The role of trifluoromethanesulfonate ion (OTf -) in asymmetric cyclopropanation of styrene catalyzed by ruthenium complex of chiral N, P ligand is investigated by in situ variable temperature 19 F NMR. The temperatur...The role of trifluoromethanesulfonate ion (OTf -) in asymmetric cyclopropanation of styrene catalyzed by ruthenium complex of chiral N, P ligand is investigated by in situ variable temperature 19 F NMR. The temperature of NMR experiment varies from 243 K to 283 K. After ethyl diazoacetate and styrene are added into the catalytic system, the process that the OTf - leaves from the central metal is observed from the change of the 19 F NMR spectra. Owing to the weakly coordinating behavior, trifluoromethanesulfonate ion can be easily removed from the central metal and replaced by substrates to form the reactive intermediate during the reaction. So that the catalytic reactivity can be improved greatly when the silver trifluoromethanesulfonate is added to the catalytic system.展开更多
Caffeic acid phenethyl ester(CAPE)is a rare,naturally occurring phenolic food additive.This work systematically reported fundamental data on conversion of caffeic acid(CA),yield of CAPE,and reactive selectivity during...Caffeic acid phenethyl ester(CAPE)is a rare,naturally occurring phenolic food additive.This work systematically reported fundamental data on conversion of caffeic acid(CA),yield of CAPE,and reactive selectivity during the lipase-catalyzed esterification process of CA and phenylethanol(PE)in ionic liquids(ILs).Sixteen ILs were selected as the reaction media,and the relative lipase-catalyzed synthesis properties of CAPE were measured in an effort to enhance the yield of CAPE with high selectivity.The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE.[Emim][Tf2N]was selected as the optimal reaction media.The optimal parameters were as follows by response surface methodology(RSM):reaction temperature,84.0°C;mass ratio of Novozym 435 to CA,14︰1;and molar ratio of PE to CA,16︰1.The highest reactive selectivity of CAPE catalyzed by Novozym 435 in[Emim][Tf2N]reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%,respectively).Thus,lipase-catalyzed esterification in ILs is a promising method suitable for CAPE production.展开更多
A new silicate fluoride,NaBa3 Si207 F,has been successfully synthesized by a high-temperature solution method.It crystallizes in the orthorhombic space group Cmcm(No.63).NaBa3 Si2 O7 F is the first barium-containing a...A new silicate fluoride,NaBa3 Si207 F,has been successfully synthesized by a high-temperature solution method.It crystallizes in the orthorhombic space group Cmcm(No.63).NaBa3 Si2 O7 F is the first barium-containing alkali metal silicate fluoride with the[NaO6]polyhedra,the[BaO8 F]polyhedra and isolated[Si2 O7]units.The optical characterizations indicate that NaBa3 Si2 O7 F possesses wide transparent window and available luminescence properties.To confirm the coordination surroundings of anionic groups and its thermostability,infrared spectroscopy and thermal behaviors were also analyzed,which proved the existence of tetrahedronly coordinated silicium atoms and the good stability of NaBa3 Si2 O7 F at high temperature.First-principles calculation was also implemented for better understanding the relationship between the structure of NaBa3 Si207 F and its property.Additionally,to further explore the structural novelty of NaBa3 Si2 O7 F,the comparison of the anionic structures was carried out in mixed alkali and alkaline-earth metal silicate fluorides.Interestingly,the result indicates the isolated[Si2 O7]dimer is rare among the above systems,which enriches the structural chemistry of silicate fluorides.展开更多
文摘The role of trifluoromethanesulfonate ion (OTf -) in asymmetric cyclopropanation of styrene catalyzed by ruthenium complex of chiral N, P ligand is investigated by in situ variable temperature 19 F NMR. The temperature of NMR experiment varies from 243 K to 283 K. After ethyl diazoacetate and styrene are added into the catalytic system, the process that the OTf - leaves from the central metal is observed from the change of the 19 F NMR spectra. Owing to the weakly coordinating behavior, trifluoromethanesulfonate ion can be easily removed from the central metal and replaced by substrates to form the reactive intermediate during the reaction. So that the catalytic reactivity can be improved greatly when the silver trifluoromethanesulfonate is added to the catalytic system.
基金Supported by the Natural Science Foundation of Jiangsu Province（BK2009213） China Postdoctoral Science Foundation funded Project（2012M510124）+2 种基金 Qing Lan Project of Jiangsu Province,National Natural Science Foundation of China（21206061） Research Project of Jiangsu University of Science and Technology（35211002） Modern Agro-industry Technology Research System of China（CARS-22）
文摘Caffeic acid phenethyl ester(CAPE)is a rare,naturally occurring phenolic food additive.This work systematically reported fundamental data on conversion of caffeic acid(CA),yield of CAPE,and reactive selectivity during the lipase-catalyzed esterification process of CA and phenylethanol(PE)in ionic liquids(ILs).Sixteen ILs were selected as the reaction media,and the relative lipase-catalyzed synthesis properties of CAPE were measured in an effort to enhance the yield of CAPE with high selectivity.The results indicated that ILs containing weakly coordinating anions and cations with adequate alkyl chain length improved the synthesis of CAPE.[Emim][Tf2N]was selected as the optimal reaction media.The optimal parameters were as follows by response surface methodology(RSM):reaction temperature,84.0°C;mass ratio of Novozym 435 to CA,14︰1;and molar ratio of PE to CA,16︰1.The highest reactive selectivity of CAPE catalyzed by Novozym 435 in[Emim][Tf2N]reached 64.55%(CA conversion 98.76%and CAPE yield 63.75%,respectively).Thus,lipase-catalyzed esterification in ILs is a promising method suitable for CAPE production.
基金supported by the National Natural Science Foundation of China(U1703132,51872325 and 61835014)Tianshan Innovation Team Program(2018D14001)+5 种基金Xinjiang International Science&Technology Cooperation Program(2017E01014)the National Key Research Project(2016YFB0402104)the Science and Technology Project of Urumqi(P161010002)Xinjiang Key Research and Development Program(2016B02021)Major Program of Xinjiang Uygur Autonomous Region of China during the 13th Five-Year Plan Period(2016A02003)West Light Foundation of the Chinese Academy of Sciences(2016-YJRC-2)
文摘A new silicate fluoride,NaBa3 Si207 F,has been successfully synthesized by a high-temperature solution method.It crystallizes in the orthorhombic space group Cmcm(No.63).NaBa3 Si2 O7 F is the first barium-containing alkali metal silicate fluoride with the[NaO6]polyhedra,the[BaO8 F]polyhedra and isolated[Si2 O7]units.The optical characterizations indicate that NaBa3 Si2 O7 F possesses wide transparent window and available luminescence properties.To confirm the coordination surroundings of anionic groups and its thermostability,infrared spectroscopy and thermal behaviors were also analyzed,which proved the existence of tetrahedronly coordinated silicium atoms and the good stability of NaBa3 Si2 O7 F at high temperature.First-principles calculation was also implemented for better understanding the relationship between the structure of NaBa3 Si207 F and its property.Additionally,to further explore the structural novelty of NaBa3 Si2 O7 F,the comparison of the anionic structures was carried out in mixed alkali and alkaline-earth metal silicate fluorides.Interestingly,the result indicates the isolated[Si2 O7]dimer is rare among the above systems,which enriches the structural chemistry of silicate fluorides.
