Cyclohexanone oxime serves as a crucial intermediate in the synthesis of caprolactam,which is an essential precursor for manufacturing nylonfibers,high-performance engineering plastics,and specialized plasticfilms.Cat...Cyclohexanone oxime serves as a crucial intermediate in the synthesis of caprolactam,which is an essential precursor for manufacturing nylonfibers,high-performance engineering plastics,and specialized plasticfilms.Catalytic hydrogenation of nitrocyclohexane to cyclohexanone oxime has been documented to be an atom-economical,green and environmentally friendly process.In this review,wefirst introduce the current design rules of catalysts for catalytic hydrogenation of nitrocyclohexane in terms of both active metals and supports.Secondly,we discuss the influence of solvent effects on the cyclohexanone oxime from the nitrocyclohexane conversion.In addition,we concisely discuss typically proposed reaction pathways for the hydrogenation of nitrocyclohexane to produce cyclohexanone oxime.Finally,we provide our perspectives on some issues for catalytic conversion of nitrocyclohexane to cyclohexanone oxime in the future.展开更多
As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneou...As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.展开更多
The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-c...The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-centered radical initiated transformations remain largely elusive.Herein,a visible-lightinduced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst-and metal-free conditions.This protocol features mild conditions,broad substrate scope,good functional tolerance,and operational simplicity,yielding a diverse array ofα-phosphinoyl oximes in moderate to good yields with high stereoselectivities.The photomediated homolytic cleavage of O–NO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.展开更多
To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated th...To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated the in vitro antifungal activity of these compounds against six common plant pathogenic fungi.Among them,compounds B1-6,B1-17 and B2-6 displayed great in vitro activity against Rhizoctonia solani with EC50 values of 7.28,4.64,and 7.62μg/mL.The HOMO and LUMO calculations indicated that strong electronwithdrawing halogen elements exhibit better activity compared to electron-donating alkyl groups.Preliminary mechanistic studies,using SEM and TEM,indicated that compound B1-17 induced disordered entanglement of hyphae,shrinkage of hyphal surfaces,and vacuole swelling and rupture,which disrupted normal hyphal growth.Additionally,compound B1-17 induced the production and accumulation of ROS,disrupted MMP,and effectively inhibited the germination and formation of sclerotia in Rhizoctonia solani.These compounds hold potential as new antifungal agents for further research.展开更多
The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were us...The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were used to build 3D-QSAR models for a series of N-benzyl isatin oximes JNK inhibitors. The best models were obtained for the receptor-based alignment with CoMSIA combining steric （S）, electrostatic （E）, and hydrogen bond donor （D） and hydrogen bond acceptor （A） fields （q2 = 0.759, r2 = 0.966, r2 pred = 0.703）. Based on the contour maps of RB CoMSIA model, some key structural factors responsible for inhibitory activity were investigated. Large groups at N-substituent or R6 position are preferred to interact with hydrophobic residues Ile70, Asp150, Ala151, Asn152 and Ser193. Electron-donating or hydrogen bond donor groups on the isatin ring would form polar and hydrogen bond with the negative-charged residue Glu147. In addition, electron-withdrawing groups or hydrogen bond acceptor group near the N-substituent would enhance inhibitory activity. The results are in good accordance and complementary to each other. The developed models could provide guidance in the rational design of more potent and selective JNK inhibitors.展开更多
06001 The Exposure Standard. Lin Yunzhu,MaRunshan,. Guo Zhengqiang:1(4). 1980. pp.258--265.An exposure Standard apparatus developed in NIM ispresented, The exposure range of this apparatus isfrom 0.001 to 10 lux·...06001 The Exposure Standard. Lin Yunzhu,MaRunshan,. Guo Zhengqiang:1(4). 1980. pp.258--265.An exposure Standard apparatus developed in NIM ispresented, The exposure range of this apparatus isfrom 0.001 to 10 lux·second. and the uncertainty ofthe exposure is not exceed ±0.01 logarithmic unit. Itbasically satisfies the requirements of Sensitometry andCan be used to calibrate different types ofsensitometers.展开更多
A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotati...A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotation test,zeta potential,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis techniques.Compared with benzohydroxamic acid(BA),1-(2-hydroxyphenyl)ethan-1-one oxime(HPEO)and sodium isobutyl xanthate(SIBX),HPHO exhibited excellent collecting power to malachite without additional reagents,such as Na2S regulator and methyl isobutyl carbinol(MIBC)frother.Results of zeta potential indicated that HPHO was coated on malachite surfaces through a chemisorption process.FTIR and XPS data gave clear evidence for the formation of Cu−oxime complex on malachite surfaces after HPHO adsorption through the linkage between C=C,—OH,N—OH group and Cu species.展开更多
An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of ...An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% (by mass); H 2 O 2 /yclohexanone molar ratio of 1.10; NH 3 /cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime (both>99%) were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.展开更多
Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reactio...Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reaction can be used for protection-deprotection,purification,and characterization of carbonyl compounds in organic synthesis,especially for the synthesis of medicines as well as the natural products.Moreover,because many oximes can be synthesized from non-carbonyl starting materials,the deoximation reaction is also widely used in the production of many carbonyl-contained fine chemicals.Deoximation methods by using stoichiometric reagents are mature and can produce the related carbonyl products in very high yield with broad substrate application scopes.But for environment-protection consideration as well as the production cost controlling purpose in fine chemical industry,developing catalytic deoximation methods is the trend of the field and there are a series of references on this topic in recent years.This short review summarized recent advances on the development of deoximation methods from stoichiometric reaction to catalytic reaction and the mechanisms of some important transformations were discussed in detail for reader reference.展开更多
A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that ...A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.展开更多
An intrinsic kinetics of cyclohexanone ammoximation in the liquid phase over titanium silicate molecular sieves is investigated in an isothermal slurry reactor at different initial reactant concentrations, catalyst lo...An intrinsic kinetics of cyclohexanone ammoximation in the liquid phase over titanium silicate molecular sieves is investigated in an isothermal slurry reactor at different initial reactant concentrations, catalyst loading, and reaction temperature. The rate equations are developed by analyzing data of kinetic measurements. More than 10 side reactions were found. H2O2 decomposition reaction must be considered and other side reactions can be neglected in the kinetic modeling. The predicted values of reaction rates based on the kinetic models are almost consistent with experimental ones. The models have guidance to the selection of reactor types and they are useful to the design and operation of reactor used.展开更多
Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at roo...Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at room temperature for 10 minutes.展开更多
The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density fun...The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density functional theory(DFT) calculations illustrated that the introduced phenyl group at the R^(1) position could enhance the acidity,while the heptyl group could effectively increase the hydrophobicity and benefit van der Waals interactions. Meanwhile,the introduced amino group at the R^(2) position could provide cationic sites to interact with negatively charged surfaces of minerals, while the introduced hydroxyl group could provide additional action sites to form stable chelates with metal ions. Based on the structure-activity relationships, structural optimization was carried out to obtain three efficient collectors, which possessed superior flotation separation performances, proving the effectiveness of the structural modification to oxime compounds in this work.展开更多
Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Re...Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Recent advances for the synthesis of nitriles through photoinduced C—C bond cleavage of cycloketone oximes classified by the type of C—X bond forming are summarized.Various compounds possessing nitriles can be efficiently accessed via this method.展开更多
Caprolactam, which is mainly produced via the Beckmann rearrangement reaction, is an important chemical material. The strict specifications of caprolactam products make the refining process of caprolactam extremely im...Caprolactam, which is mainly produced via the Beckmann rearrangement reaction, is an important chemical material. The strict specifications of caprolactam products make the refining process of caprolactam extremely important. According to the different rearrangement process, the refining process of caprolactam is also different. The main refining sequence of liquid phase rearrangement products includes extraction, ion exchange, hydrogenation, and distillation. The refining process of gas phase rearrangement products is conducted mainly through distillation, crystallization, and hydrogenation. In this paper, the research progress of caprolactam refining technology will be summarized according to different rearrangement reaction processes, which will provide a reference for the selection of appropriate caprolactam refining process.展开更多
The crystal structure of the title compound （C18H18N4O, Mr = 306.36） has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with α = 4.783（0）, b = 13.577（1）, c = 13...The crystal structure of the title compound （C18H18N4O, Mr = 306.36） has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with α = 4.783（0）, b = 13.577（1）, c = 13.830（1） A, α = 63.581（2）, β = 88.326（2）, γ = 86.161（2）°, V= 802.5（1） A3, Z= 2, Dc = 1.268 g/cm^3, F（000） = 324, μ（MoKa） = 0.082 mm^-1, the final R = 0.0497 and wR = 0.1199 for 3094 observed reflections （I 〉 2σ（I））. The dihedral angles between the phenyl （C（1）-C（4）-（6）） and triazole, the phenyl （C（13）-C（15）-C（18）） and triazole, and the two phenyl rings are 7.9（1）, 69.9（1） and 67.8（1）°, respectively. Strong C-H…π interaction joins molecules into a chain along the c axis and contributes to the stability of the structure. Preliminary bioassay results show that the title compound possesses excellent and selective fungicidal activity against Colletotrichum gossypii but displays moderate to weak insecticidal activity against aphides.展开更多
基金financial support from the National Natural Science Foundation of China(22125202,92461312,U24A20487,92361201)Natural Science Foundation of Jiangsu Province(BK20220033).
文摘Cyclohexanone oxime serves as a crucial intermediate in the synthesis of caprolactam,which is an essential precursor for manufacturing nylonfibers,high-performance engineering plastics,and specialized plasticfilms.Catalytic hydrogenation of nitrocyclohexane to cyclohexanone oxime has been documented to be an atom-economical,green and environmentally friendly process.In this review,wefirst introduce the current design rules of catalysts for catalytic hydrogenation of nitrocyclohexane in terms of both active metals and supports.Secondly,we discuss the influence of solvent effects on the cyclohexanone oxime from the nitrocyclohexane conversion.In addition,we concisely discuss typically proposed reaction pathways for the hydrogenation of nitrocyclohexane to produce cyclohexanone oxime.Finally,we provide our perspectives on some issues for catalytic conversion of nitrocyclohexane to cyclohexanone oxime in the future.
基金National Nature Science Foundation of China(Nos.52025032,52103144 and 523B2026)for their financial supportsupported by the Postdoctoral Fellowship Program of China Postdoctoral Science Foundation(No.GZC20231544)。
文摘As one of the most essential components in photocuring system,photoinitiators(PIs)exert a crucial influence on the properties of the cured product.However,commercially available PIs encounter challenges in simultaneously achieving efficient photoinitiation performance and excellent light absorption properties,significantly limiting their applications in various fields.Here,two bis-chalcones and four corresponding oxime esters(OXEs)were designed and synthesized as highly efficient PIs.Featuring a structure comprising bis-chalcone and two diphenyl sulfides,the conjugated systems in these compounds enhance their light-absorption properties in near-ultraviolet and visible region,effectively.Both the frontier molecular orbital simulations and excited state calculations suggest the contribution of sulfur atoms to electron delocalization and the formation of conjugated structure.Due to the high reactivity of the N–O bond in OXE moiety,the four OXEs exhibit exceptional free radical photoinitiating ability in commercial acrylic monomers/oligomers with LED@365nm as light source.Notably,one of them demonstrates superior performance in the photoinitiation of multifunctional crosslinker,achieving more than 70%conversion within 3 s,coupled with outstanding absorption at 365 nm.These chalcone-based OXEs are considered to exert significant potential in the realm of free radical photocuring.
基金the financial support from the National Natural Science Foundation of China(Nos.22201265,22201264)the China Postdoctoral Science Foundation(Nos.2022M710133,2022TQ0287)。
文摘The tert-butyl nitrite as a bifunctional reagent mediated radical alkene difunctionalization has emerged as a powerful strategy for synthesis of structurally diverse oxime-containing compounds.However,the phosphorus-centered radical initiated transformations remain largely elusive.Herein,a visible-lightinduced radical phosphinoyloximation of alkenes with secondary phosphine oxides and tert-butyl nitrite has been developed under photocatalyst-and metal-free conditions.This protocol features mild conditions,broad substrate scope,good functional tolerance,and operational simplicity,yielding a diverse array ofα-phosphinoyl oximes in moderate to good yields with high stereoselectivities.The photomediated homolytic cleavage of O–NO bond of tert-butyl nitrite generates the reactive tert-butoxyl radical and persistent NO radical to act as both HAT reagent and the source of oximes.
基金the Fundamental Research Funds for the Central Universities(KYCYXT2022011,KJYQ2024014)the National Key Research and Development Program of China(2021YFD1700102)for the generous financial support for our programs.
文摘To develop new environmentally friendly fungicides,we designed and synthesized a novel series of D/Lconfigured camphor oxime ester derivatives based on the natural product camphor as a lead compound.We investigated the in vitro antifungal activity of these compounds against six common plant pathogenic fungi.Among them,compounds B1-6,B1-17 and B2-6 displayed great in vitro activity against Rhizoctonia solani with EC50 values of 7.28,4.64,and 7.62μg/mL.The HOMO and LUMO calculations indicated that strong electronwithdrawing halogen elements exhibit better activity compared to electron-donating alkyl groups.Preliminary mechanistic studies,using SEM and TEM,indicated that compound B1-17 induced disordered entanglement of hyphae,shrinkage of hyphal surfaces,and vacuole swelling and rupture,which disrupted normal hyphal growth.Additionally,compound B1-17 induced the production and accumulation of ROS,disrupted MMP,and effectively inhibited the germination and formation of sclerotia in Rhizoctonia solani.These compounds hold potential as new antifungal agents for further research.
基金supported by the Beijing Natural Science Foundation(Grant No.2123062)Research Fund for the Doctoral Program of Higher Education of China(Grant No.20121103120008)Science and Tech-nology Foundation of Beijing University of Technology(Grant No.ykj-2012-8725)
文摘The c-Jun N-terminal kinase （JNK） is involved in a variety of important cellular processes and aberrant JNK activity is associated with many human diseases.The ligand-based and receptor-based alignment rules were used to build 3D-QSAR models for a series of N-benzyl isatin oximes JNK inhibitors. The best models were obtained for the receptor-based alignment with CoMSIA combining steric （S）, electrostatic （E）, and hydrogen bond donor （D） and hydrogen bond acceptor （A） fields （q2 = 0.759, r2 = 0.966, r2 pred = 0.703）. Based on the contour maps of RB CoMSIA model, some key structural factors responsible for inhibitory activity were investigated. Large groups at N-substituent or R6 position are preferred to interact with hydrophobic residues Ile70, Asp150, Ala151, Asn152 and Ser193. Electron-donating or hydrogen bond donor groups on the isatin ring would form polar and hydrogen bond with the negative-charged residue Glu147. In addition, electron-withdrawing groups or hydrogen bond acceptor group near the N-substituent would enhance inhibitory activity. The results are in good accordance and complementary to each other. The developed models could provide guidance in the rational design of more potent and selective JNK inhibitors.
文摘06001 The Exposure Standard. Lin Yunzhu,MaRunshan,. Guo Zhengqiang:1(4). 1980. pp.258--265.An exposure Standard apparatus developed in NIM ispresented, The exposure range of this apparatus isfrom 0.001 to 10 lux·second. and the uncertainty ofthe exposure is not exceed ±0.01 logarithmic unit. Itbasically satisfies the requirements of Sensitometry andCan be used to calibrate different types ofsensitometers.
基金Projects(2018GDASCX-0934,2020GDASYL-20200302009)supported by Guangdong Academy of Sciences,China。
文摘A novel collector 1-(2-hydroxyphenyl)hex-2-en-1-one oxime(HPHO)was synthesized from 2-hydroxy acetophenone and butyraldehyde.Its flotation performance and adsorption mechanism to malachite were investigated by flotation test,zeta potential,Fourier transform infrared(FTIR)and X-ray photoelectron spectroscopy(XPS)analysis techniques.Compared with benzohydroxamic acid(BA),1-(2-hydroxyphenyl)ethan-1-one oxime(HPEO)and sodium isobutyl xanthate(SIBX),HPHO exhibited excellent collecting power to malachite without additional reagents,such as Na2S regulator and methyl isobutyl carbinol(MIBC)frother.Results of zeta potential indicated that HPHO was coated on malachite surfaces through a chemisorption process.FTIR and XPS data gave clear evidence for the formation of Cu−oxime complex on malachite surfaces after HPHO adsorption through the linkage between C=C,—OH,N—OH group and Cu species.
基金Supported by the National Natural Science Foundation of China and Sinopec (20736009)
文摘An innovative green process of producing ε-caprolactam was proposed by integrating ammoximation and Beckmann rearrangement effectively. As a first part of the new process, TS-1 molecular sieve-catalyzed synthesis of cyclohexanone oxime from cyclohexanone, ammonia and hydrogen peroxide was carried out in a batch plant. Cyclohexane was used as the solvent in the three-phase reaction system. The influences of essential process parameters on ammoximation were investigated. Under the reaction conditions as catalyst content of 2.5% (by mass); H 2 O 2 /yclohexanone molar ratio of 1.10; NH 3 /cyclohexanone molar ratio of 2.20; reaction temperature of 343 K; reaction time of 5 h, high conversion of cyclohexanone and selectivity to oxime (both>99%) were obtained. Thus, the three-phase ammoximation process showed equal catalytic activity as TS-1 but much more convenient and simpler for the separation of catalyst in comparison to the industrial two-phase system with t-butanol used as solvent.
基金supported by National Key Research and Development Program of China (No. 2018YFD0200100)Natural Science Foundation of Guangling College (Key Project: No. ZKZD17005+4 种基金 major special project: No. ZKZZ18001)Natural Science Foundation of Jiangsu Province (No. BK20181449)Jiangsu Provincial Six Talent Peaks Project (No. XCL-090)Opening Foundation of the Key Laboratory of Green Pesticide and Agricultural Bioengineering, Ministry of Education, Guizhou University (No. 2016GDGP0104)Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
文摘Deoximation reaction is one of the most important transformations in organic synthesis and for fine chemical production.Since oximes are easily synthesized from carbonyl compounds and are stable compounds,this reaction can be used for protection-deprotection,purification,and characterization of carbonyl compounds in organic synthesis,especially for the synthesis of medicines as well as the natural products.Moreover,because many oximes can be synthesized from non-carbonyl starting materials,the deoximation reaction is also widely used in the production of many carbonyl-contained fine chemicals.Deoximation methods by using stoichiometric reagents are mature and can produce the related carbonyl products in very high yield with broad substrate application scopes.But for environment-protection consideration as well as the production cost controlling purpose in fine chemical industry,developing catalytic deoximation methods is the trend of the field and there are a series of references on this topic in recent years.This short review summarized recent advances on the development of deoximation methods from stoichiometric reaction to catalytic reaction and the mechanisms of some important transformations were discussed in detail for reader reference.
基金financial supported by the National Natural Science Foundation of China(No.21202089)China Postdoctoral Science Foundation(No.2013M531145)the Research Foundation of the Six People Peak of Jiangsu Province(No.2013-SWYY-013)
文摘A series of new pyrazole oximes bearing substituted thiazole ring were designed and prepared. The structures of the title compounds were identified by spectral analyses, The results of primary bioassay indicated that some targeted compounds exhibited promising insecticidal activity besides acaricidal activity, particularly; compounds 8c and 8d were more potent against Tetranychus cinnabarinus and Plutella xylostella than other analogues.
文摘An intrinsic kinetics of cyclohexanone ammoximation in the liquid phase over titanium silicate molecular sieves is investigated in an isothermal slurry reactor at different initial reactant concentrations, catalyst loading, and reaction temperature. The rate equations are developed by analyzing data of kinetic measurements. More than 10 side reactions were found. H2O2 decomposition reaction must be considered and other side reactions can be neglected in the kinetic modeling. The predicted values of reaction rates based on the kinetic models are almost consistent with experimental ones. The models have guidance to the selection of reactor types and they are useful to the design and operation of reactor used.
文摘Oximes of ketones and aldehydes are efficiently converted to the corresponding carbonyl compounds, using a combination of NaHSO4.H20 and paraformaldehyde in good to excellent yields under solid state conditions at room temperature for 10 minutes.
基金the support of the National Natural Science Foundation of China(Nos.51774329 and 51904337)the High Performance Computing Center of Central South University,China。
文摘The relationships between the structure of oxime compounds(R^(1)R^(2)C=NOH,R^(1)/R^(2)=alkyl groups) with different substituents and their corresponding flotation performances were studied. The analyses of density functional theory(DFT) calculations illustrated that the introduced phenyl group at the R^(1) position could enhance the acidity,while the heptyl group could effectively increase the hydrophobicity and benefit van der Waals interactions. Meanwhile,the introduced amino group at the R^(2) position could provide cationic sites to interact with negatively charged surfaces of minerals, while the introduced hydroxyl group could provide additional action sites to form stable chelates with metal ions. Based on the structure-activity relationships, structural optimization was carried out to obtain three efficient collectors, which possessed superior flotation separation performances, proving the effectiveness of the structural modification to oxime compounds in this work.
基金support from the Natural Science Foundation of Gansu Province(No.3ZS061-A25-019)the Scientific Research fund of Gansu Provincial Education Department(No.0601-25)
文摘Under mild conditions, conversion of a variety of ketoximes and aldoximes to their corresponding amides and nitriles proceeded in the presence of PEG-SO3H with high yields.
基金the National Natural Science Foundation of China(Nos.21672037 and 21532001)the Leading Innovative and Entrepreneur Team Introduction Program of Zhejiang(No.2019R01005)。
文摘Nitriles are widely existed in many bioactive compounds,and they can be easily transformed into other functional groups.Therefore,the synthesis of nitriles under cyanide-free conditions is of significant importance.Recent advances for the synthesis of nitriles through photoinduced C—C bond cleavage of cycloketone oximes classified by the type of C—X bond forming are summarized.Various compounds possessing nitriles can be efficiently accessed via this method.
文摘Caprolactam, which is mainly produced via the Beckmann rearrangement reaction, is an important chemical material. The strict specifications of caprolactam products make the refining process of caprolactam extremely important. According to the different rearrangement process, the refining process of caprolactam is also different. The main refining sequence of liquid phase rearrangement products includes extraction, ion exchange, hydrogenation, and distillation. The refining process of gas phase rearrangement products is conducted mainly through distillation, crystallization, and hydrogenation. In this paper, the research progress of caprolactam refining technology will be summarized according to different rearrangement reaction processes, which will provide a reference for the selection of appropriate caprolactam refining process.
基金Supported by NNSFC (20302002 and 20872046)the SRF for ROCS, SEM (No. [2007] 1108)
文摘The crystal structure of the title compound （C18H18N4O, Mr = 306.36） has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with α = 4.783（0）, b = 13.577（1）, c = 13.830（1） A, α = 63.581（2）, β = 88.326（2）, γ = 86.161（2）°, V= 802.5（1） A3, Z= 2, Dc = 1.268 g/cm^3, F（000） = 324, μ（MoKa） = 0.082 mm^-1, the final R = 0.0497 and wR = 0.1199 for 3094 observed reflections （I 〉 2σ（I））. The dihedral angles between the phenyl （C（1）-C（4）-（6）） and triazole, the phenyl （C（13）-C（15）-C（18）） and triazole, and the two phenyl rings are 7.9（1）, 69.9（1） and 67.8（1）°, respectively. Strong C-H…π interaction joins molecules into a chain along the c axis and contributes to the stability of the structure. Preliminary bioassay results show that the title compound possesses excellent and selective fungicidal activity against Colletotrichum gossypii but displays moderate to weak insecticidal activity against aphides.
