A novel route for tandem C-C/C-N formation,annulation and aromatization of hydrazones with 1,2-dichloroethane to synthesize 1 H-pyrazoles has been developed.Furthermore,the 1,2-dichloroethane serves as alkylation reag...A novel route for tandem C-C/C-N formation,annulation and aromatization of hydrazones with 1,2-dichloroethane to synthesize 1 H-pyrazoles has been developed.Furthermore,the 1,2-dichloroethane serves as alkylation reagent in good to excellent yields.This methodology features mild reaction conditions and good functional group tolerance,providing a direct approach for the preparation of 1 Hpvrazoles.展开更多
By using 1-methyl-2-formyl-5 -Y-substituted pyrrole (4-nitrophenyl)hydrazones as a model for nitrogen-containing heterocyclic aromatic compounds, the emission wavelength [lambda(max(em))] values df their fluorescence ...By using 1-methyl-2-formyl-5 -Y-substituted pyrrole (4-nitrophenyl)hydrazones as a model for nitrogen-containing heterocyclic aromatic compounds, the emission wavelength [lambda(max(em))] values df their fluorescence spectra have been measured. Correlation results show that the Delta E-em values are mainly affected by polar effects, but spin-delocalizatin effects also exist.展开更多
A new series of dimeric Cu（II） and Ni（II） complexes with some aroylhydrazones of a-pyridoin were synthesized and characterized using different physical techniques. Their chemical formulae were based on their micro...A new series of dimeric Cu（II） and Ni（II） complexes with some aroylhydrazones of a-pyridoin were synthesized and characterized using different physical techniques. Their chemical formulae were based on their microanalysis and IR data. The structures of the solid complexes were determined from the electronic, IR and ESR spectral studies as well as their magnetic susceptibility measurements. The ligands acted as bi-, tri- and tetra-dentate forming different dinuclear complexes with different structures. The assumed molecular structures based on the experimental results were also confirmed by the molecular mechanics calculations. The extraction ability of the hydrazones has been investigated by liquid-liquid extraction for Cu（II） and Ni（II）.展开更多
Two new Schiff base benzoyl hydrazone compounds, C14H10FN3O3 （Ⅰ） and C14H10F2N2O （Ⅱ）, have been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. Both compounds cr...Two new Schiff base benzoyl hydrazone compounds, C14H10FN3O3 （Ⅰ） and C14H10F2N2O （Ⅱ）, have been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. Both compounds crystallize in monoclinic, space group P21/c with a = 7.0514（14）, b = 25.928（5）, c = 7.7099（15）, β = 111.823（2）°, V = 1308.6（4）3, Z = 4, C14H10FN3O3, Mr = 287.25, Dc = 1.458 g/cm3, μ（MoKα） = 0.115 mm-1, F（000） = 592, the final R = 0.0841 and wR = 0.2489 for 1901 observed reflections （I 2σ（I）） for I; a = 11.232（3）, b =12.735（4）, c = 8.612（2） , β = 90.869（3）°, V = 1231.7（6）3, Z = 4, C14H10F2N2O, Mr = 260.24, Dc = 1.403 g/cm3, μ（MoKα） = 0.111 mm-1, F（000） = 536, the final R = 0.0453 and wR = 0.1085 for 1317 observed reflections （I 2σ（I）） for Ⅱ. The antibacterial activities of both compounds against two bacteria were first studied and one compound showed considerable antibacterial activity against K. Pneumonia and S. aureus.展开更多
The complexes of four ferrocenylaldehyde aroylhydrazones with lead(Ⅱ) were synthesized and characterized. Their compositions, bonding forms and properties were researched by means of elemental analysis, IR, UV Vis,...The complexes of four ferrocenylaldehyde aroylhydrazones with lead(Ⅱ) were synthesized and characterized. Their compositions, bonding forms and properties were researched by means of elemental analysis, IR, UV Vis, 1H NMR spectra, thermal analysis and molar conductance. The free ligands which existed in the keto form coordinated to lead(Ⅱ) in the enol form to form neutral complexes. The molar ratio of the ligand to lead(Ⅱ) is 2∶1 and the thermal stability of the complex is higher than that of the corresponding ligand because of the formation of the stable chelate ring. The ligands and the complexes are all non electrolytes.展开更多
A facile synthesis of tetraarylpyrazoles has been developed via t-BuOK/DMF promoted intermolecular cycloaddition of hydrazones and 1,2-diarylalkynes. A possible reaction pathway via a hydrazone radical is proposed.
We synthesized a series of hydrazones, a novel type of nitrogen-containing prostaglandins, from different aromatic hydrazines and variant 2-substituted amino-3-hydroxy bicycle [3.2.0]hept-6-ones IV.
Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations t...Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve.This critical review summarizes the major advancements in the carbene chemistry of N-sulfonyl hydrazones.The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field.The individual carbene transfer reactions and their mechanisms,as well as the potential applications in the synthesis of natural products and complex bioactive molecules,are thoroughly discussed.展开更多
Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-su...Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.展开更多
The oxovanadium（IV） complexes of the Schiff base hydrazones, synthesized from 3-hydrazinoquinoxaline-2- one （HQO） with salicylaldehyde （HSHQO）, o-hydroxyacetophenone （HHAHQO）, dehydroacetic acid （HDHAHQO） an...The oxovanadium（IV） complexes of the Schiff base hydrazones, synthesized from 3-hydrazinoquinoxaline-2- one （HQO） with salicylaldehyde （HSHQO）, o-hydroxyacetophenone （HHAHQO）, dehydroacetic acid （HDHAHQO） and o-nitrobenzaldehyde （NBHQO） were synthesized and characterized on the basis of analytical, conductance, magnetic moment, infrared, NMR, ESR and electronic spectral data. The ligands HSHQO, HDHAHQO behaved as monobasic tridentate ONN donors through phenolic oxygen, azomethine nitrogens. The ligand HAHQO acted as a monobasic bidentate ON donor through the phenolic oxygen, azomethine （free） nitrogen and the ligand NBHQO acted as neutral bidentate ON donor through oxygen of the nitro group and azomethine （free） nitrogen.展开更多
Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted...Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra- zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to the corresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or aryl benzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6- (p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo- furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenone hydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and 3-methyl-4-(m-nitrobenzyloxy)indazole.展开更多
Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoe...Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoelectronic materials,including materials displaying high-performance circularly polarized luminescence(CPL).Herein,we report the first chiral supramolecular polymer systems based on hydrazone–pyridinium conjugates comprising alkyl chains of different lengths,which afforded control of the apparent supramolecular chirality.Although supramolecular chirality is governed basically by the remote chiral centers of alkyl chains,helicity inversion was achieved by controlling the conditions under which the hydrazone building blocks underwent aggregation(i.e.,solvent compositions or temperature).More importantly,the addition of water to the system led to aggregationinduced hydrazone deprotonation,which resulted in a completely different selfassembly behavior.Structural water molecules played an essential role,forming the assembly’s channel-like backbone,around which hydrazone molecules gathered as a result of hydrogen bonding interactions.Further co-assembly of an achiral hydrazone luminophore with the given supramolecular polymer system allowed the fabrication of a novel CPL-active hydrazone-based material exhibiting a high maximum value for the photoluminescence dissymmetry factor of -2.6×10^(-2).展开更多
A series of large macrocyclic calixarene bishydrazones were efficiently synthesized by [2 ＋ 2] condensation reactions of calix[4]arene 1,3-disubstituted aldehydes with hydrated hydrazine. The X-ray single crystal dif...A series of large macrocyclic calixarene bishydrazones were efficiently synthesized by [2 ＋ 2] condensation reactions of calix[4]arene 1,3-disubstituted aldehydes with hydrated hydrazine. The X-ray single crystal diffraction showed that macrocycles form a distinctive calixtube-liking shape.展开更多
Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional...Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional grouptolerance anda broadsubstrate scope under mild conditions.Mechanistic studies showed that the addition of hydrazone anion to a styrene double bond was the key step,different from previoushydroacylationpathways(viaorganometallic complexes or radical intermediates).展开更多
Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles (2a–1), with five of them as new compounds, is described. Their derivatives, i.e., 1-methyl-2-formyl-5-substituted pyrrole phenyl hydrazones (3a–1) and ...Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles (2a–1), with five of them as new compounds, is described. Their derivatives, i.e., 1-methyl-2-formyl-5-substituted pyrrole phenyl hydrazones (3a–1) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl) hydrazones (4a–1) are all new compounds. They have also been prepared and further identified.展开更多
As a common active substructure,hydrazone has attracted increasing attention and is considered essential for pesticide discovery.It has been widely regarded as a potential insecticidal,antibacterial,antifungal,antivir...As a common active substructure,hydrazone has attracted increasing attention and is considered essential for pesticide discovery.It has been widely regarded as a potential insecticidal,antibacterial,antifungal,antiviral,and herbicidal agent.In this review,we highlight the pesticide versatility of hydrazone fragments and provide a comprehensive summary of the biological activity,structure-activity relationship analysis(SARs),and primary mechanism of their analogs.This profile is expected to give valuable information for discovering new pesticides.展开更多
Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited pheny...Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited phenylhydrazone anion was potential to reduce aryl iodides via single electron transfer process for the subsequent radical chain reaction. A redox-neutral photochemical carbonylation of aryl iodides was developed on basis of the special spectroscopic features of phenylhydrazone anion. This protocol provided a convenient and efficient synthetic tool for accessing carbonylation products under redox neutral conditions without the need of transition-metals.展开更多
This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is ...This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.展开更多
Hydrazone derivatives of vanillin are found to possess anti-bacterial activities. Based on higher bio-activity of hydrazones, new hydrazone derivatives were synthesized from Piperdine-4-carboxylicacid methyl ester (1)...Hydrazone derivatives of vanillin are found to possess anti-bacterial activities. Based on higher bio-activity of hydrazones, new hydrazone derivatives were synthesized from Piperdine-4-carboxylicacid methyl ester (1). The compounds 1-pyrimidine-2-yl piperidine-4-carboxylicacid(4-hydroxy-3-methoxy benzylidine)-hy- drazide (10), 1-pyrimidine-2-yl piperidine-4-carboxylicacid (3,4-dimethoxy benzylidine) hydrazide (11), 1-pyrimidine-2-yl piperidine-4-carboxylicacid(4-butoxy-3-methoxy benzylidine)-hydrazide (12), 1-pyr- imidine-2-yl piperidine-4-carboxylicacid(3-methoxy-4(2-methoxy ethoxy) benzylidine)-hydrazide (13) were synthesized, purified and characterized by 1HNMR, 13CNMR, LCMS, FT-IR and HPLC techniques. The synthesized hydrazone derivatives were further checked for anti-bacterial activities by paper disc diffusion method against Pseudomonas aeruginosa and Staphylococcus aureus bacterial strains.展开更多
This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculation...This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.展开更多
基金financial support for this research from Shandong Provincial Natural Science Foundation(No.ZR2017LB006)Academic promotion programme of Shandong First Medical University(No.2019LJ003)。
文摘A novel route for tandem C-C/C-N formation,annulation and aromatization of hydrazones with 1,2-dichloroethane to synthesize 1 H-pyrazoles has been developed.Furthermore,the 1,2-dichloroethane serves as alkylation reagent in good to excellent yields.This methodology features mild reaction conditions and good functional group tolerance,providing a direct approach for the preparation of 1 Hpvrazoles.
文摘By using 1-methyl-2-formyl-5 -Y-substituted pyrrole (4-nitrophenyl)hydrazones as a model for nitrogen-containing heterocyclic aromatic compounds, the emission wavelength [lambda(max(em))] values df their fluorescence spectra have been measured. Correlation results show that the Delta E-em values are mainly affected by polar effects, but spin-delocalizatin effects also exist.
文摘A new series of dimeric Cu（II） and Ni（II） complexes with some aroylhydrazones of a-pyridoin were synthesized and characterized using different physical techniques. Their chemical formulae were based on their microanalysis and IR data. The structures of the solid complexes were determined from the electronic, IR and ESR spectral studies as well as their magnetic susceptibility measurements. The ligands acted as bi-, tri- and tetra-dentate forming different dinuclear complexes with different structures. The assumed molecular structures based on the experimental results were also confirmed by the molecular mechanics calculations. The extraction ability of the hydrazones has been investigated by liquid-liquid extraction for Cu（II） and Ni（II）.
基金supported by the National Natural Science Foundation of China(No.81102791)
文摘Two new Schiff base benzoyl hydrazone compounds, C14H10FN3O3 （Ⅰ） and C14H10F2N2O （Ⅱ）, have been synthesized and characterized by elemental analysis, IR, UV and X-ray single-crystal diffraction. Both compounds crystallize in monoclinic, space group P21/c with a = 7.0514（14）, b = 25.928（5）, c = 7.7099（15）, β = 111.823（2）°, V = 1308.6（4）3, Z = 4, C14H10FN3O3, Mr = 287.25, Dc = 1.458 g/cm3, μ（MoKα） = 0.115 mm-1, F（000） = 592, the final R = 0.0841 and wR = 0.2489 for 1901 observed reflections （I 2σ（I）） for I; a = 11.232（3）, b =12.735（4）, c = 8.612（2） , β = 90.869（3）°, V = 1231.7（6）3, Z = 4, C14H10F2N2O, Mr = 260.24, Dc = 1.403 g/cm3, μ（MoKα） = 0.111 mm-1, F（000） = 536, the final R = 0.0453 and wR = 0.1085 for 1317 observed reflections （I 2σ（I）） for Ⅱ. The antibacterial activities of both compounds against two bacteria were first studied and one compound showed considerable antibacterial activity against K. Pneumonia and S. aureus.
文摘The complexes of four ferrocenylaldehyde aroylhydrazones with lead(Ⅱ) were synthesized and characterized. Their compositions, bonding forms and properties were researched by means of elemental analysis, IR, UV Vis, 1H NMR spectra, thermal analysis and molar conductance. The free ligands which existed in the keto form coordinated to lead(Ⅱ) in the enol form to form neutral complexes. The molar ratio of the ligand to lead(Ⅱ) is 2∶1 and the thermal stability of the complex is higher than that of the corresponding ligand because of the formation of the stable chelate ring. The ligands and the complexes are all non electrolytes.
基金the National Natural Science Foundation of China (No. 21472248)Department of Science and Technology of Guangdong Province(No. 2017A020211011)for the financial support
文摘A facile synthesis of tetraarylpyrazoles has been developed via t-BuOK/DMF promoted intermolecular cycloaddition of hydrazones and 1,2-diarylalkynes. A possible reaction pathway via a hydrazone radical is proposed.
文摘We synthesized a series of hydrazones, a novel type of nitrogen-containing prostaglandins, from different aromatic hydrazines and variant 2-substituted amino-3-hydroxy bicycle [3.2.0]hept-6-ones IV.
基金the financial support from the National Natural Science Foundation of China(22331004)。
文摘Over the past few decades,N-sulfonyl hydrazones have been recognized as alternative precursors for hazardous diazo compounds in organic synthesis,allowing for diverse innovative and original chemical transformations that were otherwise difficult to achieve.This critical review summarizes the major advancements in the carbene chemistry of N-sulfonyl hydrazones.The contents of this review are organized based on research conducted by leading scientists who have made significant contributions to this field.The individual carbene transfer reactions and their mechanisms,as well as the potential applications in the synthesis of natural products and complex bioactive molecules,are thoroughly discussed.
基金the National Natural Science Foundation of China(21871043,21961130376)Department of Science and Technology of Jilin Province(20180101185JC,20190701012GH,20200801065GH)the Fundamental Research Funds for the Central Universities(2412019ZD001,2412019FZ006)。
文摘Fluoroalkyl N-sulfonyl hydrazones are versatile reagents that can be used to synthesize a wide range of diverse fluoroalkylated organic molecules.Although it has been known since 1975,the chemistry of fluoroalkyl N-sulfonyl hydrazones has recently only received great attention from the scientific community.Generally,they are used as either safe and bench-stable diazo precursors in carbene transfer reactions or as 1,3-dipoles in cycloaddition and cyclization reactions.Notably,fluoroalkyl N-sulfonyl hydrazones to replace toxic fluoroalkyl diazo compounds in carbene transfer reactions reduce the risk of rapid accumulation of explosive diazo compounds and improve functional group compatibility and substrate scope.Given the growing importance of fluoroalkyl N-sulfonyl hydrazones in chemical synthesis,a comprehensive review of this topic in the literature is essential to demonstrate their synthetic potential.In this review,we critically summarize and comprehensively analyze the publications in various literatures on the chemistry of fluoroalkyl N-sulfonyl hydrazones starting from 1990 to date.The classification of the different reactivity profiles of fluoroalkyl N-sulfonyl hydrazones and the efficiencies of similar types of reactions or substrates with fluoroalkyl diazo compounds are compared.
文摘The oxovanadium（IV） complexes of the Schiff base hydrazones, synthesized from 3-hydrazinoquinoxaline-2- one （HQO） with salicylaldehyde （HSHQO）, o-hydroxyacetophenone （HHAHQO）, dehydroacetic acid （HDHAHQO） and o-nitrobenzaldehyde （NBHQO） were synthesized and characterized on the basis of analytical, conductance, magnetic moment, infrared, NMR, ESR and electronic spectral data. The ligands HSHQO, HDHAHQO behaved as monobasic tridentate ONN donors through phenolic oxygen, azomethine nitrogens. The ligand HAHQO acted as a monobasic bidentate ON donor through the phenolic oxygen, azomethine （free） nitrogen and the ligand NBHQO acted as neutral bidentate ON donor through oxygen of the nitro group and azomethine （free） nitrogen.
文摘Cyclization of 2-methoxy-6-benzyloxy acetophenone hydrazone gave 3-methyl-4-meth- oxy indazole and 3-methyl-4-methoxy-7-benzyl indazole in the presence of polyphosphoric acid (PPA).The hydrazone was probably converted to 2-hydroxy-6-methoxy acetophenone hydra- zone and 2-hydroxy-3-benzyl-6-methoxy acetophenone hydrazone followed by cyclization to the corresponding indazoles in acidic conditions.Cyelization of 2-methoxy-6-(halo or alkyl or aryl benzyloxy)acetophenone hydrazones gave similar products.Cyclization of 2-methoxy-6- (p-nitrobenzyloxy)acetophenone hydrazone gave 2-(p-nitrophenyl)-3-methyl-4-methoxy benzo- furan and 3-methyl-4-methoxy indazole while 2-methoxy-6-(m-nitrobenzyloxy)acetophenone hydrazone gave 3-methyl-4-methoxy indazole,3-methyl-4-methoxy-7-(m-nitrophenyl)indazole and 3-methyl-4-(m-nitrobenzyloxy)indazole.
基金National Research Foundation of Korea,Grant/Award Number:2012M3A7B4049677Nano Material Development Program,Grant/Award Number:2020R1A6A3A01100092+1 种基金Basic ScienceResearch ProgramInstitute forBasic Science,Grant/Award Number:IBS-R019-D1。
文摘Understanding the precise molecular arrangement of chiral supramolecular polymers is essential not only to comprehend complex superstructures like proteins and DNA but also for the development of next-generation optoelectronic materials,including materials displaying high-performance circularly polarized luminescence(CPL).Herein,we report the first chiral supramolecular polymer systems based on hydrazone–pyridinium conjugates comprising alkyl chains of different lengths,which afforded control of the apparent supramolecular chirality.Although supramolecular chirality is governed basically by the remote chiral centers of alkyl chains,helicity inversion was achieved by controlling the conditions under which the hydrazone building blocks underwent aggregation(i.e.,solvent compositions or temperature).More importantly,the addition of water to the system led to aggregationinduced hydrazone deprotonation,which resulted in a completely different selfassembly behavior.Structural water molecules played an essential role,forming the assembly’s channel-like backbone,around which hydrazone molecules gathered as a result of hydrogen bonding interactions.Further co-assembly of an achiral hydrazone luminophore with the given supramolecular polymer system allowed the fabrication of a novel CPL-active hydrazone-based material exhibiting a high maximum value for the photoluminescence dissymmetry factor of -2.6×10^(-2).
基金Supporting information for this article is available on the WWW under http：//dx.doi.org/10.1002/cjoc.201200072 or from the author.Acknowledgement This work was financially supported by the National Natural Science Foundation of China （No. 20972132） and the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘A series of large macrocyclic calixarene bishydrazones were efficiently synthesized by [2 ＋ 2] condensation reactions of calix[4]arene 1,3-disubstituted aldehydes with hydrated hydrazine. The X-ray single crystal diffraction showed that macrocycles form a distinctive calixtube-liking shape.
基金from the National Natural Science Foundation of China(grant no.21971093)the International Joint Research Centre for Green Catalysis and Synthesis(grant no.2016B01017),and the 111 project.
文摘Wereport a base-promoted catalyst-free protocol for the highly regioselective hydroacylation of styrenes with hydrazones derived from naturally abundant aldehydes.This protocolgeneratedlinearketoneswith goodfunctional grouptolerance anda broadsubstrate scope under mild conditions.Mechanistic studies showed that the addition of hydrazone anion to a styrene double bond was the key step,different from previoushydroacylationpathways(viaorganometallic complexes or radical intermediates).
基金Project supported by the National Natural Science Foundation of China (No. 29472075)the Postdoctoral Science Foundation of China
文摘Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles (2a–1), with five of them as new compounds, is described. Their derivatives, i.e., 1-methyl-2-formyl-5-substituted pyrrole phenyl hydrazones (3a–1) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl) hydrazones (4a–1) are all new compounds. They have also been prepared and further identified.
基金The financial support from the National Natural Science Foundation of China(Nos.32072445,22007022)the Program of Introducing Talents to Chinese Universities(No.D20023)+2 种基金the Natural Science Research Project of Guizhou Education Department(No.KY(2018)009)the Graduate Research Fund in Guizhou Province(No.YJSKYJJ[2021]038)The Specific Research Fund of the Innovation Platform for Academicians of Hainan Province(No.SQ2020PTZ0009)。
文摘As a common active substructure,hydrazone has attracted increasing attention and is considered essential for pesticide discovery.It has been widely regarded as a potential insecticidal,antibacterial,antifungal,antiviral,and herbicidal agent.In this review,we highlight the pesticide versatility of hydrazone fragments and provide a comprehensive summary of the biological activity,structure-activity relationship analysis(SARs),and primary mechanism of their analogs.This profile is expected to give valuable information for discovering new pesticides.
基金supported by the National Natural Science Foundation of China (Nos.22271246 and 22101251)Yunling Scholar Project of "Yunnan Revitalization Talent Support Program" for financial support。
文摘Spectroscopic investigations discovered that the in-situ generated phenylhydrazone anion was significantly bathochromically shifted to visible light region for photoactivation under irradiation. The photoexcited phenylhydrazone anion was potential to reduce aryl iodides via single electron transfer process for the subsequent radical chain reaction. A redox-neutral photochemical carbonylation of aryl iodides was developed on basis of the special spectroscopic features of phenylhydrazone anion. This protocol provided a convenient and efficient synthetic tool for accessing carbonylation products under redox neutral conditions without the need of transition-metals.
文摘This work deals with the synthesis and physicochemical characterizations of a new group of novel retinoidal ligands and their metal complexes. Their in vitro anti-proliferative activities have shown that ligand L1 is effective against human breast cancer BT-20 and MCF-7 cell lines. At the same time, compound L2 exerts its effect on human prostate cancer PC-3 and human breast cancer MDA-MB-231 and MCF-7 cell lines respectively. The retinoid ligands exert their pleiotropic action toward retinoic acid receptors (RARs) than their metal complexes but all compounds exhibit concentration-dependent.
文摘Hydrazone derivatives of vanillin are found to possess anti-bacterial activities. Based on higher bio-activity of hydrazones, new hydrazone derivatives were synthesized from Piperdine-4-carboxylicacid methyl ester (1). The compounds 1-pyrimidine-2-yl piperidine-4-carboxylicacid(4-hydroxy-3-methoxy benzylidine)-hy- drazide (10), 1-pyrimidine-2-yl piperidine-4-carboxylicacid (3,4-dimethoxy benzylidine) hydrazide (11), 1-pyrimidine-2-yl piperidine-4-carboxylicacid(4-butoxy-3-methoxy benzylidine)-hydrazide (12), 1-pyr- imidine-2-yl piperidine-4-carboxylicacid(3-methoxy-4(2-methoxy ethoxy) benzylidine)-hydrazide (13) were synthesized, purified and characterized by 1HNMR, 13CNMR, LCMS, FT-IR and HPLC techniques. The synthesized hydrazone derivatives were further checked for anti-bacterial activities by paper disc diffusion method against Pseudomonas aeruginosa and Staphylococcus aureus bacterial strains.
基金supported by the National Natural Science Foundation of China(Nos.22003006,21822303,22103008,22271034)Project supported by graduate research and innovation foundation of Chongqing,China(No.CYB20045)a project(No.2018CDXZ0002)supported by the Fundamental Research Funds for the Central Universities(Chongqing University)。
文摘This report describes the oxidative cyclopalladation activation of a C≡C bond during the Pd-catalyzed hydroalkylation of alkynes and analyzes potential reaction pathways based on density functional theory calculations. The more favorable pathway in-volves an oxidative cyclopalladation to generate a palladacyclopropene intermediate, which is rarely examined in Pd-catalyzed alkyne transformations. The reaction pathway proposed herein is kinetically favorable relative to the commonly proposed alkyne insertion mode. Furthermore, the Laplacians of the electron density, interaction region indicators, Mayer bond orders, and localized orbital bonding are evaluated to determine the reaction processes and characterize the key intermediates. Theoretical calculations indicate covalent bonding between a Pd(II) center and the two C-atoms in three-membered palladacycle species. Finally, electrostatic potential analysis reveals that the regioselectivity is governed by the charge distribution on the palladacycle moiety during the protonation step.
