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
A novel La complex with methyl-2-pyridyl ketone benzoyl hydrazone has been synthesized and determined by single crystal X-ray diffraction. The crystal is monoclinic with space group C2/c, a =1 7081(3) nm, b =1 ...A novel La complex with methyl-2-pyridyl ketone benzoyl hydrazone has been synthesized and determined by single crystal X-ray diffraction. The crystal is monoclinic with space group C2/c, a =1 7081(3) nm, b =1 5660(3) nm, c =1 3512(3) nm, α=90 00°, β=94 39(1)°, γ=90 00°, V =3 6037(12) nm 3, Z =4 . The complex is a ten-coordinated one with a lanthanum ion surrounded by a N 4O 6 set. The crystal structure is stabilized by hydrogen bonds between water molecules and NO - 3 anions.展开更多
The novel title compound 4-chlorobenzaldehyde （2-trifluoromethyl-5,6,7,8- tetrahydro- benzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazone monohydrate （C18H14C1F3N4S.H20, Mr = 428.86） has been synthesized by a condensa...The novel title compound 4-chlorobenzaldehyde （2-trifluoromethyl-5,6,7,8- tetrahydro- benzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazone monohydrate （C18H14C1F3N4S.H20, Mr = 428.86） has been synthesized by a condensation reaction of 4-chlorobenzaldehyde with （2-trifuoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazine, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 7.4252（7）, b = 26.344（2）, c = 10.3095（9） A, /3 = 109.407（2）~, V= 1902.0（3） A3, Z = 4, Dc = 1.498 g/cm^3, p = 0.356 mm-1, F（000） = 880, the final R = 0.0564 and wR = 0.1681 for 2343 observed reflections with I 〉 2o（/）. X-ray diffraction analysis reveals that the title hydrazone molecule is nearly planar except for the cyclohexene and trifluoromethyl moieties. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N（3）-H（3）...O（1）, O（1）-H（1B）...N（2）, O（1）- H（1B）...N（4） and O（1）-H（1A）...F（1） hydrogen bonds via water molecules together with π-π stacking interactions. Molecular geometry of the title compound in the ground state optimized by B3LYP functional with 6-311G＊＊ basis sets indicates that the calculations are in agreement with the experimental data. The preliminary bioassay suggested that the title compound exhibits relatively good fungicidal activity against Fusarium oxysporium fsp.vasinfectum and Dothiorella gregaria.展开更多
The mononuclear vanadium（V） complex with 2-hydroxyl-l-naphthaldehyde isonicotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monocfinic, space group P2 1/n wi...The mononuclear vanadium（V） complex with 2-hydroxyl-l-naphthaldehyde isonicotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monocfinic, space group P2 1/n with α = 10.3153（15）, b = 7.4024（11 ）, c = 24.413（4） A, β = 101.911（2）°, V= 1824.0（5） A^3, Z= 4, Mr = 427.28, Dc = 1.556 g/cm^3, F（000） = 880,μ（MoKα） = 0.591, the final R = 0.0372 and wR = 0.0926. The vanadium（V） atom adopts a distorted square-pyramidal geometry coordinated by the tridentate ligand and two oxygen atoms. The hydrogen bonds and strong π-π stacking interactions link the complex molecules into a 3-D network structure.展开更多
A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At ...A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.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 new cis-dioxovanadium （V） complex [VO2（C9H8N3O3）]（C5H5N） involving a carboxyl group coordination employing a tridentate Schiff Base derived from pyruvic acid and isonicotinyl hydrazide is reported. This comple...A new cis-dioxovanadium （V） complex [VO2（C9H8N3O3）]（C5H5N） involving a carboxyl group coordination employing a tridentate Schiff Base derived from pyruvic acid and isonicotinyl hydrazide is reported. This complex crystallizes in triclinic, space group P1^- with a = 7.3522 （12）, b = 7.8376（13）, c = 14.898（2） ,A°, a = 84.010（2）, β = 86.568（2）, γ= 64.586（2）°, V = 771.1（2）A °^3 ,Z = 2, F（000） = 376, Mr = 368.22, D, = 1.586 g/cm^3, g = 0.677 mm ^-1, R = 0.0421 and wR = 0.1253. The vanadium atom of the dioxovanadium （V） is five-coordinated to furnish a distorted trigonal bipyramid geometry.展开更多
Two hydrazone ligands （E）-N＇-（2-hydroxy-5-methoxybenzylidene）-2-hydroxybenzo- hydrazide （HLa） and （E）-N＇-（3,5-dichloro-2- hydroxybenzylidene）-4-methoxybenzohydrazide （HLb） were prepared and characterized...Two hydrazone ligands （E）-N＇-（2-hydroxy-5-methoxybenzylidene）-2-hydroxybenzo- hydrazide （HLa） and （E）-N＇-（3,5-dichloro-2- hydroxybenzylidene）-4-methoxybenzohydrazide （HLb） were prepared and characterized by IR, UV-Vis and 1H NMR spectra. Based on the hydrazone ligands, two new structurally similar vanadium（V） complexes, [VOLaL].CH3OH （1） and [vOLbL] （2）, where L is the monoanionic form of benzohydroxamic acid （HL）, were prepared and characterized by IR and UV-Vis spectra, and single-crystal X-ray diffraction. Complex 1 crystallizes as the monoclinic space group P21/n, with a = 7.5208（10）, b = 15.490（2）, c = 20.8929（18） A, β = 96.373（2）°, V = 2418.9（5） A3, Z = 4, R = 0.0831, wR = 0.2607 and GOOF = 1.061. Complex 2 crystallizes as the monoclinic space group P21/c, with a = 11.8577（18）, b = 16.468（2）, c = 12.2288（18） A, β = 106.064（2）°, V= 2294.7（6） A3, Z = 4, R= 0.0741, wR= 0.1745 and GOOF= 1.014. X-ray analysis indicates that the complexes are mononuclear vanadium （V） species, with the V atoms located in the octahedral coordination. The hydrazone ligands and the complexes were evaluated for their antibacterial （Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence） and antifungal （Candida albicans and Aspergillus niger） activities by MTT （3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl tetrazolium bromide） method.展开更多
2-Oxo-butyric acid salicylacylhydrazone dibenzyltin（IV） complexes 1 {[o-OHC6H4（O）C=N-N=C（Et）COO]（CH3OH）[（C6H5CH2）2Sn]}2 and 2 {[o-OH-C6H4（O）C=N-N=C（Et）-COO]（CH3OH）[（2,4-Cl2C6H3CH2）2Sn]}2 have been sy...2-Oxo-butyric acid salicylacylhydrazone dibenzyltin（IV） complexes 1 {[o-OHC6H4（O）C=N-N=C（Et）COO]（CH3OH）[（C6H5CH2）2Sn]}2 and 2 {[o-OH-C6H4（O）C=N-N=C（Et）-COO]（CH3OH）[（2,4-Cl2C6H3CH2）2Sn]}2 have been synthesized. The complexes were characterized by IR, 1H, 13C and 119Sn NMR spectra, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex 1 belongs to triclinic system, space group P1 with a = 8.9121（6）, b = 10.3875（7）, c = 14.5658（10） ？, α = 89.534（5）, β = 86.790（5）, γ = 70.103（6）°, Z = 1, V = 1265.85（15） ？3, Dc = 1.488 Mg·m^（-3）, m（Mo Kα） = 1.047 mm-1, F（000） = 576, R = 0.0466 and w R = 0.1054. The crystal of complex 2 belongs to monoclinic system, space group P21/n, a = 12.7165（10）, b = 17.8466（14）, c = 12.8538（10） ？, β = 95.1310（10）°, Z = 2, V = 2905.4（4） ？~3, Dc = 1.612 Mg·m^（-3）, m（Mo Kα） = 1.286 mm-1, F（000） = 1408, R = 0.0369 and w R = 0.0958. In vitro antitumor activities of both complexes were evaluated by the 3-（4,5-dimethylthiazoly-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay against three human cancer cell lines（NCI-H460, HepG2, MCF7） and one human cell line（HL7702）. Two complexes exhibited strong antitumor activity, and then they were expected after further chemical optimization of candidate compounds as anti-cancer drugs. The interaction between complexes and calf thymus DNA were studied by EB fluorescent probe. The interactions of the two complexes with calf thymus DNA were intercalation.展开更多
To find new lead compounds with high biological activity,a series of novel 4-methyl-1,2,3-thiadiazole-5-carboxaldehyde benzoyl hydrazone derivatives were designed and synthesized.Their structures were confirmed by -1H...To find new lead compounds with high biological activity,a series of novel 4-methyl-1,2,3-thiadiazole-5-carboxaldehyde benzoyl hydrazone derivatives were designed and synthesized.Their structures were confirmed by -1H NMR,-（13）C NMR,IR spectrum and elemental analysis.Preliminary bioassay indicated that the title compounds exhibited moderate to strong fungicidal activity against six fungi in vitro at50 μg/mL.Moreover,some of the title compounds exhibited good curative activity against TMV in vivo at500 μg/mL.The structure-activity relationship analysis of compounds against Valsa mali showed that compounds containing halogen at the para position on phenyl exhibited the best activity.Especially compound 8k showed broad spectrum fungicidal activities against Valsa mali,Botrytis cinerea,Pythium aphamdermatum,Rhizoctonia solani,Fusarium moniliforme and Altemaria solani with the EC（50） values of8.20,24.42,15.80,40.53,41.48,and 34.16 μg/mL,respectively.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
A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by...A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by physical state determination, melting point and solubility measurements in different solvents, infrared, proton nuclear magnetic resonance, mass spectrometric and powder X-ray spectroscopic techniques. The thermal properties of the prepared compounds were obtained from TG/DTG measurements. On the basis of the analytical techniques, the ligand was found to be bidentate in nature coordinating to the metal ions through the azomethine nitrogen and carbonyl oxygen atoms leading to distorted octahedral geometries of the metal complexes which were modeled using MM2 force field. The ligand and its metal(II) complexes were evaluated for antifungal activity against <i>Aspergillus fumigatus, Aspergillus niger, Candida albicans and Rhizopus stolonifera.</i> The antifungal evaluation results revealed an enhanced activity upon coordination of the ligand with the metal(II) ions. The activity of the metal complex to the tested fungal strains was in the order Ni(II) > Mn(II).展开更多
Some light-lanthanide nitrate complexes were obtained by the reaction of lanthanide nitrate with isonicotinoyl hydrazone (HL = N,N'-diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) in methanol. Th...Some light-lanthanide nitrate complexes were obtained by the reaction of lanthanide nitrate with isonicotinoyl hydrazone (HL = N,N'-diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) in methanol. The general formula of the complexes is Ln(L) (NO3)(2) . nH(2)O(Ln = La, Ce, Pr, Nd and Sm; n = 0, 1). The complexes were characterized by elemental analyses, conductance, thermal analyses, UV and IR spectra. The results show that the lanthanide ion in each complex is coordinated by oxygen and nitrogen atoms of the ligand (L) and the oxygen atoms of the nitrate. The amide-oxygen atoms of L coordinate to the Ln ions in its keto-form. The magnetic susceptibility of the neodymium complex shows that the magnetic data obey Curie-Weiss law in the range of 75K < T < 300K.展开更多
The ytterbium complex of isonicotinoyl hydrazone was synthesized and the structure was determined by X-ray diffraction analysis. The crystal and molecular structure of the title complex [Yb-2(L)(3)](OH)(3) shows that ...The ytterbium complex of isonicotinoyl hydrazone was synthesized and the structure was determined by X-ray diffraction analysis. The crystal and molecular structure of the title complex [Yb-2(L)(3)](OH)(3) shows that the complex has two identical nine-coordinated ytterbium ions with each surrounded by N3O6 donor set, Two ytterbium ions are bridged by three phenolate oxygen atoms, The geometry around each ytterbium ions can be considered as a three-capped trigonal prism.展开更多
In order to study the coordination character of the rare earth elements with hydrazones and the antioxidative activity of the ligand and the complexes, 3,5 dibenzyloxybenzoyl 2,4 dihydroxybenzaldehyde hydrazone (H ...In order to study the coordination character of the rare earth elements with hydrazones and the antioxidative activity of the ligand and the complexes, 3,5 dibenzyloxybenzoyl 2,4 dihydroxybenzaldehyde hydrazone (H 2L), a new chelating ligand, and its six lanthanide complexes, Ln (HL)(OAc) 2· n H 2O [Ln=La, Sm, Eu, Gd, Tb, Dy; n =2, 4, 5], were synthesized and characterized on the basis of elemental analyses, IR and 1H NMR spectra, molar conductivity. The results show that the lanthanide ions are coordinated by O, O and N donors of the phenol (Ar OH) without deprotonation, the enol oxygen of the hydrazone group (NCO -) and the azomethine group (CH=N) from the ligand respectively, and by the four carboxylic oxygen from two acetate groups (CH 3COO -) in the bidentate form. The scavenging activity of the ligand and the six lanthanides complexes on the 2,2 Diphenyl 1 picrylhydrazyl (DPPH) free radicals is also evaluated. The results show that both the ligand and the complexes have the scavenging activity on the DPPH radicals, and the scavenging activity of the complexes is better than the ligand.展开更多
Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reacti...Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.展开更多
Photo-isomerization of aromatic α-hydroxy hydrazone was reported. We investigated the structures of salicylaldehyde phenylhydrozone（SP） in the ground state using density functional theory（DFT） with the B3LYP func...Photo-isomerization of aromatic α-hydroxy hydrazone was reported. We investigated the structures of salicylaldehyde phenylhydrozone（SP） in the ground state using density functional theory（DFT） with the B3LYP functional and the 6-311＋G（d） basis set. All nine possible isomers of SP in the ground state consist of seven phenol forms and two ketone forms. Intrisic reaction coordinate（IRC） analysis discloses the existence of a cycle driven by the two proton transfer processes in the ground and excited states of SP, which suggests that no ketonic form could exist in the ground state. Further theoretical studies of the potential energy surfaces support a trans-cis conversion followed by a relaxation to the stable form of SP in the excited states.展开更多
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.
基金Supported by the National Natural Science Foundation of China( No. 2 98710 14 ) and the Foundation of Doctor byL anzhou U niversit
文摘A novel La complex with methyl-2-pyridyl ketone benzoyl hydrazone has been synthesized and determined by single crystal X-ray diffraction. The crystal is monoclinic with space group C2/c, a =1 7081(3) nm, b =1 5660(3) nm, c =1 3512(3) nm, α=90 00°, β=94 39(1)°, γ=90 00°, V =3 6037(12) nm 3, Z =4 . The complex is a ten-coordinated one with a lanthanum ion surrounded by a N 4O 6 set. The crystal structure is stabilized by hydrogen bonds between water molecules and NO - 3 anions.
基金supported by the National Natural Science Foundation of China (No.21262012)the Natural Science Foundation of Hubei Province (No.2011CDB087)+1 种基金the Scientific Research Fund of Hubei Provincial Education Department (No.Q20122909)the Project of Team Research for Excellent Mid-Aged & Young Teachers of Higher Education of Hubei Province, China (No.T201006)
文摘The novel title compound 4-chlorobenzaldehyde （2-trifluoromethyl-5,6,7,8- tetrahydro- benzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazone monohydrate （C18H14C1F3N4S.H20, Mr = 428.86） has been synthesized by a condensation reaction of 4-chlorobenzaldehyde with （2-trifuoromethyl-5,6,7,8-tetrahydrobenzo[4,5]thieno[2,3-d]pyrimidin-4-yl）hydrazine, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/c with a = 7.4252（7）, b = 26.344（2）, c = 10.3095（9） A, /3 = 109.407（2）~, V= 1902.0（3） A3, Z = 4, Dc = 1.498 g/cm^3, p = 0.356 mm-1, F（000） = 880, the final R = 0.0564 and wR = 0.1681 for 2343 observed reflections with I 〉 2o（/）. X-ray diffraction analysis reveals that the title hydrazone molecule is nearly planar except for the cyclohexene and trifluoromethyl moieties. In the crystal packing, the molecules form stacks by a three-dimensional framework, which results from intermolecular N（3）-H（3）...O（1）, O（1）-H（1B）...N（2）, O（1）- H（1B）...N（4） and O（1）-H（1A）...F（1） hydrogen bonds via water molecules together with π-π stacking interactions. Molecular geometry of the title compound in the ground state optimized by B3LYP functional with 6-311G＊＊ basis sets indicates that the calculations are in agreement with the experimental data. The preliminary bioassay suggested that the title compound exhibits relatively good fungicidal activity against Fusarium oxysporium fsp.vasinfectum and Dothiorella gregaria.
基金Supported by the Science Foundation of Guangxi Province (No. 0342025), the Youth Science Foundation of Guangxi Province (No. 0542020) and the Teaching and Research Award Programme for Outstanding Young Teachers in Higher Education Institutions of MOE, China
文摘The mononuclear vanadium（V） complex with 2-hydroxyl-l-naphthaldehyde isonicotinoyl hydrazone was synthesized and characterized by single-crystal X-ray diffraction. The crystal is of monocfinic, space group P2 1/n with α = 10.3153（15）, b = 7.4024（11 ）, c = 24.413（4） A, β = 101.911（2）°, V= 1824.0（5） A^3, Z= 4, Mr = 427.28, Dc = 1.556 g/cm^3, F（000） = 880,μ（MoKα） = 0.591, the final R = 0.0372 and wR = 0.0926. The vanadium（V） atom adopts a distorted square-pyramidal geometry coordinated by the tridentate ligand and two oxygen atoms. The hydrogen bonds and strong π-π stacking interactions link the complex molecules into a 3-D network structure.
文摘A selective and sensitive reagent of 2-pyridine carboxaldehyde isonicotinyl hydrazone（2-PYAINH） was synthesized and studied for the spectrophotometric determination of nickel, copper, cobalt, and iron in detail. At a pH value of 7.0, 9,0, 9.0, and 8.0, respectively, which greatly increased the selectivity; nickel, copper, cobalt, and iron reacted with 2-PYAINH to form a 1：2 yellow-orange, 1：2 yellow-green, 1：2 yellow and 1：1 yellow complexes, with absorption peaks at 363, 352, 346, and 359 nm, respectively. Under the optimal conditions, Beer＇s law was obeyed over the ranges of 0.01-1.4, 0.01-1.5, 0.01-2.7, and 0.01-5.4 mg/L respectively. The apparent molar absorptivity and Sandell＇s sensitivities were 8.4×10^4, 5.2×10^4, 7.1×10^4, and 3.9×10^4 L·mol^-l·cm^-1, respectively, and 0.00069, 0.0012, 0.00078, and 0.0014 μg·cm2, respectively. The detection limits were found to be 0.001, 0.002, 0.003, and 0.01 mg/L, respectively. The detailed study of various interfering ions to make the method more sensitive was carried out and selective and several real samples were analyzed with satisfactory results.
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Project was supported by Scientific Research common program of Beijing municipal commission of education (KM20051028005)
文摘A new cis-dioxovanadium （V） complex [VO2（C9H8N3O3）]（C5H5N） involving a carboxyl group coordination employing a tridentate Schiff Base derived from pyruvic acid and isonicotinyl hydrazide is reported. This complex crystallizes in triclinic, space group P1^- with a = 7.3522 （12）, b = 7.8376（13）, c = 14.898（2） ,A°, a = 84.010（2）, β = 86.568（2）, γ= 64.586（2）°, V = 771.1（2）A °^3 ,Z = 2, F（000） = 376, Mr = 368.22, D, = 1.586 g/cm^3, g = 0.677 mm ^-1, R = 0.0421 and wR = 0.1253. The vanadium atom of the dioxovanadium （V） is five-coordinated to furnish a distorted trigonal bipyramid geometry.
基金the Educational Commission of Henan Province (No. 14B150036)the Natural Science Foundation of Henan Province (No. 142300410252)the Key Disciplines of Analytical Chemistry of Henan Province
文摘Two hydrazone ligands （E）-N＇-（2-hydroxy-5-methoxybenzylidene）-2-hydroxybenzo- hydrazide （HLa） and （E）-N＇-（3,5-dichloro-2- hydroxybenzylidene）-4-methoxybenzohydrazide （HLb） were prepared and characterized by IR, UV-Vis and 1H NMR spectra. Based on the hydrazone ligands, two new structurally similar vanadium（V） complexes, [VOLaL].CH3OH （1） and [vOLbL] （2）, where L is the monoanionic form of benzohydroxamic acid （HL）, were prepared and characterized by IR and UV-Vis spectra, and single-crystal X-ray diffraction. Complex 1 crystallizes as the monoclinic space group P21/n, with a = 7.5208（10）, b = 15.490（2）, c = 20.8929（18） A, β = 96.373（2）°, V = 2418.9（5） A3, Z = 4, R = 0.0831, wR = 0.2607 and GOOF = 1.061. Complex 2 crystallizes as the monoclinic space group P21/c, with a = 11.8577（18）, b = 16.468（2）, c = 12.2288（18） A, β = 106.064（2）°, V= 2294.7（6） A3, Z = 4, R= 0.0741, wR= 0.1745 and GOOF= 1.014. X-ray analysis indicates that the complexes are mononuclear vanadium （V） species, with the V atoms located in the octahedral coordination. The hydrazone ligands and the complexes were evaluated for their antibacterial （Bacillus subtilis, Staphylococcus aureus, Escherichia coli, and Pseudomonas fluorescence） and antifungal （Candida albicans and Aspergillus niger） activities by MTT （3-（4,5-dimethylthiazol-2-yl）-2,5-diphenyl tetrazolium bromide） method.
基金Supported by Natural Science Foundation of Hunan Province(No.2016JJ4008)the Innovation Platform Open Fund Project of Hunan Provincial Education Department of China(No.16K011)+1 种基金the Open Fund Project of Key Laboratory of Functional Organometallic Materials of Hengyang Normal University(Nos.GN16k01,GN16K03)the Scientific and Technological Projects of Hengyang(No.2016KJ04)
文摘2-Oxo-butyric acid salicylacylhydrazone dibenzyltin（IV） complexes 1 {[o-OHC6H4（O）C=N-N=C（Et）COO]（CH3OH）[（C6H5CH2）2Sn]}2 and 2 {[o-OH-C6H4（O）C=N-N=C（Et）-COO]（CH3OH）[（2,4-Cl2C6H3CH2）2Sn]}2 have been synthesized. The complexes were characterized by IR, 1H, 13C and 119Sn NMR spectra, elemental analysis and thermal stability analysis, and the crystal structures were determined by X-ray diffraction. The crystal of complex 1 belongs to triclinic system, space group P1 with a = 8.9121（6）, b = 10.3875（7）, c = 14.5658（10） ？, α = 89.534（5）, β = 86.790（5）, γ = 70.103（6）°, Z = 1, V = 1265.85（15） ？3, Dc = 1.488 Mg·m^（-3）, m（Mo Kα） = 1.047 mm-1, F（000） = 576, R = 0.0466 and w R = 0.1054. The crystal of complex 2 belongs to monoclinic system, space group P21/n, a = 12.7165（10）, b = 17.8466（14）, c = 12.8538（10） ？, β = 95.1310（10）°, Z = 2, V = 2905.4（4） ？~3, Dc = 1.612 Mg·m^（-3）, m（Mo Kα） = 1.286 mm-1, F（000） = 1408, R = 0.0369 and w R = 0.0958. In vitro antitumor activities of both complexes were evaluated by the 3-（4,5-dimethylthiazoly-2-yl）-2,5-diphenyltetrazolium bromide（MTT） assay against three human cancer cell lines（NCI-H460, HepG2, MCF7） and one human cell line（HL7702）. Two complexes exhibited strong antitumor activity, and then they were expected after further chemical optimization of candidate compounds as anti-cancer drugs. The interaction between complexes and calf thymus DNA were studied by EB fluorescent probe. The interactions of the two complexes with calf thymus DNA were intercalation.
基金financial support from the National Natural Science Foundation of China(No.21132003)
文摘To find new lead compounds with high biological activity,a series of novel 4-methyl-1,2,3-thiadiazole-5-carboxaldehyde benzoyl hydrazone derivatives were designed and synthesized.Their structures were confirmed by -1H NMR,-（13）C NMR,IR spectrum and elemental analysis.Preliminary bioassay indicated that the title compounds exhibited moderate to strong fungicidal activity against six fungi in vitro at50 μg/mL.Moreover,some of the title compounds exhibited good curative activity against TMV in vivo at500 μg/mL.The structure-activity relationship analysis of compounds against Valsa mali showed that compounds containing halogen at the para position on phenyl exhibited the best activity.Especially compound 8k showed broad spectrum fungicidal activities against Valsa mali,Botrytis cinerea,Pythium aphamdermatum,Rhizoctonia solani,Fusarium moniliforme and Altemaria solani with the EC（50） values of8.20,24.42,15.80,40.53,41.48,and 34.16 μg/mL,respectively.
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.
文摘A novel ligand N-4-hydroxyacetophenone isonicotinoyl hydrazone and its manganese(II) and nickel(II) metal complexes have been synthesized. The synthesized Schiff base and its metal complexes have been characterized by physical state determination, melting point and solubility measurements in different solvents, infrared, proton nuclear magnetic resonance, mass spectrometric and powder X-ray spectroscopic techniques. The thermal properties of the prepared compounds were obtained from TG/DTG measurements. On the basis of the analytical techniques, the ligand was found to be bidentate in nature coordinating to the metal ions through the azomethine nitrogen and carbonyl oxygen atoms leading to distorted octahedral geometries of the metal complexes which were modeled using MM2 force field. The ligand and its metal(II) complexes were evaluated for antifungal activity against <i>Aspergillus fumigatus, Aspergillus niger, Candida albicans and Rhizopus stolonifera.</i> The antifungal evaluation results revealed an enhanced activity upon coordination of the ligand with the metal(II) ions. The activity of the metal complex to the tested fungal strains was in the order Ni(II) > Mn(II).
文摘Some light-lanthanide nitrate complexes were obtained by the reaction of lanthanide nitrate with isonicotinoyl hydrazone (HL = N,N'-diisonicotinoyl-2-hydroxy-5-methyl-isophthalaldehyde dihydrazone) in methanol. The general formula of the complexes is Ln(L) (NO3)(2) . nH(2)O(Ln = La, Ce, Pr, Nd and Sm; n = 0, 1). The complexes were characterized by elemental analyses, conductance, thermal analyses, UV and IR spectra. The results show that the lanthanide ion in each complex is coordinated by oxygen and nitrogen atoms of the ligand (L) and the oxygen atoms of the nitrate. The amide-oxygen atoms of L coordinate to the Ln ions in its keto-form. The magnetic susceptibility of the neodymium complex shows that the magnetic data obey Curie-Weiss law in the range of 75K < T < 300K.
文摘The ytterbium complex of isonicotinoyl hydrazone was synthesized and the structure was determined by X-ray diffraction analysis. The crystal and molecular structure of the title complex [Yb-2(L)(3)](OH)(3) shows that the complex has two identical nine-coordinated ytterbium ions with each surrounded by N3O6 donor set, Two ytterbium ions are bridged by three phenolate oxygen atoms, The geometry around each ytterbium ions can be considered as a three-capped trigonal prism.
文摘In order to study the coordination character of the rare earth elements with hydrazones and the antioxidative activity of the ligand and the complexes, 3,5 dibenzyloxybenzoyl 2,4 dihydroxybenzaldehyde hydrazone (H 2L), a new chelating ligand, and its six lanthanide complexes, Ln (HL)(OAc) 2· n H 2O [Ln=La, Sm, Eu, Gd, Tb, Dy; n =2, 4, 5], were synthesized and characterized on the basis of elemental analyses, IR and 1H NMR spectra, molar conductivity. The results show that the lanthanide ions are coordinated by O, O and N donors of the phenol (Ar OH) without deprotonation, the enol oxygen of the hydrazone group (NCO -) and the azomethine group (CH=N) from the ligand respectively, and by the four carboxylic oxygen from two acetate groups (CH 3COO -) in the bidentate form. The scavenging activity of the ligand and the six lanthanides complexes on the 2,2 Diphenyl 1 picrylhydrazyl (DPPH) free radicals is also evaluated. The results show that both the ligand and the complexes have the scavenging activity on the DPPH radicals, and the scavenging activity of the complexes is better than the ligand.
基金Supported by the National Natural Science Foundation of China(No.20402002)Natural Science Foundation of Fujian Province,China(No.2009J01019)
文摘Refluxing calix[4]-1,3-substituted benzaldehyde derivative（4） with glycine hydrazide derivative, we obtained a novel calix[4]arene hydrazone derivative（5） via ＂1＋2＂ condensation in a yield of 78%. In the reaction of compound 4 with L-leucine hydrazide derivative at room temperature, lariat calix[4]-1,3-aza-crown（6） with chiral amino acid group as branched chain was synthesized via ＂1＋ 1＂ addition in a yield of 70%. The preliminary extraction experiments suggested that hosting compounds 5 and 6 possessed good complexation abilities for a-amino acids.
基金Supported by the National Natural Science Foundation of China(Nos.20771030, 20671025)
文摘Photo-isomerization of aromatic α-hydroxy hydrazone was reported. We investigated the structures of salicylaldehyde phenylhydrozone（SP） in the ground state using density functional theory（DFT） with the B3LYP functional and the 6-311＋G（d） basis set. All nine possible isomers of SP in the ground state consist of seven phenol forms and two ketone forms. Intrisic reaction coordinate（IRC） analysis discloses the existence of a cycle driven by the two proton transfer processes in the ground and excited states of SP, which suggests that no ketonic form could exist in the ground state. Further theoretical studies of the potential energy surfaces support a trans-cis conversion followed by a relaxation to the stable form of SP in the excited states.
