Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over...Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over NiV-layered double hydroxides(LDHs) thin films.Mechanistic studies confirmed the hydroxyl active intermediate(-OH*) generated on the surface of NiV-LDHs films by employing electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy.By using advanced techniques,e.g.,extended X-ray absorption fine structure and high-angle annular dark-field scanning transmission electron microscopy,NiV-LDHs films with 2.6 nm could expose larger specific surface area.Taking benzaldehyde as a model,high current density of 200 mA cm^(-2)at 1.8 V vs.RHE,81.1% conversion,77.6% yield of benzoic acid and 90.8% Faradaic efficiency were reached,which was superior to most of previous studies.Theoretical DFT analysis was well matched with experimental findings and documented that NiV-LDHs had high adsorption capacity for the aldehydes to suppress the side reaction,and the aldehydes were oxidized by the electrophilic hydroxyl radicals formed on NiV-LDHs.Our findings offer a universal strategy for the robust upgrading of diverse biomass-derived platform chemicals.展开更多
As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective...As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.展开更多
A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochlor...A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide(ZnO) as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration(〈1 min),high selectivity;and high yield(90-98%).展开更多
Ferrous methanesulfonate catalysing the conversion of aromatic, heteroaromatic, unsaturated, and aliphatic aldehydes to 1,1- diacetates at room temperature under solvent-free condition has been developed. The catalyti...Ferrous methanesulfonate catalysing the conversion of aromatic, heteroaromatic, unsaturated, and aliphatic aldehydes to 1,1- diacetates at room temperature under solvent-free condition has been developed. The catalytic activity of seventeen metal methanesulfonates was compared under the same condition, ferrous methanesufonate proved to be the best. It can be easily recovered and reused for several times without distinct deterioration in catalytic activity. During the competitive protection between a ketone and an aldehyde group with Ac20, 1,1-diacetate formed exclusively with the aldehyde group. 2009 Min Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.展开更多
A facile, efficient and substrate-selective oxidation of aldehydes to carboxylic acids with NaClO catalyzed by β-cyclodextrin in water has been developed. A series of aldehydes which could form inclusion complex with...A facile, efficient and substrate-selective oxidation of aldehydes to carboxylic acids with NaClO catalyzed by β-cyclodextrin in water has been developed. A series of aldehydes which could form inclusion complex with β-cyclodextrin (β-CD) were oxidized selectively with excellent yields.展开更多
Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via...Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.展开更多
An efficient and environmentally benign conversion of aldehydes into the corresponding gem-dicarboxylates was realized by using hydrated ferric sulfate as a heterogeneous catalyst. In addition to its high efficiency,...An efficient and environmentally benign conversion of aldehydes into the corresponding gem-dicarboxylates was realized by using hydrated ferric sulfate as a heterogeneous catalyst. In addition to its high efficiency, the catalyst can be recovered simply and reused efficiently for at least seven times.展开更多
The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImB...The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImBF4 could be reused.展开更多
Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides sever...Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides several advantages such as environmentally friendly,short reaction times,high yields,non-hazardous and simple work-up procedure.展开更多
Highly efficient aerobic oxidation of benzylic aldehydes to the corresponding acids catalyzed by iron (Ⅲ) meso-tetrapbenylporphyrin chloride (Fe(TPP)Cl) under ambient conditions was developed. The catalyst has ...Highly efficient aerobic oxidation of benzylic aldehydes to the corresponding acids catalyzed by iron (Ⅲ) meso-tetrapbenylporphyrin chloride (Fe(TPP)Cl) under ambient conditions was developed. The catalyst has been proved to be an excellent catalyst for the system in the presence of molecular oxygen and isobutryaldehyde at room temperature.展开更多
An efficient procedure for the synthesis ofβ-keto esters from the reaction of aldehydes and ethyl diazoacetate catalyzed by iodine at room temperature under solvent-free conditions has been described. The catalytic p...An efficient procedure for the synthesis ofβ-keto esters from the reaction of aldehydes and ethyl diazoacetate catalyzed by iodine at room temperature under solvent-free conditions has been described. The catalytic procedure has the advantages of easily available catalyst, mild reaction conditions, high yields, and easy work-up.展开更多
Cobalt methanesulfonate in combination with acetic acid catalysed the chemoselective diacetylation of aldehyde with acetic anhydride at room temperature under solvent free conditions. After reaction, cobalt methanesul...Cobalt methanesulfonate in combination with acetic acid catalysed the chemoselective diacetylation of aldehyde with acetic anhydride at room temperature under solvent free conditions. After reaction, cobalt methanesulfonate can be easily recovered and reused many times. The reaction was mild and efficient with good to high yields.展开更多
Clean liquid oxidation of aldehydes can be accomplished using solid catalyst in the presence of molecular oxygen at room temperature, which is a valuable alternative to traditional counterparts.
The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione, bartbituric acid and 2-thiobarbituric acid proceede...The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione, bartbituric acid and 2-thiobarbituric acid proceeded very efficiently in water in the presence of triethylbenzylammonium chloride (TEBA) and the products were isolated simply by filtration.展开更多
Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indiu...Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.展开更多
1 Introduction Ionic liquids(ILs) are environmentally acceptable solvents because they have low vapor pressure, high thermal stability and chemical stability, excellent solvent for organic and inorganic compounds. T...1 Introduction Ionic liquids(ILs) are environmentally acceptable solvents because they have low vapor pressure, high thermal stability and chemical stability, excellent solvent for organic and inorganic compounds. Therefore, they can be used as green solvents for a number of chemical processes, such as separa- tions and reactions. ILs are also used as catalysts in chemical reactions to accelerate reaction rate and improve selectivity.展开更多
The contents of terpenoid aldehydes in Bt transgenic cotton and their non-Bt parental varieties were analyzed by the HPLC method. Statistical analysis of variance showed that Bt insecticidal protein Bt-ICP expression ...The contents of terpenoid aldehydes in Bt transgenic cotton and their non-Bt parental varieties were analyzed by the HPLC method. Statistical analysis of variance showed that Bt insecticidal protein Bt-ICP expression has no negative effect on the synthesis of gossypol, total heliocides and total resistant terpenoids. The results of the combined dosage test of Bt-ICP and gossypol in vitro showed that there is no interaction between gossypol and Bt-ICP on the mortality of cotton bollworm larvae Helicoverpa armigera (Hubnner). It is indicated that the actions of Bt-ICP and gossypol on cotton bollworm are additive. Therefore, it is advantageous to combine Bt-ICP with cotton terpenoid aldehydes in controlling cotton bollworm.展开更多
SBA-15 supported Mo catalysts (Moy/SBA-15) were prepared by an ultrasonic assisted incipient-wetness impregnation method. The physical and chemical properties of the catalysts were characterized by means of N2-adsor...SBA-15 supported Mo catalysts (Moy/SBA-15) were prepared by an ultrasonic assisted incipient-wetness impregnation method. The physical and chemical properties of the catalysts were characterized by means of N2-adsorption-desorption, XRD, TEM, UV-Vis, Raman, XANES and H2-TPR. The results showed that a trace amount of MoO3 was produced on high Mo content samples. Tum-over frequency (TOF) and product selectivity are dependent on the molybdenum content. Both Mo0.75/SBA-15 and Mo1.75/SBA-15 catalysts give the higher catalytic activity and the selectivity to the total aldehydes for the selective oxidation of C2H6. At the reaction temperature of 625℃, the maximum yield of aldehydes reached 4.2% over Mo0.75/SBA-15 catalyst. The improvement of the activity and selectivity was related with the state of MoOx species.展开更多
The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols wit...The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.展开更多
The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configurat...The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configuration by 1H NMR.展开更多
基金supported by the National Natural Science Foundation of China(22078374,21776324)the Scientific and Technological Planning Project of Guangzhou(202206010145)+2 种基金the National Ten Thousand Talent Plan,Key-Area Research and Development Program of Guangdong Province(2019B110209003)the Guangdong Basic and Applied Basic Research Foundation(2019B1515120058,2020A1515011149)the Start-up Fund for Senior Talents in Jiangsu University(21JDG060)。
文摘Selective upgrading of C=O bonds to afford carboxylic acid is significant for the petrochemical industry and biomass utilization.Here we declared the efficient electrooxidation of biomass-derived aldehydes family over NiV-layered double hydroxides(LDHs) thin films.Mechanistic studies confirmed the hydroxyl active intermediate(-OH*) generated on the surface of NiV-LDHs films by employing electrochemical impedance spectroscopy and the electron paramagnetic resonance spectroscopy.By using advanced techniques,e.g.,extended X-ray absorption fine structure and high-angle annular dark-field scanning transmission electron microscopy,NiV-LDHs films with 2.6 nm could expose larger specific surface area.Taking benzaldehyde as a model,high current density of 200 mA cm^(-2)at 1.8 V vs.RHE,81.1% conversion,77.6% yield of benzoic acid and 90.8% Faradaic efficiency were reached,which was superior to most of previous studies.Theoretical DFT analysis was well matched with experimental findings and documented that NiV-LDHs had high adsorption capacity for the aldehydes to suppress the side reaction,and the aldehydes were oxidized by the electrophilic hydroxyl radicals formed on NiV-LDHs.Our findings offer a universal strategy for the robust upgrading of diverse biomass-derived platform chemicals.
基金supported by the National Key Research and Development Program of China(2019YFA0210302)the National Natural Science Foundation of China(21878009).
文摘As one of the few renewable aromatic resources,the research of depolymerization of lignin into highvalue chemicals has attracted extensive attention in recent years.Catalytic wet aerobic oxidation(CWAO)is an effective technology to convert lignin like sodium lignosulfonate(SL),a lignin derivative,into aromatic aldehydes such as vanillin and syringaldehyde.However,how to improve the yield of aromatic aldehyde and conversion efficiency is still a challenge,and many operating conditions that significantly affect the yield of these aromatic compounds have rarely been investigated systematically.In this work,we adopted the stirred tank reactor(STR)for the CWAO process with nano-CuO as catalyst to achieve the conversion of SL into vanillin and syringaldehyde.The effect of operating conditions including reaction time,oxygen partial pressure,reaction temperature,SL concentration,rotational speed,catalyst amount,and NaOH concentration on the yield of single phenolic compound was systematically investigated.The results revealed that all these operating conditions exhibit a significant effect on the aromatic aldehyde yield.Therefore,they should be regulated in an optimal value to obtain high yield of these aldehydes.More importantly,the reaction kinetics of the lignin oxidation was explored.This work could provide basic data for the optimization and design of industrial operation of lignin oxidation.
文摘A rapid and eco-friendly one-pot protocol for the synthesis of nitriles has been developed by treating various araldehydes bearing electron withdrawing as well as electron donating groups with hydroxylamine hydrochloride in the presence of non-toxic,non-corrosive and reusable zinc oxide(ZnO) as the catalyst under solvent-free microwave irradiation.The present approach offers the advantages of a clean reaction,simple methodology,employing readily available catalyst,short reaction duration(〈1 min),high selectivity;and high yield(90-98%).
文摘Ferrous methanesulfonate catalysing the conversion of aromatic, heteroaromatic, unsaturated, and aliphatic aldehydes to 1,1- diacetates at room temperature under solvent-free condition has been developed. The catalytic activity of seventeen metal methanesulfonates was compared under the same condition, ferrous methanesufonate proved to be the best. It can be easily recovered and reused for several times without distinct deterioration in catalytic activity. During the competitive protection between a ketone and an aldehyde group with Ac20, 1,1-diacetate formed exclusively with the aldehyde group. 2009 Min Wang. Published by Elsevier B.V. on behalf of Chinese Chemical Society. All rights reserved.
基金the National Natural Science Foundation of China(No.20776053)the Program for New Century Excellent Talents in University(No.NCET-06-740)for providing financial support for this project.
文摘A facile, efficient and substrate-selective oxidation of aldehydes to carboxylic acids with NaClO catalyzed by β-cyclodextrin in water has been developed. A series of aldehydes which could form inclusion complex with β-cyclodextrin (β-CD) were oxidized selectively with excellent yields.
基金supported by the National Nature Science Foundation of China (J1210060, 21143002)
文摘Sulfonated carbon as a strong and stable solid acid catalyst exhibited excellent catalytic performance in various acid-catalyzed reactions. Here, sulfonated carbon, as catalyst for oxidation reaction, was prepared via the carbonization of starch followed by sulfonation with concentrated sulfuric acid. N2 physisorption, X-ray diffraction, Fourier transform infrared spectroscopy, X-ray fluorescence and acid-base titration were used to characterize the obtained materials. The catalytic activity of sulfonated carbon was studied in the oxidation of aldehydes to carboxylic acids using 30 wt% H2O2 as oxidant. This oxidation protocol works well for various aldehydes including aromatic and aliphatic aldehydes. The sulfonated carbon can be recycled for three times without obvious loss of activity.
文摘An efficient and environmentally benign conversion of aldehydes into the corresponding gem-dicarboxylates was realized by using hydrated ferric sulfate as a heterogeneous catalyst. In addition to its high efficiency, the catalyst can be recovered simply and reused efficiently for at least seven times.
文摘The sodium borohydride reduction of aldehydes and ketones to corresponding alcohols has been accomplished via the use of ionic liquids. The alcohols are easily obtained with excellent yields and the ionic liquid BMImBF4 could be reused.
文摘Green,mild and efficient iodination of hydroxylated aromatic aldehydes and ketones using iodine and iodic acid in the solidstate by grinding under solvent-free conditions at room temperature.This method provides several advantages such as environmentally friendly,short reaction times,high yields,non-hazardous and simple work-up procedure.
基金The authors thank the National Natural Science Foundation of China (No. 20576045)the Program for New Century Excellent Talents in University (NCET) for the financial support.
文摘Highly efficient aerobic oxidation of benzylic aldehydes to the corresponding acids catalyzed by iron (Ⅲ) meso-tetrapbenylporphyrin chloride (Fe(TPP)Cl) under ambient conditions was developed. The catalyst has been proved to be an excellent catalyst for the system in the presence of molecular oxygen and isobutryaldehyde at room temperature.
基金Supported by the Special Scientific Research Project of Shaanxi Education Commission(No.08JZ09) the Science Re-search Foundation of Baoji University of Arts and Sciences, China(No.ZK064)
文摘An efficient procedure for the synthesis ofβ-keto esters from the reaction of aldehydes and ethyl diazoacetate catalyzed by iodine at room temperature under solvent-free conditions has been described. The catalytic procedure has the advantages of easily available catalyst, mild reaction conditions, high yields, and easy work-up.
文摘Cobalt methanesulfonate in combination with acetic acid catalysed the chemoselective diacetylation of aldehyde with acetic anhydride at room temperature under solvent free conditions. After reaction, cobalt methanesulfonate can be easily recovered and reused many times. The reaction was mild and efficient with good to high yields.
文摘Clean liquid oxidation of aldehydes can be accomplished using solid catalyst in the presence of molecular oxygen at room temperature, which is a valuable alternative to traditional counterparts.
文摘The condensation of aromatic aldehydes with acidic methylene compounds such as malononitrile, methyl cyanoacetate, cyanoacetamide, 5,5-dimethyl-1,3-cyclohexanedione, bartbituric acid and 2-thiobarbituric acid proceeded very efficiently in water in the presence of triethylbenzylammonium chloride (TEBA) and the products were isolated simply by filtration.
文摘Recent investigations have shown the oxone-mediated oxidative methyl esterification of benzaldehyde derivatives using methanol. The reactions were accelerated in the presence of indium(III) triflate, a trivalent indium reagent, in many cases. Based on this method of methyl esterification of benzaldehyde derivatives, we further explored an application to heterocyclic aldehydes. The reactions were examined using methanol as well as other alcohols in order to establish a suitable range.
基金Supported by the National Natural Science Foundation of China(No.20802008)
文摘1 Introduction Ionic liquids(ILs) are environmentally acceptable solvents because they have low vapor pressure, high thermal stability and chemical stability, excellent solvent for organic and inorganic compounds. Therefore, they can be used as green solvents for a number of chemical processes, such as separa- tions and reactions. ILs are also used as catalysts in chemical reactions to accelerate reaction rate and improve selectivity.
文摘The contents of terpenoid aldehydes in Bt transgenic cotton and their non-Bt parental varieties were analyzed by the HPLC method. Statistical analysis of variance showed that Bt insecticidal protein Bt-ICP expression has no negative effect on the synthesis of gossypol, total heliocides and total resistant terpenoids. The results of the combined dosage test of Bt-ICP and gossypol in vitro showed that there is no interaction between gossypol and Bt-ICP on the mortality of cotton bollworm larvae Helicoverpa armigera (Hubnner). It is indicated that the actions of Bt-ICP and gossypol on cotton bollworm are additive. Therefore, it is advantageous to combine Bt-ICP with cotton terpenoid aldehydes in controlling cotton bollworm.
基金supported by NSFC(21376261,21173270,21177160)Beijing Natural Science Foundation(2142027)+1 种基金863 Program of China(2013AA065302)the Doctor Select Foundation(20130007110007)
文摘SBA-15 supported Mo catalysts (Moy/SBA-15) were prepared by an ultrasonic assisted incipient-wetness impregnation method. The physical and chemical properties of the catalysts were characterized by means of N2-adsorption-desorption, XRD, TEM, UV-Vis, Raman, XANES and H2-TPR. The results showed that a trace amount of MoO3 was produced on high Mo content samples. Tum-over frequency (TOF) and product selectivity are dependent on the molybdenum content. Both Mo0.75/SBA-15 and Mo1.75/SBA-15 catalysts give the higher catalytic activity and the selectivity to the total aldehydes for the selective oxidation of C2H6. At the reaction temperature of 625℃, the maximum yield of aldehydes reached 4.2% over Mo0.75/SBA-15 catalyst. The improvement of the activity and selectivity was related with the state of MoOx species.
文摘The reduction of TiCl4(THF)2 with Al in CH2Cl2 gave a green solution of [Ti2(μ-Cl)2Cl4· (THF)4] (1) which was found to promote the reductive homocoupling of aromatic aldehydes to yield symmetrical 1, 2-diols with high diasterepselectivities.
文摘The title compounds 3 and 4 condensed with aromatic aldehydes to give a--aroylsicinnamoyl ketene cyclic dithioacetals 5 and 6 with sodium ethoxide as the base. The stereochemistryofs and 6 was assigned as E-configuration by 1H NMR.