A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion ...A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.展开更多
The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the fie...The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the field of organofluorine chemistry and have thus made significant contributions.Furthermore,these newly developed methods are typically safer and more effective than the traditional methods.In this review,wewill summarize the representative contributions of new reagents and reactions developed in the past decade.展开更多
The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challen...The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challenge due to indirect synthetical strategies and volatile reagent which is hard to handle. Until very recently, several innovative reagents were developed to facilitate the trifluoromethoxylation reaction and make CF_3O-containing compounds more accessible. This review mainly focuses on the recent advances in new trifluoromethoxylation reagents and their usage.展开更多
The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1...The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(benzenesulfonylimide)salt.In its fluorination to oxindoles,the fluorinating products 6 were afforded in moderate to high yields.展开更多
N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed ...N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.展开更多
基金supported by the National Natural Science Foundation of China (No. 20976149)
文摘A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.
基金support from the National Natural Science Foundation of China(grant nos.21991121,21931013,21925105,22025103,and 21961142015)the National Key Research and Development Program of China(grant no.2021YFF0701700).
文摘The development of synthetic methods for the introduction of the fluorine atom and fluoroalklyl groups into organic molecules has gained increased attention.Synthetic organic chemists have recently jumped into the field of organofluorine chemistry and have thus made significant contributions.Furthermore,these newly developed methods are typically safer and more effective than the traditional methods.In this review,wewill summarize the representative contributions of new reagents and reactions developed in the past decade.
基金supported by the National Key Research and Development Program of China(2016YFA0602900)the National Natural Science Foundation of China(21522205,21672110)the Fundamental Research Funds for the Central Universities
文摘The trifluoromethoxy(CF_3O) group has become a novel moiety in various fields because of its unique features. However, despite the promising applications, the synthesis of CF_3O-containing compounds is still a challenge due to indirect synthetical strategies and volatile reagent which is hard to handle. Until very recently, several innovative reagents were developed to facilitate the trifluoromethoxylation reaction and make CF_3O-containing compounds more accessible. This review mainly focuses on the recent advances in new trifluoromethoxylation reagents and their usage.
基金the National Natural Science Foundation of China(No.21372077)for their financial supports.
文摘The direct preparation of a kind of fluorinating reagent 1[F-TEDA-N(SO_(2)Ph)_(2)]was realized in high yield via the complexation of N-fluorobenzenesulfonimide(NFSI)with 1-(chloromethyl)-1,4-diazabicyclo[2.2.2]octan-1-ium N',N'-bis-(benzenesulfonylimide)salt.In its fluorination to oxindoles,the fluorinating products 6 were afforded in moderate to high yields.
基金The National Natural Science Foundation of China(21991211)the National Key Research and Development Program of China(2021YFF0701700)are greatly acknowledged for funding this work.
文摘N-Fluorobenzenesulfonimide (NFSI) is one of the most popular fluorine-containing reagents for fluorination, imidation, sulfonylation, and oxidation reactions. Consequently, a variety of NFSI derivatives were designed and synthesized to modify the reactivity and/or selectivity of the parent reagent. However, the hazardous F_(2) was inevitably required for the synthesis of NFSI derivatives. Herein, we disclosed a practical synthesis of various NFSI derivatives without F_(2) in common organic chemistry laboratories. This synthetic protocol started from NFSI through pyridine-promoted desulfonylation for formation of N-fluoroarenesulfonamide (ArSO_(2)NHF) and followed by condensation with arenesulfonyl chlorides. The reduction potentials and fluorinating reactivities of these NFSI derivatives demonstrated that NFSI derivatives bearing the electron-withdrawing groups on benzene ring had the higher oxidizing and fluorinating abilities than NFSI.