Synthesis and Physico-Chemical Characterizations of Novel Hydrazone Ligands and Their Metal Complexes against Hormone-Dependent and Independent Cancers

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.

Silica Gel Supported Trifluoromethanesulfonic Acid Catalyzed Beckmann Rearrangement of Cyclohexanone Oxime in Liquid Phase

The liquid phase Beckmann rearrangement of cyclohexanone oxime (CHO) using fuming sulfuric acid as a catalyst is a traditional method for preparing ε-caprolactam (CPL). This process has drawbacks, such as environmental pollution, corrosion of equipment, and low added value of by-product ammonium sulfate. This article designed and prepared a green silica gel-supported trifluoromethanesulfonic acid catalyst for the liquid-phase Beckmann rearrangement of CHO to prepare (CPL). The influencing factors of catalyst preparation and the optimal reaction conditions for Beckmann rearrangement were investigated. It was found that the optimal conditions for catalyst preparation were as follows: raw material silica gel:trifluoromethanesulfonic acid = 1:0.2 (mass ratio), room temperature, stirring time of 2.5 hours, and solvent of acetonitrile, silica gel mesh size is 100 - 200. The optimal reaction conditions for Beckmann rearrangement are CHO: catalyst = 1:2 (mass ratio), temperature of 130˚C, solvent of benzonitrile, volume of 30 mL/g CHO, and reaction time of 4 hours. Under the above conditions, the conversion of CHO is 90%, and the selectivity of CPL is 90%.

Analytical, Spectral, Thermal and Molecular Modeling Studies of Hg2+-2,3-Butanedionemonoxime Girard’s T Hydrazone Complex and Its Application

The coordination behavior of 2,3-butanedionemonoxime Girard’s T hydrazone (L1) towards Hg2+ ion has been investigated. The structure of Hg2+ complex, [Hg(L1)Cl]Cl·5H2O, is elucidated using elemental analyses, spectral (IR, UV-visible, 1H-NMR and mass) and TGA measurements. IR spectrum suggests that L1 behaves in a bidentate manner through the azomethine groups. The molecular modeling of L1 and its Hg2+ complex has been investigated. The bond lengths, bond angles, HOMO and LUMO have been calculated. The thermal behavior and kinetic parameters are determined using Coats-Redfern method. The use of L1 for preconcentration and separation via flotation of Hg2+ complex and determination using cold vapor atomic spectrometry (CVAAS) is described. The effects on the percentage of recovered Hg2+ by pH of sample solutions, oleic acid (HOL) concentration, Hg2+ and L1 concentrations are studied in details. The method is applied for the determination of the total Hg2+ (mg·mL-1) in natural water samples.

Milbemycin Oxime半抗原设计及其抗体制备

通过milbemycin oxime A4、A3(MILO)肟羟基与琥珀酸酐反应,合成了半抗原MILO-5-琥珀酰半酯,采用碳化二亚胺法将其与载体蛋白BSA偶联制备人工抗原.以此人工抗原免疫新西兰大白兔获得多克隆抗体,抗体效价达1:12 800;用此抗体建立的间接竞争酶联免疫吸附(CI-ELISA)检测方法,线性范围在16.00～4 394.18 ng/mL,最低检测限(I10)为6.28 ng/mL.

Synthesis and Crystal Structure of Lanthanum Nitrate with Methyl-2-pyridyl Ketone Benzoyl Hydrazone

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.

Flotation performance and adsorption mechanism of novel 1-(2-hydroxyphenyl)hex-2-en-1-one oxime flotation collector to malachite

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.

PEG-SO_3H as catalyst for the Beckmann rearrangement and dehydration of oximes

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.

Synthesis, Crystal Structure, and Biological Activity of 4-Chlorobenzaldehyde (2-trifluoromethylTrifluoromethyl-5,6,7,8-tetrahydrobenzo[4 ,5]-thieno[2,3-d]pyrimidin-4-yl)hydrazone Monohydrate

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.

Synthesis and Crystal Structure of a Vanadium(V) Complex with 2-Hydroxy-1-naphthaldehyde Isonicotinoyl Hydrazone

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.

Synthesis,Crystal Structure and Biological Activities of O-[(Z)-2-Methylbenzyl] 1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone Oxime

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.

Synthesis, Crystal Structure and Antibacterial Activity of Two Hydrazones Derived from 2-Fluorobenzhydrazide

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.

A Convenient and Efficient Procedure for Oxime Ethers

Acetophenone oxime and benzaldehyde oxime were converted to oxime ethers in the presence of alkyl halide or methyl sulfate and KOH in aqueous DMSO in 5 to 70 min. The yields of oxime ethers were 70 - 96%.

AmmAmmoximation of Cyclohexanone to Cyclohexanone Oxime Catalyzed by Titanium Silicalite-1 Zeolite in Three-phase System

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.

A Mild Oxidant for the Regeneration of Carbonyl Compounds from Oximes in Nonaqueous Condition

Dioxane-NO2 was employed to oxidize oximes to corresponding aldehydes and ketones in high yield in nonaqueous condition at room temperature. Thr reaction proved to be mild and selective.

Studies on Lead(Ⅱ) Complexes of Ferrocenylaldehyde Aroylhydrazones

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.

Synthesis and Crystal Structure of (E)-2-phenyl-6,7dihydrobenzofuran-4(5H)-one O-cyanomethyl Oxime

A pair of E/Z-isomers of 2-phenyl-6,7-dihydrobenzofuran-4（5H）-one O-cyanomethyl oxime,C16H14N2O2,as potential drugs for treating peptic ulcer and other acid-related diseases have been synthesized and characterized by IR,MS and NMR spectra.Meanwhile,the crystal of IIIa was obtained and determined by X-ray single-crystal diffraction.Crystal data： monoclinic system,space group P21 /c,a = 8.423（8）,b = 19.596（16）,c = 8.770（8）,β = 107.750（12）°,V = 1379（2）3,Z = 4,F（000） = 560,Dc = 1.283 g/cm3,μ = 0.086 mm 1,R = 0.0681 and wR = 0.2029 for 14472 independent reflections（Rint = 0.0782） and 2428 observed ones（I 2σ（I））.

Simple, Selective, and Sensitive Spectrophotometric Method for Determination of Trace Amounts of Nickel(Ⅱ), Copper (Ⅱ), Cobalt (Ⅱ), and Iron (Ⅲ) with a Novel Reagent 2-Pyridine Carboxaldehyde Isonicotinyl Hydrazone

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.

Synthesis, Characterization and Antibacterial Activity of Biologically Important Vanillin Related Hydrazone Derivatives

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.

Comparative Process for the Preparation of 9-Oxime Erythromycin A

The comparative process for preparing 9-oxime erythromycin A (EMAO) is investigated. EMAO was synthesized and compared by the reaction of erythromycin and hydroxylamine hydrochloride with various bases such as sodium acetate, triethylamine, etc. A new synthetic method is established. The oximation is performed under dynamic buffer system; less degradation impurities are formed. The yield of EMAO reaches more than 95%, HPLC analysis shows that the purity of EMAO is more than 90%, and the E/Z isomeric ratio preponderates over 7∶1.

Syntheses, Crystal Structures and Antimicrobial Activities of Vanadium(V) Complexes with Similar Tridentate Hydrazone Ligands

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.