Aromatic aldehydes are the most fundamentally important compounds used in organic synthesis.The development of new synthetic methods for introduction of a formyl group into an organic scaffold is highly desirable.In t...Aromatic aldehydes are the most fundamentally important compounds used in organic synthesis.The development of new synthetic methods for introduction of a formyl group into an organic scaffold is highly desirable.In this report,a nickel-catalyzed reductive coupling between aryl halides andα–chloro N-methoxyphthalimide has been documented for the synthesis of a diverse array of aromatic aldehydes.Because of mild reductive coupling conditions,excellent functional group tolerance,especially for substrates containing free-OH and-NH_(2),was observed.Due to the simple operation mode,a large library of aromatic aldehydes can be quickly constructed by this process.Moreover,the present protocol is amenable for late-stage functionalization of bioactive compound.A combined computational and experimental investigation suggested the reaction may undergo a reaction mechanism of active Ni(I)catalyst formation and the formation of key formyl radical intermediate under zinc reductive conditions.展开更多
For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at...For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.展开更多
Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3-hexamethyldisilazane（HMDS） as silylating agent,in the presence of polyvinylpolypyrrolidonium tribromide in acetonitrile at room temperature.Also a varie...Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3-hexamethyldisilazane（HMDS） as silylating agent,in the presence of polyvinylpolypyrrolidonium tribromide in acetonitrile at room temperature.Also a variety of alcohols were converted into alkyl formates by ethyl formate and a catalytic amount of polyvinylpolypyrrolidonium tribromide under solvent free conditions at room temperature.展开更多
2-（Sulfooxy）propane-1,2,3-tricarboxylic acid（supported on silica gel） has been introduced as novel and green catalyst for the formylation of alcohols and amines with ethyl formate,as mild formylation agent,under n...2-（Sulfooxy）propane-1,2,3-tricarboxylic acid（supported on silica gel） has been introduced as novel and green catalyst for the formylation of alcohols and amines with ethyl formate,as mild formylation agent,under neat conditions at room temperature.展开更多
Two species of N-arylpyrazoles containing active amino group were synthesized.And formylations of N-arylpyazoles containing amino in different position of pyrazole rings using Vilsmeier-Haack reaction gave a series of...Two species of N-arylpyrazoles containing active amino group were synthesized.And formylations of N-arylpyazoles containing amino in different position of pyrazole rings using Vilsmeier-Haack reaction gave a series of useful pyrazole intermediates.The important features of this protocol were cheap materials,easy process,mild reaction conditions and good yield of products.展开更多
NaY zeolite functionalized by sulfamic acid/Cu（OAc）_2[NaY/SA/Cu（Ⅱ）] was synthesized and used as a new,efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst ...NaY zeolite functionalized by sulfamic acid/Cu（OAc）_2[NaY/SA/Cu（Ⅱ）] was synthesized and used as a new,efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis.Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.展开更多
A highly efficient and selective bimetallic Pd0.88Co0.12 nanoparticle catalyst was developed for the direct N-formylation of amines by carbon monoxide. This catalyst is compatible with a wide range of substrates, affo...A highly efficient and selective bimetallic Pd0.88Co0.12 nanoparticle catalyst was developed for the direct N-formylation of amines by carbon monoxide. This catalyst is compatible with a wide range of substrates, affording various synthetically useful formamides under practical and mild reaction conditions.展开更多
A facile and efficient method for the formylation of Grignard reagent was reported, and a new approach for the preparation of aldehydes from Grignard reagent and benzimidazolium salts was provided.
Functionalised mesoporous poly(ionic liquid)s are valuable carbon dioxide capture and conversion materials.Here,an imidazole poly(ionic liquid)PIL-s1-HCO_(3) with a mesoporous structure was formed by the copolymerisat...Functionalised mesoporous poly(ionic liquid)s are valuable carbon dioxide capture and conversion materials.Here,an imidazole poly(ionic liquid)PIL-s1-HCO_(3) with a mesoporous structure was formed by the copolymerisation of vinyl-modified ionic liquids and crosslinking agents.The material has excellent adsorption properties for carbon dioxide.Using it as the catalyst,the formylation of carbon dioxide with various amides was realised at room temperature and pressure without metal participation.In addition,the material is stable in performance,easily separated,and has good reusability.In this work,relying on the new PIL as a multi-functional platform,carbon dioxide capture and the transformation to high-value-added chemicals were completed simultaneously.展开更多
Objective:Premature rupture of membranes(PROM)is a common pregnancy disorder that is closely associated with structural weakening of fetal membranes.Studies have found that formyl peptide receptor 1(FPR1)activates inf...Objective:Premature rupture of membranes(PROM)is a common pregnancy disorder that is closely associated with structural weakening of fetal membranes.Studies have found that formyl peptide receptor 1(FPR1)activates inflammatory pathways and amniotic epithelial-mesenchymal transition(EMT),stimulates collagen degradation,and leads to membrane weakening and membrane rupture.The purpose of this study was to investigate the anti-inflammatory and EMT inhibitory effects of FPR1 antagonist(BOC-MLF)to provide a basis for clinical prevention of PROM.Methods:The relationship between PROM,FPR1,and EMT was analyzed in human fetal membrane tissue and plasma samples using Western blotting,PCR,Masson staining,and ELISA assays.Lipopolysaccharide(LPS)was used to establish a fetal membrane inflammation model in pregnant rats,and BOC-MLF was used to treat the LPS rat model.We detected interleukin(IL)-6 in blood from the rat hearts to determine whether the inflammatory model was successful and whether the anti-inflammatory treatment was effective.We used electron microscopy to analyze the structure and collagen expression of rat fetal membrane.Results:Western blotting,PCR and Masson staining indicated that the expression of FPR1 was significantly increased,the expression of collagen was decreased,and EMT appeared in PROM.The rat model indicated that LPS caused the collapse of fetal membrane epithelial cells,increased intercellular gaps,and decreased collagen.BOC-MLF promoted an increase in fetal membrane collagen,inhibited EMT,and reduced the weakening of fetal membranes.Conclusion:The expression of FPR1 in the fetal membrane of PROM was significantly increased,and EMT of the amniotic membrane was obvious.BOC-MLF can treat inflammation and inhibit amniotic EMT.展开更多
The photodissociation dynamics of jet-cooled HCO radical was investigated in the region of 490 nm to 715 nm using the H-atom high-n Rydberg time-of-flight(HRTOF)technique.The CO product rovibrational state populations...The photodissociation dynamics of jet-cooled HCO radical was investigated in the region of 490 nm to 715 nm using the H-atom high-n Rydberg time-of-flight(HRTOF)technique.The CO product rovibrational state populations are well resolved in the H+CO product translational energy distributions,and an accurate H-C bond dissociation energy D0(H-CO)=5086±5 cm^(-1)is obtained.展开更多
The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We d...The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to CO2.The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of CO2.Consequently,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.展开更多
Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental ...Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.展开更多
Different alcohols were formylated by formic acid under solvent-free conditions in the presence of iodine as the catalyst with good-to-high yields at room temperature.I2 generated in situ from Fe(NO3)3·9H2O/NaI a...Different alcohols were formylated by formic acid under solvent-free conditions in the presence of iodine as the catalyst with good-to-high yields at room temperature.I2 generated in situ from Fe(NO3)3·9H2O/NaI also catalyzed the formylation of the alcohols under solvent-free conditions.This gives a green and efficient reaction at room temperature,in which the use of toxic and corrosive molecular I2 is avoided.展开更多
The title compound 5,17-diformyl-11,23-di（tert-butyl）-25,26,27,28-tetrapropoxycalix[4]arene has been synthesized by selective formylation of 5,11,17,23-tetra（tert-butyl）25,26,27,28-tetrahydroxycalix[4]arene in thr...The title compound 5,17-diformyl-11,23-di（tert-butyl）-25,26,27,28-tetrapropoxycalix[4]arene has been synthesized by selective formylation of 5,11,17,23-tetra（tert-butyl）25,26,27,28-tetrahydroxycalix[4]arene in three steps and characterized by1H NMR and X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group C2/c with a = 25.760（3）,b = 10.9952（10）,c = 18.630（2）,β = 119.985（4）°,V = 4570.4（9）3,Z = 4,Dc = 1.106 g/cm3,Mr = 761.01,F（000） = 1648,μ = 0.071 mm-1,MoKa radiation（λ = 0.71073）,R = 0.0710 and wR = 0.2411 for 3234 observed reflections with I 2σ（I）.X-ray analysis reveals that the title compound adopts a pinched cone conformation which leads to an open cavity.Intermolecular C–H O weak interactions link the molecules along the bc plane,which are effective in the stabilization of the crystal structure.展开更多
[Objective]The paper was to study a synthetic method suitable for industrial production of intermediate N-Chloroformyl-N-[4-(trifluoromethoxy)phenyl]methyl carbamate of indoxacarb.[Method]Using 4-trifluoromethoxy anil...[Objective]The paper was to study a synthetic method suitable for industrial production of intermediate N-Chloroformyl-N-[4-(trifluoromethoxy)phenyl]methyl carbamate of indoxacarb.[Method]Using 4-trifluoromethoxy aniline as the starting material,[4-(trifluoromethoxy)phenyl]carbamate was synthesized by homogeneous formylation method without acid-binding agent.Subsequently,it was reacted with sodium methoxide/potassium methoxide by reactive distillation to obtain[4-(trifluoromethoxy)phenyl]carbamate ammonium sodium/potassium,then directly reacted with triphosgene to obtain crude products of N-carbonochloridoyl-N-[4-(trifluoromethoxy)phenyl]carbamate;finally,competing product was obtained by recrystallization.[Result]The intermediate N-chloroformyl-N-[4-(trifluoromethoxy)phenyl]carbamate was synthesized by the method.The content of products was higher than 98%.The yield of product reached above 96%(calculated by 4-trifluoromethoxy aniline).[Conclusion]The method used for the synthesis of intermediate N-chloroformyl-N-[4-(trifluoromethoxy)phenyl]methyl carbamate was simple,with less three wastes,higher safety and lower cost.展开更多
3-(Dimethylamino)-1-phenylprop-2-en-1-ones (formylated acetophenones) 1 reacted with aliphatic diamines in water assisted by KHSO4 to give bis-enaminones 2a-h in good yields. Compound 1 also reacted with o-phenylenedi...3-(Dimethylamino)-1-phenylprop-2-en-1-ones (formylated acetophenones) 1 reacted with aliphatic diamines in water assisted by KHSO4 to give bis-enaminones 2a-h in good yields. Compound 1 also reacted with o-phenylenediamine under similar conditions to produce bis-enaminones 3 instead of benzodiazepines 4 in excellent yields.展开更多
Inert gas-clustered systems (Xn, X = He, Ne, Ar and n = 2 - 20) were established in this study and their stability as a result of interparticulate interaction was examined. Ferric chloride and ferrous oxides were used...Inert gas-clustered systems (Xn, X = He, Ne, Ar and n = 2 - 20) were established in this study and their stability as a result of interparticulate interaction was examined. Ferric chloride and ferrous oxides were used as catalysts to promote reaction, and 5-nitro-1,2,4-triazol-3-one (NTO) was theoretically synthesized under an inert gas (X6)-clustered environment in this study. The raw material, urea, initially underwent chlorination using chlorine as the reagent, followed by amination, formylation and nitration. Reaction routes closely related to the experimental processes were successfully constructed, and the corresponding energy barriers were estimated for each elementary reaction. The findings revealed that the average errors in the B3LYP/6-31G(d, p)-calculated geometry and vibrational frequency of NTO in an Ne6 system relative to the observed values were 0.83% and 1.84%, respectively. The neon gas-clustered system achieved greater stabilization, which results from the difference in self-consistent field energy (ESCF), than the corresponding stabilization acquired in a helium- or argon-based system. Ferric chloride serves as a good catalyst to reduce the energy barrier of the chlorination reaction, and ferrous oxide is suitable for catalyzing the amination, formylation and nitration reactions, although nitric acid is the better agent for nitration. The catalytic Ne6-clustered reaction system is suggested to be a more feasible pathway for the synthesis of NTO.展开更多
Two asymmetric porphyrins, 5-(4-chloromethylphenyl)-10, 15, 20-triphenyl porphyrin and 5-(4-formylphenyl)-10, 15, 20-triphenyl porphyrin, were successfully prepared by the symmetric meso-tetraphenyl porphyrin and rela...Two asymmetric porphyrins, 5-(4-chloromethylphenyl)-10, 15, 20-triphenyl porphyrin and 5-(4-formylphenyl)-10, 15, 20-triphenyl porphyrin, were successfully prepared by the symmetric meso-tetraphenyl porphyrin and relative molecular configurations and properties were characterized by spectral determinations. This work presented an example for synthesis of asymmetric porphyrin derivatives from the symmetric porphyrin. Both asymmetric porphyrins are reactive in molecular assembly, the concerned reactions including alkylation with Grignard reagents, etherification with alcohols, aldol condensation and Mannich reaction for modification and enhancing their functionality. In this work, the reaction conditions were improved, synthetic strategy and route were confirmed.展开更多
The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically invest...The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically investigated at the CCSD（T）/6-311＋＋G（3df, 3pd）//MO6-2X/6- 311＋＋G（3df, 3pd） level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which reflects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun- neling correction, the kinetic data demonstrate that the entrance channel X…FCHO＋OH （X=H2O, FA, or SA） is significantly more favorable than the pathway X…OH＋FCHO. More- over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH＋FCHO reaction because the concentration of the formed X…FCHO or X…OH complex is quite low in the atmosphere.展开更多
基金financial support from the National Natural Science Foundation of China(No.22001147)Taishan Scholars Project of Shandong Province(No.tsqn202103027)+1 种基金Distinguished Young Scholars of Shandong Province(Overseas)(No.2022HWYQ-001)Qilu Youth Scholar Funding of Shandong University。
文摘Aromatic aldehydes are the most fundamentally important compounds used in organic synthesis.The development of new synthetic methods for introduction of a formyl group into an organic scaffold is highly desirable.In this report,a nickel-catalyzed reductive coupling between aryl halides andα–chloro N-methoxyphthalimide has been documented for the synthesis of a diverse array of aromatic aldehydes.Because of mild reductive coupling conditions,excellent functional group tolerance,especially for substrates containing free-OH and-NH_(2),was observed.Due to the simple operation mode,a large library of aromatic aldehydes can be quickly constructed by this process.Moreover,the present protocol is amenable for late-stage functionalization of bioactive compound.A combined computational and experimental investigation suggested the reaction may undergo a reaction mechanism of active Ni(I)catalyst formation and the formation of key formyl radical intermediate under zinc reductive conditions.
基金supported by the National Natural Science Foundation of China(91745106,21633013)the Major Projects of the National Natural Science Foundation of Gansu,China(18JR4RA001)+1 种基金the Youth Innovation Promotion Association CAS(2019409)Fujian Institute of Innovation,CAS and Key Research Program of Frontier Sciences of CAS(QYZDJ-SSW-SLH051)~~
文摘For the first time, Pd supported on natural palygorskite was developed for amine formylation with CO2 and H2. Both secondary and primary amines with diverse structures could be converted into the desired formamides at < 100 °C, and good to excellent yields were obtained.
文摘Trimethylsilylation of alcohols was achieved using 1,1,1,3,3,3-hexamethyldisilazane（HMDS） as silylating agent,in the presence of polyvinylpolypyrrolidonium tribromide in acetonitrile at room temperature.Also a variety of alcohols were converted into alkyl formates by ethyl formate and a catalytic amount of polyvinylpolypyrrolidonium tribromide under solvent free conditions at room temperature.
基金Financial support for this work by the Ilam University,Ilam,Iran is gratefully acknowledged
文摘2-（Sulfooxy）propane-1,2,3-tricarboxylic acid（supported on silica gel） has been introduced as novel and green catalyst for the formylation of alcohols and amines with ethyl formate,as mild formylation agent,under neat conditions at room temperature.
基金Project supported by the National Natural Science Foundation of China(No.20572079)the Natural Science Foundation of Zhejiang Province(No.Y407079)the Foundation of Science and Technology Department of Zhejiang Province(No.2007C21116).
文摘Two species of N-arylpyrazoles containing active amino group were synthesized.And formylations of N-arylpyazoles containing amino in different position of pyrazole rings using Vilsmeier-Haack reaction gave a series of useful pyrazole intermediates.The important features of this protocol were cheap materials,easy process,mild reaction conditions and good yield of products.
基金Arak University for financial support for this work
文摘NaY zeolite functionalized by sulfamic acid/Cu（OAc）_2[NaY/SA/Cu（Ⅱ）] was synthesized and used as a new,efficient and recyclable catalyst for preparation of formamides. This novel organic-inorganic hybrid catalyst was characterized by several techniques such as FT-IR, XRD, SEM, EDX and TG analysis.Chemoselectivity, easy procedure, excellent yields, very short reaction times, solvent-free and mild reaction conditions are some benefits of this new protocol.
基金We acknowledge financial support from the China Ministry of Science and Technology （No. 2016YFA0202801）, National Natural Science Foundation of China （No. 21371107）, Tsinghua-Peking Joint Centers for Life Sciences and CAMS Initiative for Innovative Medicine （No. 2016-I2M-3-014）.
文摘A highly efficient and selective bimetallic Pd0.88Co0.12 nanoparticle catalyst was developed for the direct N-formylation of amines by carbon monoxide. This catalyst is compatible with a wide range of substrates, affording various synthetically useful formamides under practical and mild reaction conditions.
基金supported by the National Natural Science Foundation of China(Grant No.20172041)the Provincial Natural Science Foundation of Shaanxi Province(Grant No.2003B12).
文摘A facile and efficient method for the formylation of Grignard reagent was reported, and a new approach for the preparation of aldehydes from Grignard reagent and benzimidazolium salts was provided.
基金We thank the financial support from the Guangxi Key R&D Program(No.AB18221005)the National Natural Science Foundation of China(Nos.41965006 and 52170107)the Innovation Project of GUET Graduate Education(No.2021YCXS170).
文摘Functionalised mesoporous poly(ionic liquid)s are valuable carbon dioxide capture and conversion materials.Here,an imidazole poly(ionic liquid)PIL-s1-HCO_(3) with a mesoporous structure was formed by the copolymerisation of vinyl-modified ionic liquids and crosslinking agents.The material has excellent adsorption properties for carbon dioxide.Using it as the catalyst,the formylation of carbon dioxide with various amides was realised at room temperature and pressure without metal participation.In addition,the material is stable in performance,easily separated,and has good reusability.In this work,relying on the new PIL as a multi-functional platform,carbon dioxide capture and the transformation to high-value-added chemicals were completed simultaneously.
文摘Objective:Premature rupture of membranes(PROM)is a common pregnancy disorder that is closely associated with structural weakening of fetal membranes.Studies have found that formyl peptide receptor 1(FPR1)activates inflammatory pathways and amniotic epithelial-mesenchymal transition(EMT),stimulates collagen degradation,and leads to membrane weakening and membrane rupture.The purpose of this study was to investigate the anti-inflammatory and EMT inhibitory effects of FPR1 antagonist(BOC-MLF)to provide a basis for clinical prevention of PROM.Methods:The relationship between PROM,FPR1,and EMT was analyzed in human fetal membrane tissue and plasma samples using Western blotting,PCR,Masson staining,and ELISA assays.Lipopolysaccharide(LPS)was used to establish a fetal membrane inflammation model in pregnant rats,and BOC-MLF was used to treat the LPS rat model.We detected interleukin(IL)-6 in blood from the rat hearts to determine whether the inflammatory model was successful and whether the anti-inflammatory treatment was effective.We used electron microscopy to analyze the structure and collagen expression of rat fetal membrane.Results:Western blotting,PCR and Masson staining indicated that the expression of FPR1 was significantly increased,the expression of collagen was decreased,and EMT appeared in PROM.The rat model indicated that LPS caused the collapse of fetal membrane epithelial cells,increased intercellular gaps,and decreased collagen.BOC-MLF promoted an increase in fetal membrane collagen,inhibited EMT,and reduced the weakening of fetal membranes.Conclusion:The expression of FPR1 in the fetal membrane of PROM was significantly increased,and EMT of the amniotic membrane was obvious.BOC-MLF can treat inflammation and inhibit amniotic EMT.
基金supported by the US National Science Foundation(grant number CHE-2155232).
文摘The photodissociation dynamics of jet-cooled HCO radical was investigated in the region of 490 nm to 715 nm using the H-atom high-n Rydberg time-of-flight(HRTOF)technique.The CO product rovibrational state populations are well resolved in the H+CO product translational energy distributions,and an accurate H-C bond dissociation energy D0(H-CO)=5086±5 cm^(-1)is obtained.
基金supported by the National Natural Science Foundation of China (21676306,21425627)the National Key Research and Development Program of China (2016YFA0602900)+1 种基金the Natural Science Foundation of Guangdong Province (2016A030310211)the Characteristic Innovation Project (Natural Science) of Guangdong Colleges and Universities~~
文摘The combination of a zinc phthalocyanine(ZnPc)catalyst and a stoichiometric amount of dimethyl formamide(DMF)provided a simple route to formamide derivatives from amines,CO2,and hydrosilanes under mild conditions.We deduced that formation of an active zinc‐hydrogen(Zn‐H)species promoted hydride transfer from the hydrosilane to CO2.The cooperative activation of the Lewis acidic ZnPc by strongly polar DMF,led to formation of activated amines and hydrosilanes,which promoted the chemical reduction of CO2.Consequently,the binary ZnPc/DMF catalytic system showed excellent yields and superior chemoselectivity,representing a simple and sustainable pathway for the reductive transformation of CO2into valuable chemicals as an alternative to conventional halogen‐containing process.
文摘Nano‐catalysis plays a vital role in the chemical transformations and significantly impacts the booming modern chemical industry.The rapid technological enhancements have resulted in serious energy and environmental issues,which are currently spurring the exploration of the novel nano‐catalysts in diverse fields.In order to develop the efficient nano‐catalysts,it is essential to understand their fundamental physicochemical properties,including the coordination structures of the active centers and substrate‐adsorbate interactions.Subsequently,the nano‐catalyst design with precise manipulation at the atomic level can be attained.In this account,we have summarized our extensive investigation of the factors impacting nano‐catalysis,along with the synthetic strategies developed to prepare the nano‐catalysts for applications in electrocatalysis,photocatalysis and thermocatalysis.Finally,a brief conclusion and future research directions on nano‐catalysis have also been presented.
基金Supported by Bu-Ali Sina University and University of Kurdistan Research Councils
文摘Different alcohols were formylated by formic acid under solvent-free conditions in the presence of iodine as the catalyst with good-to-high yields at room temperature.I2 generated in situ from Fe(NO3)3·9H2O/NaI also catalyzed the formylation of the alcohols under solvent-free conditions.This gives a green and efficient reaction at room temperature,in which the use of toxic and corrosive molecular I2 is avoided.
基金Supported by the National Natural Science Foundation of China(No.21002009)Major Program for the Natural Science Research of Jiangsu Colleges and Universities(12KJA150002)+3 种基金Jiangsu Key Laboratory of Advanced Catalytic Materials and Technology(BM2012110)the Scientific and Technological Project of Changzhou(CJ20115019)Priority Academic Program Development of Jiangsu Higher Education Institutionsthe Qing-Lan Project of Jiangsu Province
文摘The title compound 5,17-diformyl-11,23-di（tert-butyl）-25,26,27,28-tetrapropoxycalix[4]arene has been synthesized by selective formylation of 5,11,17,23-tetra（tert-butyl）25,26,27,28-tetrahydroxycalix[4]arene in three steps and characterized by1H NMR and X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group C2/c with a = 25.760（3）,b = 10.9952（10）,c = 18.630（2）,β = 119.985（4）°,V = 4570.4（9）3,Z = 4,Dc = 1.106 g/cm3,Mr = 761.01,F（000） = 1648,μ = 0.071 mm-1,MoKa radiation（λ = 0.71073）,R = 0.0710 and wR = 0.2411 for 3234 observed reflections with I 2σ（I）.X-ray analysis reveals that the title compound adopts a pinched cone conformation which leads to an open cavity.Intermolecular C–H O weak interactions link the molecules along the bc plane,which are effective in the stabilization of the crystal structure.
文摘[Objective]The paper was to study a synthetic method suitable for industrial production of intermediate N-Chloroformyl-N-[4-(trifluoromethoxy)phenyl]methyl carbamate of indoxacarb.[Method]Using 4-trifluoromethoxy aniline as the starting material,[4-(trifluoromethoxy)phenyl]carbamate was synthesized by homogeneous formylation method without acid-binding agent.Subsequently,it was reacted with sodium methoxide/potassium methoxide by reactive distillation to obtain[4-(trifluoromethoxy)phenyl]carbamate ammonium sodium/potassium,then directly reacted with triphosgene to obtain crude products of N-carbonochloridoyl-N-[4-(trifluoromethoxy)phenyl]carbamate;finally,competing product was obtained by recrystallization.[Result]The intermediate N-chloroformyl-N-[4-(trifluoromethoxy)phenyl]carbamate was synthesized by the method.The content of products was higher than 98%.The yield of product reached above 96%(calculated by 4-trifluoromethoxy aniline).[Conclusion]The method used for the synthesis of intermediate N-chloroformyl-N-[4-(trifluoromethoxy)phenyl]methyl carbamate was simple,with less three wastes,higher safety and lower cost.
文摘3-(Dimethylamino)-1-phenylprop-2-en-1-ones (formylated acetophenones) 1 reacted with aliphatic diamines in water assisted by KHSO4 to give bis-enaminones 2a-h in good yields. Compound 1 also reacted with o-phenylenediamine under similar conditions to produce bis-enaminones 3 instead of benzodiazepines 4 in excellent yields.
文摘Inert gas-clustered systems (Xn, X = He, Ne, Ar and n = 2 - 20) were established in this study and their stability as a result of interparticulate interaction was examined. Ferric chloride and ferrous oxides were used as catalysts to promote reaction, and 5-nitro-1,2,4-triazol-3-one (NTO) was theoretically synthesized under an inert gas (X6)-clustered environment in this study. The raw material, urea, initially underwent chlorination using chlorine as the reagent, followed by amination, formylation and nitration. Reaction routes closely related to the experimental processes were successfully constructed, and the corresponding energy barriers were estimated for each elementary reaction. The findings revealed that the average errors in the B3LYP/6-31G(d, p)-calculated geometry and vibrational frequency of NTO in an Ne6 system relative to the observed values were 0.83% and 1.84%, respectively. The neon gas-clustered system achieved greater stabilization, which results from the difference in self-consistent field energy (ESCF), than the corresponding stabilization acquired in a helium- or argon-based system. Ferric chloride serves as a good catalyst to reduce the energy barrier of the chlorination reaction, and ferrous oxide is suitable for catalyzing the amination, formylation and nitration reactions, although nitric acid is the better agent for nitration. The catalytic Ne6-clustered reaction system is suggested to be a more feasible pathway for the synthesis of NTO.
文摘Two asymmetric porphyrins, 5-(4-chloromethylphenyl)-10, 15, 20-triphenyl porphyrin and 5-(4-formylphenyl)-10, 15, 20-triphenyl porphyrin, were successfully prepared by the symmetric meso-tetraphenyl porphyrin and relative molecular configurations and properties were characterized by spectral determinations. This work presented an example for synthesis of asymmetric porphyrin derivatives from the symmetric porphyrin. Both asymmetric porphyrins are reactive in molecular assembly, the concerned reactions including alkylation with Grignard reagents, etherification with alcohols, aldol condensation and Mannich reaction for modification and enhancing their functionality. In this work, the reaction conditions were improved, synthetic strategy and route were confirmed.
文摘The mechanisms and kinetics of the gas phase reactions that the hydrogen atom in formyl fluoride （FCHO） abstracted by OH in the presence of water, formic acid （FA）, or sulfuric acid （SA） are theoretically investigated at the CCSD（T）/6-311＋＋G（3df, 3pd）//MO6-2X/6- 311＋＋G（3df, 3pd） level of theory. The calculated results show that the barriers of the transition states involving catalysts are lowered to -2.89, -6.25, and -7.76 kcal/mol from 3.64 kcal/mol with respect to the separate reactants, respectively, which reflects that those catalysts play an important role in reducing the barrier of the hydrogen abstraction reaction of FCHO with OH. Additionally, using conventional transition state theory with Eckart tun- neling correction, the kinetic data demonstrate that the entrance channel X…FCHO＋OH （X=H2O, FA, or SA） is significantly more favorable than the pathway X…OH＋FCHO. More- over, the rate constants of the reactions of FCHO with OH radical with H2O, FA, or SA introduced are computed to be smaller than that of the naked OH＋FCHO reaction because the concentration of the formed X…FCHO or X…OH complex is quite low in the atmosphere.
