Our work reported that the so-called pure carbon nanotubes(CNTs)can be synthesized without metallic catalyst by chemical vapor deposition(CVD).The as-prepared CNTs have average diameter of 50 nm and length over severa...Our work reported that the so-called pure carbon nanotubes(CNTs)can be synthesized without metallic catalyst by chemical vapor deposition(CVD).The as-prepared CNTs have average diameter of 50 nm and length over several microns.Analysis of intermediate objects in the products indicates that their formation mechanism follows the wire-to-tube model.Besides,according to thermodynamic analysis of the driving force combing with experimental results,we find that the thermal gradient can effectively favor the formation of CNTs in our metallic catalyst-free CVD.展开更多
Oxidation of petroleum-based byproduct dicyclopentadiene derived diformyltricyclodecanes(DFTD) to dicarboxyltriclodecanesacids(DCTDA) was conducted under catalyst-free and ultra-low temperature conditions with O2 as o...Oxidation of petroleum-based byproduct dicyclopentadiene derived diformyltricyclodecanes(DFTD) to dicarboxyltriclodecanesacids(DCTDA) was conducted under catalyst-free and ultra-low temperature conditions with O2 as oxidant. In the perspective of industry process, oxygen pressure and contents, solvent and raw material initial concentrations were screened to evaluate their influence on DCTDA generation. Results indicate that DFTD oxidation can occur rather easily under no-catalyst and ultra-low temperature conditions with O2 as oxidant. Oxygen content and pressure had positive effect on DCTDA production, γ-valerolactone(GVL) behaved best on DFTD generation in dynamics, while methanol could be used as a protective solvent to preserve DFTD.Besides, the existence of water in solvent was not beneficial to DCTDA production because of poor DFTD compatibility with water. The mechanisms of O2 and solvent influence on DCTDA generation were discussed. Meanwhile,the oxidation route of DFTD–Intermediate–DCTDA was proposed. The present work exhibits the valued potential of DFTD, which will have a positive effect on high added value of petroleum based by-products.展开更多
A facile procedure for the synthesis, of quinoxalines is being reported starting from benzil and 1,2-diaminobenzene. The reactions were carried out catalyst-free, solvent-free and under microwave irradiation condition...A facile procedure for the synthesis, of quinoxalines is being reported starting from benzil and 1,2-diaminobenzene. The reactions were carried out catalyst-free, solvent-free and under microwave irradiation conditions in high yield (84-98%) with short time (3-6 min) and environmental benign, as well as convenient operation. The structures of all the compounds have been confirmed on the basis of their IR, 1H NMR, and/or 13C NMR, mass spectral data.展开更多
A facile procedure for the synthesis of 2,4,5-lriarylimidazoles is being reported starting from benzil, aromatic aldehyde and ammonium acetate. The reactions were carried out with catalyst-free, solvent-free and under...A facile procedure for the synthesis of 2,4,5-lriarylimidazoles is being reported starting from benzil, aromatic aldehyde and ammonium acetate. The reactions were carried out with catalyst-free, solvent-free and under microwave irradiation conditions in high yield (80-99%) with short time (3-5 min) and environmental benign, as well as convenient operation. The structures of the compounds have been confirmed on the basis of their IR, 1H NMR, and/or 13C NMR, MS, and elemental analyzer.展开更多
In the field of organic syntheses, the development of environmentally friendly methods based on the concept of green chemistry has been always required. In response to this requirement, we reported solvent- and cataly...In the field of organic syntheses, the development of environmentally friendly methods based on the concept of green chemistry has been always required. In response to this requirement, we reported solvent- and catalyst-free syntheses of imines using the pressure reduction technique as a key technology. We found that this reaction proceeded very rapidly in the initial stage, but its rate decreased with the passage of time. It was also found that the reaction of benzaldehyde with aniline had a specificity that the phase transition occurred. In this method, the desired imines could be obtained in good to excellent yields, but target compounds had to be given by purifications using organic solvents. Therefore, we tried to develop the perfect synthetic method of imine derivatives without organic or inorganic solvents. We selected two methods and took them into this investigation. One was exactly mixing (1:1, substance ratio) aldehydes and amines and the other was employing lower pressure (>0.1 mmHg, previous method: 1.0 mmHg) at the pressure reducing technique. When this improved synthetic method was performed, it was revealed that pure target imines were obtained in excellent yields without any purification.展开更多
Because imines could be used as convenient starting materials in various fields, the development of an easy synthetic method of imine was strongly desired. In response to this demand, we thought that it would be an ef...Because imines could be used as convenient starting materials in various fields, the development of an easy synthetic method of imine was strongly desired. In response to this demand, we thought that it would be an effective synthesis method if an aldehyde and an amine could be reacted to give an imine in good yield under solvent- and catalyst-free conditions. In fact, we tried the reaction of benzaldehyde with various amines under solvent- and catalyst-free conditions followed by removal of water that was produced in the reaction system by a vacuum pump, and desired imines could be obtained in good yields. Observation of this reaction using a nuclear magnetic resonance spectrometer revealed that the reaction rate was extremely fast at the initial stage but slowed over time. However, the reaction of benzaldehyde with aniline differed greatly, and the reaction rate dramatically improved in 47 - 48 minutes after the start of the reaction. At this time, we found that the reaction system underwent a phase transition from the liquid phase to the solid phase.展开更多
It has been found that microwave assisted decarboxylation of malonic acid derivatives can be achieved under solvent-free and catalyst free conditions. This new method produces the corresponding carboxylic acid in a pu...It has been found that microwave assisted decarboxylation of malonic acid derivatives can be achieved under solvent-free and catalyst free conditions. This new method produces the corresponding carboxylic acid in a pure manner and with a high yield in a very short reaction time: 3 - 10 min. In general terms, the condition under which this reaction is carried out accelerates the decarboxylation significantly of a series of disubstituted malonic acid derivatives, and makes this new process efficient, easy and environmentally friendly.展开更多
Fifteen dihydropyrimidinthiones have been synthesized by microwave-assisted Biginelli reactions without any solvent or catalyst. The advantages of this novel protocol include the excellent yield, operational simplicit...Fifteen dihydropyrimidinthiones have been synthesized by microwave-assisted Biginelli reactions without any solvent or catalyst. The advantages of this novel protocol include the excellent yield, operational simplicity, short time and the avoidance of the use of organic solvents and catalysts.展开更多
A catalyst-free and atom-economical[4+3]cycloaddition of azadienes with C,N-cyclic azomethine imines has been developed,providing an efficient and environmentally benign access to 1,2,4-triazepines with high diastereo...A catalyst-free and atom-economical[4+3]cycloaddition of azadienes with C,N-cyclic azomethine imines has been developed,providing an efficient and environmentally benign access to 1,2,4-triazepines with high diastereoselectivities and yields.This reaction can be performed in 2-methyltetrahydrofuran under mild conditions smoothly.展开更多
An efficient and practical synthesis of heterocyclic nucleosides is developed by a catalyst-free highly regioselective and diastereose-lective[3+2]annulation of a-purine-substituted acrylates with nitrones.The reactio...An efficient and practical synthesis of heterocyclic nucleosides is developed by a catalyst-free highly regioselective and diastereose-lective[3+2]annulation of a-purine-substituted acrylates with nitrones.The reaction operates with excellent functional group toler-ance,very mild reaction conditions,and with the green,sustainable,and eco-friendly 2-methyltetrahydrofuran(2-MeTHF)as sol-vent.Compared with other reactions of electron-deficient olefin dipolarophiles with nitrones,different regioselective cycloaddition products were observed in this work.This 1,3-dipolar cycloaddition reaction gives a series of isoxazolidinyl nucleosides in good to excellent yields with promising applications in biochemistry and medicinal chemistry.展开更多
The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for th...The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for the preparation of polymers in a more sustainable way.Nevertheless,due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure,the cross-link density of materials is frequently lowered.In this study,hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids,which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers.It was completely characterized by differential scanning calorimetry test,thermogravimetric analysis,shape memory test and self-healing test.The prepared vitrimers exhibited good self-healing properties,excellent heat resistance(T_(d)=352℃)as well as high mechanical properties(tensile strength of 46.75 MPa).The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton.Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy.Moreover,our work expanded the application field of rosin,increased the added value of rosin,and provided a novel method for preparing rosin-based vitrimers with ideal properties.展开更多
The importance of CF3-containing molecules in pharmaceuticals, agrochemicals and materials intrigues the intense interest in synthetic methodology of these compounds. With a purpose to enrich trifluoromethylation meth...The importance of CF3-containing molecules in pharmaceuticals, agrochemicals and materials intrigues the intense interest in synthetic methodology of these compounds. With a purpose to enrich trifluoromethylation methodology, we carefully examined the substrate scope of hydroxytrifluoromethylation of alkenes using iodotrifluoromethane, and the reaction provided β-trifluoromethyl alcohols in good yields under extremely mild conditions without catalysts. We found that our reaction can be applied to not only styrenes but also various aliphatic alkenes with excellent selectivity;no ketone was detected in most of our cases. Another feature of our discovery is “simple”. The reaction was carried out in air, irradiated by visible light, at room temperature and most importantly no catalyst was needed. A solution of CF3I in DMSO was used as the facile trifluoromethylating reagent, which simplified the utilization of gaseous CF3I. Based on 19F NMR spectroscopy, we observed a halogen bond between CF3I and tertiary amine in this reaction. The interaction may promote single electron transfer by the visible light irradiation.展开更多
The copper-catalyzed and metal-free azide-alkyne click polymerizations have become efficient tools for polymer synthesis. However,the 1,3-dipolar polycycloadditions between internal alkynes and azides are rarely emplo...The copper-catalyzed and metal-free azide-alkyne click polymerizations have become efficient tools for polymer synthesis. However,the 1,3-dipolar polycycloadditions between internal alkynes and azides are rarely employed to construct functional polymers. Herein, the polycycloadditions of dibutynoate(1) and tetraphenylethene-containing diazides(2) were carried out at 100 °C for 12 h under solvent-and catalyst-free conditions, producing soluble poly(methyltriazolylcarboxylate)s(PMTCs) with high molecular weights in high yields. The resultant polymers were thermally stable with 5% weight loss temperatures up to 377 °C. The PMTCs showed aggregation-induced emission(AIE)properties. They could work as fluorescent sensors for detecting explosive with high sensitivity, and generate two-dimensional fluorescent photopatterns with high resolution. Furthermore, their triazolium salts could be utilized for cell-imaging applications.展开更多
A series of new photodegradable poly(furan-amine)s(PFAs) were synthesized by a one-pot, catalyst-free, multicomponent cyclopolymerization between diisocyanides, dialkylacetylene dicarboxylates, and aromatic dialdehyde...A series of new photodegradable poly(furan-amine)s(PFAs) were synthesized by a one-pot, catalyst-free, multicomponent cyclopolymerization between diisocyanides, dialkylacetylene dicarboxylates, and aromatic dialdehydes. All polymerizations were conducted in toluene at 100 ℃ for 6 h without inert gas protection and furnished polymers with a satisfactory molecular weight(Mw up to32200) and yield. The PFA structure was confirmed by spectroscopic techniques, such as GPC, FTIR, and NMR, as well as by comparison with a model compound. The polymers exhibited good solubility in common organic solvents and thermal stability. All the PFAs had high refractive indices in the visible light region(400 nm to 800 nm). Moreover, the PFAs were substantially degraded by UV irradiation due to the presence of furan rings. The film thickness reduction rate could be over 90%.展开更多
The tandem reaction of photoinduced double hydrogen-atom transfer and deoxygenative transborylation for chemo-and site-selective reduction of nitroarenes into aryl amines under catalyst-free, room temperature conditio...The tandem reaction of photoinduced double hydrogen-atom transfer and deoxygenative transborylation for chemo-and site-selective reduction of nitroarenes into aryl amines under catalyst-free, room temperature conditions was disclosed in excellent yields. In this reaction, isopropanol(^(i)PrOH) was used as hydrogen donor and tetrahydroxydiboron [B_(2)(OH)_(4)] as deoxygenative reagent with green, cheap, and commercially available credentials. In particular, a wide range of reducible functional groups such as halogen(-Cl,-Br and even-I), alkenyl, alkynyl, aldehyde, ketone, carboxyl, and cyano are all tolerated. Moreover,the reaction preferentially reduces the nitro group at the electron-deficient site over another nitro group in the same molecule. A detailed mechanistic investigation in combination of experiments and theoretical calculations gave a reasonable explanation for the reaction pathway.展开更多
Aldol reaction between simple benzaldehydes and ketones successfully happened in solvent- and catalyst-free condition. The desired products were obtained in moderate yield at suitable temperature. Heat was assumed as ...Aldol reaction between simple benzaldehydes and ketones successfully happened in solvent- and catalyst-free condition. The desired products were obtained in moderate yield at suitable temperature. Heat was assumed as the driving force for the reaction. This approach has obvious advantages to fully meet the requirement of the principles of green chemistry.展开更多
A simple, efficient and eco-friendly route has been developed for the synthesis of fl-mercapto diketones via a multicomponent reaction of an aldehyde, acetylacetone and thiol in water. This methodology affords a numbe...A simple, efficient and eco-friendly route has been developed for the synthesis of fl-mercapto diketones via a multicomponent reaction of an aldehyde, acetylacetone and thiol in water. This methodology affords a number of β-mercapto diketone derivatives in moderate to good yields.展开更多
4-Methylene-1,3-oxazolidin-2-ones can be synthesized from propargylic alcohols, primary amines and carbon dioxide under supercritical condition in the absence of any additional catalyst and solvent. Various propargyli...4-Methylene-1,3-oxazolidin-2-ones can be synthesized from propargylic alcohols, primary amines and carbon dioxide under supercritical condition in the absence of any additional catalyst and solvent. Various propargylic alcohols and primary amines were examined.展开更多
A simple and efficient one-pot procedure has been developed for the construction of pyrrolo[ 1,2-a]pyrimidines via the three-component domino reaction of 5-aminopyrazoles, acetylenedicarboxylates and malononitrile und...A simple and efficient one-pot procedure has been developed for the construction of pyrrolo[ 1,2-a]pyrimidines via the three-component domino reaction of 5-aminopyrazoles, acetylenedicarboxylates and malononitrile under catalyst-free, microwave irradiation conditions. The key step in this transformation is the N--N bond cleavage reac- tion of the 5-aminopyrazole substrate, which has been reported in this context for the first time in this study. The advantages of this protocol include readily available starting materials, short reaction times and good regioselectivity.展开更多
An expedient and mild strategy for the synthesis of unconventional 2-(dimethylamino)-3,3-difluorochroman-4-one derivatives from o-hydroxyarylenaminones and Selectfluor was developed at room temperature under catalys...An expedient and mild strategy for the synthesis of unconventional 2-(dimethylamino)-3,3-difluorochroman-4-one derivatives from o-hydroxyarylenaminones and Selectfluor was developed at room temperature under catalyst-free conditions. This method showed excellent chemoselectivity and great functional groups tolerance.展开更多
基金supported by the Creative Research Group of National Science Foundation of China(Grant No.50721003)the Foundation of the Ministry of Education of China for Returned Scholars(Grant No.2005383)
文摘Our work reported that the so-called pure carbon nanotubes(CNTs)can be synthesized without metallic catalyst by chemical vapor deposition(CVD).The as-prepared CNTs have average diameter of 50 nm and length over several microns.Analysis of intermediate objects in the products indicates that their formation mechanism follows the wire-to-tube model.Besides,according to thermodynamic analysis of the driving force combing with experimental results,we find that the thermal gradient can effectively favor the formation of CNTs in our metallic catalyst-free CVD.
基金Supported by the Research Foundation of China University of Petroleum,-Beijing at Karamay(YJ2018B02006)the Chinese Government “Thousand Talent” Program(Y42H291501).
文摘Oxidation of petroleum-based byproduct dicyclopentadiene derived diformyltricyclodecanes(DFTD) to dicarboxyltriclodecanesacids(DCTDA) was conducted under catalyst-free and ultra-low temperature conditions with O2 as oxidant. In the perspective of industry process, oxygen pressure and contents, solvent and raw material initial concentrations were screened to evaluate their influence on DCTDA generation. Results indicate that DFTD oxidation can occur rather easily under no-catalyst and ultra-low temperature conditions with O2 as oxidant. Oxygen content and pressure had positive effect on DCTDA production, γ-valerolactone(GVL) behaved best on DFTD generation in dynamics, while methanol could be used as a protective solvent to preserve DFTD.Besides, the existence of water in solvent was not beneficial to DCTDA production because of poor DFTD compatibility with water. The mechanisms of O2 and solvent influence on DCTDA generation were discussed. Meanwhile,the oxidation route of DFTD–Intermediate–DCTDA was proposed. The present work exhibits the valued potential of DFTD, which will have a positive effect on high added value of petroleum based by-products.
基金Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials for financial support(No.JSKC07041)
文摘A facile procedure for the synthesis, of quinoxalines is being reported starting from benzil and 1,2-diaminobenzene. The reactions were carried out catalyst-free, solvent-free and under microwave irradiation conditions in high yield (84-98%) with short time (3-6 min) and environmental benign, as well as convenient operation. The structures of all the compounds have been confirmed on the basis of their IR, 1H NMR, and/or 13C NMR, mass spectral data.
基金the Jiangsu Key Laboratory for Chemistry of Low-Dimensional Materials for financial support(No. JSKC07041)
文摘A facile procedure for the synthesis of 2,4,5-lriarylimidazoles is being reported starting from benzil, aromatic aldehyde and ammonium acetate. The reactions were carried out with catalyst-free, solvent-free and under microwave irradiation conditions in high yield (80-99%) with short time (3-5 min) and environmental benign, as well as convenient operation. The structures of the compounds have been confirmed on the basis of their IR, 1H NMR, and/or 13C NMR, MS, and elemental analyzer.
文摘In the field of organic syntheses, the development of environmentally friendly methods based on the concept of green chemistry has been always required. In response to this requirement, we reported solvent- and catalyst-free syntheses of imines using the pressure reduction technique as a key technology. We found that this reaction proceeded very rapidly in the initial stage, but its rate decreased with the passage of time. It was also found that the reaction of benzaldehyde with aniline had a specificity that the phase transition occurred. In this method, the desired imines could be obtained in good to excellent yields, but target compounds had to be given by purifications using organic solvents. Therefore, we tried to develop the perfect synthetic method of imine derivatives without organic or inorganic solvents. We selected two methods and took them into this investigation. One was exactly mixing (1:1, substance ratio) aldehydes and amines and the other was employing lower pressure (>0.1 mmHg, previous method: 1.0 mmHg) at the pressure reducing technique. When this improved synthetic method was performed, it was revealed that pure target imines were obtained in excellent yields without any purification.
文摘Because imines could be used as convenient starting materials in various fields, the development of an easy synthetic method of imine was strongly desired. In response to this demand, we thought that it would be an effective synthesis method if an aldehyde and an amine could be reacted to give an imine in good yield under solvent- and catalyst-free conditions. In fact, we tried the reaction of benzaldehyde with various amines under solvent- and catalyst-free conditions followed by removal of water that was produced in the reaction system by a vacuum pump, and desired imines could be obtained in good yields. Observation of this reaction using a nuclear magnetic resonance spectrometer revealed that the reaction rate was extremely fast at the initial stage but slowed over time. However, the reaction of benzaldehyde with aniline differed greatly, and the reaction rate dramatically improved in 47 - 48 minutes after the start of the reaction. At this time, we found that the reaction system underwent a phase transition from the liquid phase to the solid phase.
文摘It has been found that microwave assisted decarboxylation of malonic acid derivatives can be achieved under solvent-free and catalyst free conditions. This new method produces the corresponding carboxylic acid in a pure manner and with a high yield in a very short reaction time: 3 - 10 min. In general terms, the condition under which this reaction is carried out accelerates the decarboxylation significantly of a series of disubstituted malonic acid derivatives, and makes this new process efficient, easy and environmentally friendly.
基金the Natural Science Foundation of China(No.20272047,20572086)the Natural Science Foundation of Gansu Province(No.3ZS051-A25-001)Key Laboratory of Eco-Environment-Related Polymer Material(Northwest Normal University),Ministry of Education of China.
文摘Fifteen dihydropyrimidinthiones have been synthesized by microwave-assisted Biginelli reactions without any solvent or catalyst. The advantages of this novel protocol include the excellent yield, operational simplicity, short time and the avoidance of the use of organic solvents and catalysts.
基金We thank the Marine S&T Fund of Shandong Province for Pilot National Laboratory for Marine Science and Technology(QNLM)(No.2022QNLM030003-2)the Fundamental Research Funds for the Central Universities,Ocean University of China,Qingdao National Laboratory for Marine Science and Technology(Nos.LMDBCXRC201902 and LMDBCXRC201903)+2 种基金Taishan Scholar Program of Shandong Province(Nos.tsqn201909056 and tsqn202103152)National Natural Science Foundation of China(No.22171251)Natural Science Foundation of Shandong Province(No.ZR2021QB033)for financial support.
文摘A catalyst-free and atom-economical[4+3]cycloaddition of azadienes with C,N-cyclic azomethine imines has been developed,providing an efficient and environmentally benign access to 1,2,4-triazepines with high diastereoselectivities and yields.This reaction can be performed in 2-methyltetrahydrofuran under mild conditions smoothly.
基金We gratefully acknowledge HKBU RC-Tier 2 Start-up Grant for financial support.
文摘An efficient and practical synthesis of heterocyclic nucleosides is developed by a catalyst-free highly regioselective and diastereose-lective[3+2]annulation of a-purine-substituted acrylates with nitrones.The reaction operates with excellent functional group toler-ance,very mild reaction conditions,and with the green,sustainable,and eco-friendly 2-methyltetrahydrofuran(2-MeTHF)as sol-vent.Compared with other reactions of electron-deficient olefin dipolarophiles with nitrones,different regioselective cycloaddition products were observed in this work.This 1,3-dipolar cycloaddition reaction gives a series of isoxazolidinyl nucleosides in good to excellent yields with promising applications in biochemistry and medicinal chemistry.
基金This research was supported by the National Natural Science Foundation of China(Grant No.32171734)the Scientific Research Funds of Huaqiao University(Grant No.20BS201).
文摘The emergence of vitrimer,a new class of polymer materials can address the problem of recyclability,reprocess ability and recyclability of thermosetting plastics.Rosin,a natural product,is an ideal raw material for the preparation of polymers in a more sustainable way.Nevertheless,due to the huge steric hindrance caused by the hydrogenated phenanthrene ring structure,the cross-link density of materials is frequently lowered.In this study,hydrogenated rosin was adopted for preparing hydrogenated rosin side-chain type diacids,which were reacted with mixed epoxy to obtain rosin side-chain type vitrimers.It was completely characterized by differential scanning calorimetry test,thermogravimetric analysis,shape memory test and self-healing test.The prepared vitrimers exhibited good self-healing properties,excellent heat resistance(T_(d)=352℃)as well as high mechanical properties(tensile strength of 46.75 MPa).The tricyclic diterpene structure of rosin was introduced into the side chain in order to avoid the reduction of cross-link density resulting from the huge steric hindrance of the rigid tricyclic hydrophenylene skeleton.Vitrimers can undergo dynamic transesterification reaction without external catalysts due to the autocatalytic effect of tertiary amines from epoxy.Moreover,our work expanded the application field of rosin,increased the added value of rosin,and provided a novel method for preparing rosin-based vitrimers with ideal properties.
基金the National Natural Science Foundation of China (Nos.21672239,21737004 and 21421002)Key Laboratory of Photochemical Conversion and Optoelectr onic Materials,TIPC,CAS,the Sanming Institute of Fluorochemical Industry (Nos.FCIT201704GR,FCIT201705GR,FCIT201701BR)STS Program of Chinese Academy of Science (KF-STS-QYZX-068).
文摘The importance of CF3-containing molecules in pharmaceuticals, agrochemicals and materials intrigues the intense interest in synthetic methodology of these compounds. With a purpose to enrich trifluoromethylation methodology, we carefully examined the substrate scope of hydroxytrifluoromethylation of alkenes using iodotrifluoromethane, and the reaction provided β-trifluoromethyl alcohols in good yields under extremely mild conditions without catalysts. We found that our reaction can be applied to not only styrenes but also various aliphatic alkenes with excellent selectivity;no ketone was detected in most of our cases. Another feature of our discovery is “simple”. The reaction was carried out in air, irradiated by visible light, at room temperature and most importantly no catalyst was needed. A solution of CF3I in DMSO was used as the facile trifluoromethylating reagent, which simplified the utilization of gaseous CF3I. Based on 19F NMR spectroscopy, we observed a halogen bond between CF3I and tertiary amine in this reaction. The interaction may promote single electron transfer by the visible light irradiation.
基金partially supported by the National Natural Science Foundation of China (Nos. 21875152 and 21404077)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China (No. 17KJB150034)+2 种基金the Priority Academic Program Development of Jiangsu High Education Institutions (PAPD)the financial supports from Jiangsu Planned Projects for Postdoctoral Research Funds (No. 1501023B)China Postdoctoral Science Foundation (No. 2016M591906)
文摘The copper-catalyzed and metal-free azide-alkyne click polymerizations have become efficient tools for polymer synthesis. However,the 1,3-dipolar polycycloadditions between internal alkynes and azides are rarely employed to construct functional polymers. Herein, the polycycloadditions of dibutynoate(1) and tetraphenylethene-containing diazides(2) were carried out at 100 °C for 12 h under solvent-and catalyst-free conditions, producing soluble poly(methyltriazolylcarboxylate)s(PMTCs) with high molecular weights in high yields. The resultant polymers were thermally stable with 5% weight loss temperatures up to 377 °C. The PMTCs showed aggregation-induced emission(AIE)properties. They could work as fluorescent sensors for detecting explosive with high sensitivity, and generate two-dimensional fluorescent photopatterns with high resolution. Furthermore, their triazolium salts could be utilized for cell-imaging applications.
基金financially supported by the National Natural Science Foundation of China (Nos. 21490574, 21875019, 51673024, and 51803009)Beijing Institute of Technology Research Fund Program for Young Scholars
文摘A series of new photodegradable poly(furan-amine)s(PFAs) were synthesized by a one-pot, catalyst-free, multicomponent cyclopolymerization between diisocyanides, dialkylacetylene dicarboxylates, and aromatic dialdehydes. All polymerizations were conducted in toluene at 100 ℃ for 6 h without inert gas protection and furnished polymers with a satisfactory molecular weight(Mw up to32200) and yield. The PFA structure was confirmed by spectroscopic techniques, such as GPC, FTIR, and NMR, as well as by comparison with a model compound. The polymers exhibited good solubility in common organic solvents and thermal stability. All the PFAs had high refractive indices in the visible light region(400 nm to 800 nm). Moreover, the PFAs were substantially degraded by UV irradiation due to the presence of furan rings. The film thickness reduction rate could be over 90%.
基金financial support from the National Natural Science Foundation of China (Nos. 21820102004, 91961104, 21803030, 21875104, and 51673095)Program B for outstanding Ph.D. candidates of Nanjing University+2 种基金the Fundamental Research Funds for the Central Universities (No. 020514380253)the Natural Science Foundation of Jiangsu Province (No. BK20211555)the Jiangsu Innovation and Entrepreneurship Talents Plan
文摘The tandem reaction of photoinduced double hydrogen-atom transfer and deoxygenative transborylation for chemo-and site-selective reduction of nitroarenes into aryl amines under catalyst-free, room temperature conditions was disclosed in excellent yields. In this reaction, isopropanol(^(i)PrOH) was used as hydrogen donor and tetrahydroxydiboron [B_(2)(OH)_(4)] as deoxygenative reagent with green, cheap, and commercially available credentials. In particular, a wide range of reducible functional groups such as halogen(-Cl,-Br and even-I), alkenyl, alkynyl, aldehyde, ketone, carboxyl, and cyano are all tolerated. Moreover,the reaction preferentially reduces the nitro group at the electron-deficient site over another nitro group in the same molecule. A detailed mechanistic investigation in combination of experiments and theoretical calculations gave a reasonable explanation for the reaction pathway.
基金Project supported by the Chinese Academy of Sciences (Hundreds of Talents Program) and the National Natural Science Foundation fo China (No. 20972179).
文摘Aldol reaction between simple benzaldehydes and ketones successfully happened in solvent- and catalyst-free condition. The desired products were obtained in moderate yield at suitable temperature. Heat was assumed as the driving force for the reaction. This approach has obvious advantages to fully meet the requirement of the principles of green chemistry.
基金Project supported by the National Natural Science Foun-dation of China (Nos. 20704037, 20872130 and 20874086) and the Zhejiang Provincial Natural Science Foundation (Nos. 2008-Y407086, 2009-Y4080198 and 2010-Z4090225).
文摘A simple, efficient and eco-friendly route has been developed for the synthesis of fl-mercapto diketones via a multicomponent reaction of an aldehyde, acetylacetone and thiol in water. This methodology affords a number of β-mercapto diketone derivatives in moderate to good yields.
基金supported financially by Youth Foundation of Guangdong Medical College(No.XQ1029)Science and Technology Planning Project of Zhanjiang city(No.2009c3103024)
文摘4-Methylene-1,3-oxazolidin-2-ones can be synthesized from propargylic alcohols, primary amines and carbon dioxide under supercritical condition in the absence of any additional catalyst and solvent. Various propargylic alcohols and primary amines were examined.
基金the Major Basic Research Project of the Natural Science Founda- tion of the Jiangsu Higher Education Institutions (No. 15KJA150006), the Natural Science Foundation of Jiangsu Province (No. BK20131160), a project fund from the Priority Academic Project Development of the Jiangsu Higher Education Institutions, the Foundation of the Key Laboratory of Organic Synthesis of Jiangsu Province (No. JSK1210) and the Jiangsu College Grad- uate Research and Innovation Project of the Jiangsu Province Department of Education (No. KYZZ 0336).
文摘A simple and efficient one-pot procedure has been developed for the construction of pyrrolo[ 1,2-a]pyrimidines via the three-component domino reaction of 5-aminopyrazoles, acetylenedicarboxylates and malononitrile under catalyst-free, microwave irradiation conditions. The key step in this transformation is the N--N bond cleavage reac- tion of the 5-aminopyrazole substrate, which has been reported in this context for the first time in this study. The advantages of this protocol include readily available starting materials, short reaction times and good regioselectivity.
基金Financial support from the Recruitment Program of Global Experts (1000 Talents Plan)the Natural Science Foundation of Fujian Province (No. 2016J01064)+1 种基金Fujian Hundred Talents Plan, Program of Innovative Research Team of Huaqiao University (No. Z14X0047)Subsidized Project for Cultivating Postgraduates’ Innovative Ability in Scientific Research of Huaqiao University (for Z. Kuang) are gratefully acknowledged
文摘An expedient and mild strategy for the synthesis of unconventional 2-(dimethylamino)-3,3-difluorochroman-4-one derivatives from o-hydroxyarylenaminones and Selectfluor was developed at room temperature under catalyst-free conditions. This method showed excellent chemoselectivity and great functional groups tolerance.