with the lowest Ni particle size(4.5 nm)exhibited the highest yield(66.4%)of the desired amines(ethylenediamine(EDA)and piperazine(PIP)).The results of the analysis show that the turnover frequency of MEA increased slightly(from 193 to 253 h^-1)as the Ni particle sizes of the Ni-Re/SiO2 catalysts increased from 4.5 to 18.0 nm.Moreover,the product distribution could be adjusted by varying the Ni particle size.The ratio of primary to secondary amines increased from 1.0 to 2.0 upon increasing the Ni particle size from 4.5 to 18.0 nm.Further analyses reveal that the Ni particle size influenced the electronic properties of surface Ni,which in turn affected the adsorption of MEA and the reaction pathway of MEA amination.Compared to those of small Ni particles,large particles possessed a higher proportion of high-coordinated terrace Ni sites and a higher surface electron density,which favored the amination of MEA and NH3 to form EDA.
基金Funded by the National Natural Science Foundation of China(No.51703169)Key Program of Science and Technology of Jieyang City(No.2019016)Key Research and Development Program of Shandong Province of China(No.2019JZZY010338)。
文摘The work is dedicated to develop a one-step eco-friendly method to prepare antibacterial polyethylene terephthalate(PET).We report a one-step eco-friendly method to manufacture antibacterial PET via on-line amination reaction by melt coextrusion.Beside evenly mixing of poly(hexamethylene guanidine)(PHMG)and PET in the melt coextrusion procedure,the amination reaction also occurred between PHMG and PET under high temperature(230-270℃).The antibacterial ability of composite PET showed obvious PHMG concentration dependence,and antibacterial activity reached more than 99%when PHMG content was 2.5 wt%.Moreover,LIVE/DEAD fluorescence test further confirmed that the composite PET could kill bacteria quickly and efiectively(within 30 min);while negligible cytotoxicity was observed to HSF and HUVEC cells.Onestep eco-friendly fabrication of composite antibacterial PET was accomplished by on-line melt coextrusion.The composite antibacterial PET has potential use in multiple fields to combat with pathogenic including textiles,packaging materials,decoration materials and biomedical devices,etc.
