Using 1-butyl-3-methyl-imidazolium bromide （BM1MBr） as the supporting electrolyte and magne- sium as the sacrificial anode, a new and highly efficient electrochemically catalytic route was devel- oped for the synthe...Using 1-butyl-3-methyl-imidazolium bromide （BM1MBr） as the supporting electrolyte and magne- sium as the sacrificial anode, a new and highly efficient electrochemically catalytic route was devel- oped for the synthesis of cyclic carbonates from epoxides and CO2. Based on the cooperative action of BMIMBr and an electrogenerated magnesium salt obtained under a N2 atmosphere, CO2 reacted with a wide range of epoxides to readily generate cyclic carbonates in moderate to excellent yields under mild conditions.展开更多
The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative...The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.展开更多
Photo‐catalyzed tandem dearomatization/carboxylation of benzyl o‐halogenated aryl ether with CO_(2) was achieved,which affords spirocyclic carboxylic acids under mild conditions.The reaction has good functional grou...Photo‐catalyzed tandem dearomatization/carboxylation of benzyl o‐halogenated aryl ether with CO_(2) was achieved,which affords spirocyclic carboxylic acids under mild conditions.The reaction has good functional group tolerance with high yields.Mechanism studies indicate that the transformation was realized via intramolecular radical addition and nucleophilic addition.展开更多
Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was ...Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate （CF） at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.（μmol/μL）^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L （S/N=3）. In addition, the proposed sensor was successfully applied in determination of CF in drug sample.展开更多
Inclusion complexes between β-cyclodextrin （β-CD） and a series of dicarboxylic acids （DAn, n=11-15） were prepared by co-grinding and co-precipitation methods and the [3]pseudorotaxane structure of them was eluci...Inclusion complexes between β-cyclodextrin （β-CD） and a series of dicarboxylic acids （DAn, n=11-15） were prepared by co-grinding and co-precipitation methods and the [3]pseudorotaxane structure of them was elucidated by FTIR, DTA and XRD characterizations. Inclusion complexes of β-CD and α,ω-alkanedicarboxylate anions （DAn^2-） were acquired by neutralizing β-CD/DAn different inclusion complexes with sodium hydroxide and the structure was also proved to be a pseudorotaxane structure by ^1H-NMR spectra and NOESY spectrum. Both the inclusion complexes of β-CD/DAn and β-CD/DAn^2- adopt the [3]pseudorotaxane structure with β-CD arranged in dimers threaded onto one aliphatic chain and the binding mode of 1：1 inclusion complex was excluded based on the consideration of chain conformations.展开更多
基金supported by the National Natural Science Foundation of China(21303053)the Open Project of State Key Laboratory of Chemical Engineering(SKLChE-14C02)~~
文摘Using 1-butyl-3-methyl-imidazolium bromide （BM1MBr） as the supporting electrolyte and magne- sium as the sacrificial anode, a new and highly efficient electrochemically catalytic route was devel- oped for the synthesis of cyclic carbonates from epoxides and CO2. Based on the cooperative action of BMIMBr and an electrogenerated magnesium salt obtained under a N2 atmosphere, CO2 reacted with a wide range of epoxides to readily generate cyclic carbonates in moderate to excellent yields under mild conditions.
基金supported by the National Natural Science Foundation of China(21878038)the Natural Science Foundation of Liaoning Province(20170540156)the Program for Changjiang Scholars and Innovative Research Team in University(IRT-17R14)~~
文摘The development of new catalytic methodologies to synthesize heterocyclic fine chemicals using carbon dioxide as a synthon has attracted considerable attention. Herein, we report the silver( I)-catalyzed carboxylative cyclization of a variety of alkynic hydrazones with carbon dioxide to produce the corresponding 1,3,4-oxadiazin-2-ones under mild reaction conditions. In this reaction, silver(I) salts play a π-Lewis acid role for the highly efficient activation of the alkyne moiety in the hydrazone substrates. Single-crystal X-ray analysis and NOE experiments confirm that the newly formed oxadiazinone products exhibit Z configuration. Based on control experiments and NMR studies, a mechanism including the formation of a reactive carbazate intermediate, electrophilic cyclization, and subsequent protonation is proposed. This study offers an efficient and atom- economical method for the synthesis of biologically important 1,3,4-oxadiazin-2-ones.
文摘Photo‐catalyzed tandem dearomatization/carboxylation of benzyl o‐halogenated aryl ether with CO_(2) was achieved,which affords spirocyclic carboxylic acids under mild conditions.The reaction has good functional group tolerance with high yields.Mechanism studies indicate that the transformation was realized via intramolecular radical addition and nucleophilic addition.
文摘Carboxyl graphene modified CuxO/Cu electrode was fabricated. The bare copper electrode was firstly anodic polarized in 1.0 mol/L NaOH solution in order to get CuxO nanoparticles, then the carboxyl graphene （CG） was electrodeposited on the CuxO/Cu electrode by cyclic potential sweeping. The electrocatalytic oxidation behaviors of calcium folinate （CF） at the graphene modified CuxO/Cu electrode were investigated by cyclic voltammetry. A positive scan polarization reverse catalytic voltammetry was used to obtain the pure catalytic oxidation current. The graphene modified CuxO/Cu electrode was served as the electrochemical sensor of CF, a highly sensitivity of 22.0μA.（μmol/μL）^-1cm^-2 was achieved, and the current response was linear with increasing CF concentration in the range of 2.0×10^-7 mol/L to 2.0×10^-5 mol/L, which crossed three orders of magnitude, and the detection limit was found 7.6×10^-5 mol/L （S/N=3）. In addition, the proposed sensor was successfully applied in determination of CF in drug sample.
文摘Inclusion complexes between β-cyclodextrin （β-CD） and a series of dicarboxylic acids （DAn, n=11-15） were prepared by co-grinding and co-precipitation methods and the [3]pseudorotaxane structure of them was elucidated by FTIR, DTA and XRD characterizations. Inclusion complexes of β-CD and α,ω-alkanedicarboxylate anions （DAn^2-） were acquired by neutralizing β-CD/DAn different inclusion complexes with sodium hydroxide and the structure was also proved to be a pseudorotaxane structure by ^1H-NMR spectra and NOESY spectrum. Both the inclusion complexes of β-CD/DAn and β-CD/DAn^2- adopt the [3]pseudorotaxane structure with β-CD arranged in dimers threaded onto one aliphatic chain and the binding mode of 1：1 inclusion complex was excluded based on the consideration of chain conformations.
