Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The product...Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yields under mild reaction conditions and in short reaction times.展开更多
For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were ob...For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones,providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one α-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity.Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate,which could not only result in the reversal of the diastereoselectivity,but also improve the reactivity.展开更多
An expedient and economic approach for constructing O,O,N-spiro compounds consisting of both a 1,3-oxazine and a furan ring through a catalyst-free formal[4+1]/[4+2]cycloaddition cascade sequence of isocyanides with t...An expedient and economic approach for constructing O,O,N-spiro compounds consisting of both a 1,3-oxazine and a furan ring through a catalyst-free formal[4+1]/[4+2]cycloaddition cascade sequence of isocyanides with two molecules of acylketene formed in situ through thermal-induced Wolff rearrangement of 2-diazo-1,3-diketones was developed.The reaction displayed good functional group tolerance and was compatible with different isocyanides and 2-diazo-1,3-diketones.Furthermore,preliminary asymmetric attempts of this reaction are made by utilizing optically pure isocyanides as inputs,and moderate diastereomeric induction was observed.展开更多
An efficient protocol for the synthesis of asymmetric 1,3-diketones was reported through diacylation of1,1-diborylalkanes using two different acyl sources.In this transfo rmation,an enolate boron species was initially...An efficient protocol for the synthesis of asymmetric 1,3-diketones was reported through diacylation of1,1-diborylalkanes using two different acyl sources.In this transfo rmation,an enolate boron species was initially formed by introducing an acyl group,then it was trapped by another acyl group to form 1,3-diketone.This method not only provided the gateway to obtain a series of 1,3-diketones,but also afforded an operationally simple and efficient access to pyrazoles and isoxazoles.展开更多
The clarification of the critical operating conditions and the failure mechanism of superlubricity systems is of great significance for seeking appropriate applications in industry.In this work,the superlubricity regi...The clarification of the critical operating conditions and the failure mechanism of superlubricity systems is of great significance for seeking appropriate applications in industry.In this work,the superlubricity region of 1,3-diketone oil EPND(1-(4-ethyl phenyl)nonane-1,3-dione)on steel surfaces was identified by performing a series of ball-on-disk rotation friction tests under various normal loads(3.5–64 N)and sliding velocities(100–600 mm/s).The result shows that beyond certain loads or velocities superlubricity failed to be reached due to the following negative effects:(1)Under low load(≤3.5 N),insufficient running-in could not ensure good asperity level conformity between the upper and lower surfaces;(2)the high load(≥64 N)produced excessive wear and big debris;(3)at low velocity(≤100 mm/s),the weak hydrodynamic effect and the generated debris deteriorated the lubrication performance;(4)at high velocity(≥500 mm/s),oil migration occurred and resulted in oil starvation.In order to expand the load and velocity boundaries of the superlubricity region,an optimized running-in method was proposed to avoid the above negative effects.By initially operating a running-in process under a suitable combination of load and velocity(e.g.16 N and 300 mm/s)and then switching to the target certain higher or lower load/velocity(e.g.100 N),the superlubricity region could break through its original boundaries.The result of this work suggests that oil-based superlubricity of 1,3-diketone is a promising solution to friction reduction under suitable operating conditions especially using a well-designed running-in strategy.展开更多
Zinc chloride(ZnCl_(2))was dissolved in the 1,3-dimethyl-2-imidazolinone(DMI)solvent,and the metallic zinc coatings were obtained by electrodeposition in room-temperature ambient air.The conductivity(σ),viscosity(η)...Zinc chloride(ZnCl_(2))was dissolved in the 1,3-dimethyl-2-imidazolinone(DMI)solvent,and the metallic zinc coatings were obtained by electrodeposition in room-temperature ambient air.The conductivity(σ),viscosity(η),and density(ρ)of the DMI−ZnCl_(2)solvated ionic liquid at various temperatures(T)were measured and fitted.Furthermore,cyclic voltammetry was used to study the electrochemical behavior of Zn(II)in the DMI−ZnCl_(2)solvated ionic liquid,indicating that the reduction of Zn(II)on the tungsten electrode was a one-step two-electron transfer irreversible process.XRD and SEM−EDS analysis of the cathode product confirmed that the deposited coating was metallic zinc.Finally,the effects of deposition potential,temperature and duration on the morphology of zinc coatings were investigated.The results showed that a dense and uniform zinc coating was obtained by potentiostatic electrodeposition at−2 V(vs Pt)and 353 K for 1 h.展开更多
Xanthene and Xanthenediones are structural components of several bioactive and semi-synthetic molecules. This work described an expeditious synthesis of novel and hitherto unreported bis-trifluoromethyl xanthene dione...Xanthene and Xanthenediones are structural components of several bioactive and semi-synthetic molecules. This work described an expeditious synthesis of novel and hitherto unreported bis-trifluoromethyl xanthene dione derivatives. The reaction of two equivalents of 5-trifluoromethyl cyclohexane-1,3- dione with substituted aromatic aldehydes in the presence of ethanol containing 1 - 2 drops of HCl was facile under microwave irradiation. Short reaction time (25 min), good to excellent yields (80% - 95%), good atom economy, and simple workup are the major advantages of the above procedure. Moreover, the fluorinated products represent synthetically useful stable intermediates that could find applications in pharmaceutical, agricultural and material industries.展开更多
A novel anionic trinuclear linear copper（II） complex {[Et3NH][Cul.5（CH3COO）- （TTA）3] } 2 （1, TTA = 2-thenoyltrifluoroacetonate） has been synthesized in a direct reaction involving copper（]l） acetate monohydr...A novel anionic trinuclear linear copper（II） complex {[Et3NH][Cul.5（CH3COO）- （TTA）3] } 2 （1, TTA = 2-thenoyltrifluoroacetonate） has been synthesized in a direct reaction involving copper（]l） acetate monohydrate, TTA and excess triethylamine base in dichloromethane solvent. Green colored X-ray quality crystals of 1 were grown from n-hexane solvent at room temperature. The data were collected at 100 K. Compound I crystallizes in the monoclinic P21/n space group （a = 11.2141（8）, b = 19.0965（13）, c = 17.3680（14） A, β = 90.225（2）°, V= 3719.3（5） A3, Mr = 1840.14, Dc = 1.643 Mg/m3, F（000） = 1866, μ = 1.129 mm^-1 and Z = 2）. The asymmetric unit of 1 contains two copper atoms, one of which lies on a crystallographic inversion center with 50% occupancy.展开更多
基金support from the Research Council of Mazandaran University
文摘Pyridinium bromochromate has been found to be a highly efficient and selective reagent for the α-monobromination of 1,3- diketones and β-keto-esters in the absence of base, Lewis acid, or other catalyst. The products were formed in high to excellent yields under mild reaction conditions and in short reaction times.
基金supported by the National Natural Science Foundation of China(21871255,21532006,21873096)Chinese Academy of Sciences(XDB17020300,XDB17010200)
文摘For the metal-catalyzed asymmetric hydrogenation of α-substituted ketones,cis reductive products are generally obtained due to steric hindrance of substituents.Herein,an unprecedented trans reductive products were observed in palladium-catalyzed hydrogenative desymmetrization of cyclic and acyclic 1,3-diketones,providing the chiral trans β-hydroxy ketones with two adjacent stereocenters including one α-tertiary or quaternary stereocenter with high enantioselectivity and diastereoselectivity.Mechanistic studies and DFT calculations suggested that the rarely observed diastereoselectivity reversal is ascribed to the charge-charge interaction between the palladium and aromatic ring of the substrate,which could not only result in the reversal of the diastereoselectivity,but also improve the reactivity.
基金supported by the National Natural Science Foundation of China(21801050)the Scientific Research Project of Guangzhou Municipal Colleges and Universities(201831816)。
文摘An expedient and economic approach for constructing O,O,N-spiro compounds consisting of both a 1,3-oxazine and a furan ring through a catalyst-free formal[4+1]/[4+2]cycloaddition cascade sequence of isocyanides with two molecules of acylketene formed in situ through thermal-induced Wolff rearrangement of 2-diazo-1,3-diketones was developed.The reaction displayed good functional group tolerance and was compatible with different isocyanides and 2-diazo-1,3-diketones.Furthermore,preliminary asymmetric attempts of this reaction are made by utilizing optically pure isocyanides as inputs,and moderate diastereomeric induction was observed.
基金the National Natural Science Foundation of China(Nos.91745110,21673261,21603245,21703265,21872156,21802150,21773210 and 21603190)Natural Science Foundation of Jiangsu Province(Nos.BK20190002,BK20181194 and BK20180247)+1 种基金Support from the Young Elite Scientist Sponsorship Program by CAST(No.YESS20170217)the Youth Innovation Promotion Association CAS(No.2018458)。
文摘An efficient protocol for the synthesis of asymmetric 1,3-diketones was reported through diacylation of1,1-diborylalkanes using two different acyl sources.In this transfo rmation,an enolate boron species was initially formed by introducing an acyl group,then it was trapped by another acyl group to form 1,3-diketone.This method not only provided the gateway to obtain a series of 1,3-diketones,but also afforded an operationally simple and efficient access to pyrazoles and isoxazoles.
基金supported by the National Natural Science Foundation of China(No.51975437)the Sino-German Center for Research Promotion(SGC)(GZ 1576).
文摘The clarification of the critical operating conditions and the failure mechanism of superlubricity systems is of great significance for seeking appropriate applications in industry.In this work,the superlubricity region of 1,3-diketone oil EPND(1-(4-ethyl phenyl)nonane-1,3-dione)on steel surfaces was identified by performing a series of ball-on-disk rotation friction tests under various normal loads(3.5–64 N)and sliding velocities(100–600 mm/s).The result shows that beyond certain loads or velocities superlubricity failed to be reached due to the following negative effects:(1)Under low load(≤3.5 N),insufficient running-in could not ensure good asperity level conformity between the upper and lower surfaces;(2)the high load(≥64 N)produced excessive wear and big debris;(3)at low velocity(≤100 mm/s),the weak hydrodynamic effect and the generated debris deteriorated the lubrication performance;(4)at high velocity(≥500 mm/s),oil migration occurred and resulted in oil starvation.In order to expand the load and velocity boundaries of the superlubricity region,an optimized running-in method was proposed to avoid the above negative effects.By initially operating a running-in process under a suitable combination of load and velocity(e.g.16 N and 300 mm/s)and then switching to the target certain higher or lower load/velocity(e.g.100 N),the superlubricity region could break through its original boundaries.The result of this work suggests that oil-based superlubricity of 1,3-diketone is a promising solution to friction reduction under suitable operating conditions especially using a well-designed running-in strategy.
基金The authors are grateful for the financial supports from the Fundamental Research Funds for the Central Universities,China(N182503033,N172502003)Postdoctoral Research Foundation of China(2018M640258)+1 种基金the National Natural Science Foundation of China(51804070)Guangxi Innovation-driven Development Program,China(GUIKE AA18118030).
文摘Zinc chloride(ZnCl_(2))was dissolved in the 1,3-dimethyl-2-imidazolinone(DMI)solvent,and the metallic zinc coatings were obtained by electrodeposition in room-temperature ambient air.The conductivity(σ),viscosity(η),and density(ρ)of the DMI−ZnCl_(2)solvated ionic liquid at various temperatures(T)were measured and fitted.Furthermore,cyclic voltammetry was used to study the electrochemical behavior of Zn(II)in the DMI−ZnCl_(2)solvated ionic liquid,indicating that the reduction of Zn(II)on the tungsten electrode was a one-step two-electron transfer irreversible process.XRD and SEM−EDS analysis of the cathode product confirmed that the deposited coating was metallic zinc.Finally,the effects of deposition potential,temperature and duration on the morphology of zinc coatings were investigated.The results showed that a dense and uniform zinc coating was obtained by potentiostatic electrodeposition at−2 V(vs Pt)and 353 K for 1 h.
文摘Xanthene and Xanthenediones are structural components of several bioactive and semi-synthetic molecules. This work described an expeditious synthesis of novel and hitherto unreported bis-trifluoromethyl xanthene dione derivatives. The reaction of two equivalents of 5-trifluoromethyl cyclohexane-1,3- dione with substituted aromatic aldehydes in the presence of ethanol containing 1 - 2 drops of HCl was facile under microwave irradiation. Short reaction time (25 min), good to excellent yields (80% - 95%), good atom economy, and simple workup are the major advantages of the above procedure. Moreover, the fluorinated products represent synthetically useful stable intermediates that could find applications in pharmaceutical, agricultural and material industries.
基金Financial support:South African National Research Foundation,(SA-NRF/THRIP),University of the Free State Materials and Nanoscience Research Cluster,SASOL and PETLABS pharmaceuticals
文摘A novel anionic trinuclear linear copper（II） complex {[Et3NH][Cul.5（CH3COO）- （TTA）3] } 2 （1, TTA = 2-thenoyltrifluoroacetonate） has been synthesized in a direct reaction involving copper（]l） acetate monohydrate, TTA and excess triethylamine base in dichloromethane solvent. Green colored X-ray quality crystals of 1 were grown from n-hexane solvent at room temperature. The data were collected at 100 K. Compound I crystallizes in the monoclinic P21/n space group （a = 11.2141（8）, b = 19.0965（13）, c = 17.3680（14） A, β = 90.225（2）°, V= 3719.3（5） A3, Mr = 1840.14, Dc = 1.643 Mg/m3, F（000） = 1866, μ = 1.129 mm^-1 and Z = 2）. The asymmetric unit of 1 contains two copper atoms, one of which lies on a crystallographic inversion center with 50% occupancy.
