Microwave-assisted synthesis of new N^4-[bi-(4-fluorophenyl)-methyl]-piperazine thiosemicarbazones under solvent-free conditions

Six new N4-[bi-（4-fluorophenyl）-methyl]-piperazine thiosemicarbazones 3a-f have been prepared starting from [bi-（4-fluorophenyl）-methyl]-piperazine in solvent-free condition under microwave irradiation with excellent yields. Their structures have been determined by elemental analysis, IR, MS and 1H NMR data.

GC/MS Analyses of Thiosemicarbazones Synthesized from Acetophenones: Thermal Decay and Mass Spectra Features

The mass spectral fragmentation of thiosemicarbazones synthesized from acetophenones has been studied by CG/MS. These carbonyl compounds exhibit chromatographic peaks which are not observed in aliphatic analogues or those synthesized from aldehydes. The analysis of the corresponding spectra has allowed structural assignment to the dimerization of gas phase neutral fragments. Theoretical calculations (DFT level) also provide evidence to support the experimental observations.

Thiosemicarbazones Synthesized from Acetophenones: Tautomerism, Spectrometric Data, Reactivity and Theoretical Calculations

Tautomeric forms of Thiosemicarbazones have been investigated by spectrometric methods, their chemical reactivity and theoretical calculations of the relative tautomers stabilities. The mass spectral fragmentation of thiosemicarbazones synthesized from acetophenones has been studied by CG/MS. The analysis of the corresponding spectra shows not only the regular fragmentation mechanisms but homolytic ruptures from even-electron species. 1H NMR spectra exhibit signals for the most intense open thioketo tautomeric structure, although when using TFA a ring structure is observed in the corresponding tautomeric equilibrium. Density Functional Theory calculations (DFT) also provide evidence to support the experimental observations by GC-MS and 1H NMR. Methylation reactions give support to the occurrence of the thioenol tautomeric form which would be the second most abundant according to the Density Functional Theoretical calculations.

Synthesis and Characterization of Novel Thiosemicarbazones Bearing Sugar Moieties

Six novel thiosemicarbazones containing sugar and thiosemicarbazide moieties were synthesized by a five-step procedure using D-galactose and D-xylose as the starting materials and the corresponding glycosyl isothiocyanates as the intermediates. The target compounds were characterized by IR, ^1H NMR, and elemental analysis. The coupliug constants between H1 and H2 in the sugar rings, all fail within the range of J = 9. 2-10.0 Hz, confirming the β-configuration of the compounds.

In vivo anticancer activity of vanillin,benzophenone and acetophenone thiosemicarbazones on Swiss albino mice

Objective:To study the anticancer activities of three schiff bases viz.vanillin thiosemicarbazone,benzophenone thiosemicarbazone and acetophenone thiosemicarbazone against Ehrlich ascites carcinoma(EAC)cells in Swiss albino mice.Methods:Synthesized compounds have administrated into the intraperitoneal cavity of the EAC inoculated mice at two doses.The anticancer activities have studied by monitoring the parameters such as cell growth inhibition,tumor weight measurement,survival time of EAC bearing mice as well as the changes in depleted hematological parameters due to tumorgenesis.All such data have been compared with those of a known standard drug bleomycin at the dose of 0.3 mg/kg(i.p.).Results:It has been found that these bases enhanced life span,reduced average tumor weight and inhibited tumor cell growth of EAC cell bearing mice remarkably.The results were similar in potency to those obtained with bleomycin.It was also found that the depleted hematological parameters(red blood count,white blood count and haemoglobin content)were found to be restored gradually towards normal within few weeks after ceasing the treatment.Conclusions:The compounds can be primarily considered more or less as potent anticancer agents.

SYNTHESIS AND TOXICITY ASSESSMENT OF DRUGGABLE THIOSEMICARBAZONES

Introduction:There is a renewed interest for thiosemicarbazones in terms of antimicrobial,antiviral,and antitumor activity.With notable exceptions(e.g.thiopental)thiocarbonyl-containing chemical entities are commonly considered as non-druggable.Screening of a library of thiosemicarbazones showed,however,exceptional potential.The purpose of this work was both to develop

An Expedient Method for the Synthesis of Thiosemicarbazones under Microwave Irradiation in Solvent-free Medium

A simple, efficient and eco-friendly method for the synthesis of thiosemicarbazones from thiosemicarbazides and aldehyde under microwave irradiation has been reported, and no solvent and catalyst were used. And the technique of microwave irradiation coupled with solvent-free condition proved to be a quite valuable method in the organic synthesis.

Synthesis and Crystal Structure ofp-tert-Butylcalix[4]arene 1,3-Distal and Monosubstituted Semicarbazones and Thiosemicarbazones

A series of p-tert-butylcalix[4]arene 1,3-distal and monosubstituted semicarbazones and thiosemicarbazones was preparedd by acid catalyzed condensation reaction of active calixarene aldehydes with semi- carbazide and thiocarbazide in methanol. One representative single crystal was determined by X-ray dirraction method, which shows that calixarene exists in cone configuration and intramolecular hydrogen-bands exist in the crystal.

Synthesis and Cytotoxicity of the First Arene Ruthenium Compound Containing Two Thiosemicarbazone Ligands

A Ru-arene compound containing two thiosemicarbazone ligands [(η6-p-cymene)Ru(TSC)2 Cl]Cl(1, TSC = benzophenone 4-methylthiosemicarbazone) has been synthesized and characterized by 1 H NMR, elemental analysis and HR-ESI mass spectrometry analysis. The molecular structure was determined by single-crystal X-ray diffraction analysis. The in vitro anticancer activities of the complex have been evaluated against two human cancer cell lines(SGC-7901, BEL-7404), and the IC50 values are 32.5 and 57 μM, respectively.

Cu(II) Propionyl-Thiazole Thiosemicarbazone Complexes: Crystal Structure, Inhibition of Human Topoisomerase IIα, and Activity against Breast Cancer Cells

Two new thiosemicarbazone ligands, 2-propionylthiazole ethylthiosemicarbazone (PTZ-ETSC), and 2-propionylthiazole tert-butylthiosemicarbazone (PTZ-tBTSC), along with their two copper(II) complexes, [Cu(PTZ-ETSC)Cl] and [Cu(PTZ-tBTSC)Cl], are reported here for the first time. Once characterized by NMR and MS, these mono-anionic tridentate ligands were reacted with Cu2+ to form the square planar metal complexes [Cu(PTZ-ETSC)Cl] and [Cu(PTZ-tBTSC)Cl]. The x-ray crystal structure of the [Cu(PTZ-tBTSC)Cl] complex shows that the complex adopts a square planar arrangement around the copper(II) ion, but forms a sulfur-bridged dimer in the solid state. Both of the copper complexes displayed strong inhibition of human topoisomerase IIα at activities between 2-4 μM for [Cu(PTZ-ETSC)Cl], and between 8-10 μM for the [Cu(PTZ-tBTSC)Cl] complex. The EC50 values for the MDA-MB-231 breast cancer cell line were 82.6 μM for (PTZ-ETSC), 17.9 μM for [Cu(PTZ- ETSC)Cl], 97.8 μM for (PTZ-tBTSC), and 1.41 μM for [Cu(PTZ-tBTSC)Cl]. The EC50 values for the MCF7 breast cancer cell lines were 9.36 μM for (PTZ-ETSC), 0.13 μM for [Cu(PTZ-ETSC)Cl], 0.333 μM for (PTZ-tBTSC), and 0.093 μM for [Cu(PTZ-tBTSC)Cl].

Cu(II) Benzoylpyridine Thiosemicarbazone Complexes: Inhibition of Human Topoisomerase IIα and Activity against Breast Cancer Cells

The focus of this research is on the study of a series of copper (II) benzoylpyridine thiosemicarbazone complexes. Of the six benzoylpyridine thiosemicarbazone ligands used in this study, two are reported for the first time;2-benzoylpyridine tert-butyl thiosemicarbazone (BZP-tBTSC), and 2-benzoylpyridine benzyl thiosemicarbazone (BZP-BzTSC). Once characterized by NMR, melting point, and MS, these mono-anionic tridentate ligands were then reacted with Cu2+ to form the new square planar metal complexes [Cu(BZP-tBTSC)Cl] and [Cu(BZP-BzTSC)Cl]. All of the copper complexes display marked inhibition of human topoisomerase IIα. The [Cu(BZP-tBTSC)Cl] complex shows marked activity against human breast cancer cell lines.

New Copper (II), Palladium (II), and Platinum (II) 2-Acetylpyrazine Tert-Butylthiosemicarbazone Complexes: Inhibition of Human Topoisomerase IIα and Activity against Breast Cancer Cells

The new ligand, 2-acetylpyrazine-tertbutylthiosemicarbazone (APZ-tBTSC), and its Cu(II), Pd(II) and Pt(II) complexes have been synthesized. This ligand coordinates to the metal ions in a tridentate monoanionic fashion forming monometallic complexes with the formula [M(APZ-tBTSC)Cl]. The ligand and the three metal complexes [Cu(APZ-tBTSC)Cl], [Pd(APZ-tBTSC)Cl], and [Pt(APZ-tBTSC)Cl] were tested for anti-proliferative biological behavior with a panel of seven microbes, and the copper and palladium complexes were found to be highly active against Gram positive bacteria. The 4 compounds were also tested in human topoisomerase IIα DNA relaxation assays and all three metal complexes had topoisomerase inhibition at a concentration between 4 - 6 micro-molar. The 4 compounds were also tested for activity with the HEK293T cell line and also the breast cell cancer line, MDA-MB-231. The most effective compound for activity against the HEK293T cell line was the [Cu(APZ-tBTSC)Cl] complex, and the MDA-MB-231 breast cancer cell line was the [Pt(APZ-tBTSC)Cl] complex.

1-Pyrenecarboxaldehyde thiosemicarbazone:A novel fluorescent molecular sensor towards mercury(Ⅱ) ion

A novel and simple fluorescent molecular sensor,1-pyrenecarboxaldehyde thiosemicarbazone（Hpytsc）,was synthesized.Its higher sensitivity and selectivity to mercury（Ⅱ） ion were studied through absorption and emission channels.The UV-vis spectra show that the increasing mercury（Ⅱ） ion concentrations result in the decreasing absorption intensity.The fluorescence monomer emission of Hpytsc is enhanced upon binding mercury（Ⅱ） ion,which should be due to the 1：1 complex formation between Hpytsc and metal ion.

Metal 2-Hydroxy-1-Naphthaldehyde Thiosemicarbazone (Me-HNT) Complexes-A New Kind of Biomimic Enzyme Catalyst

Metal (Me=Fe(III), Mo(VI), Mn(II), Co(II), Ni(II), Zn(II) and Cu(II)) 2-hydroxy-1-naphthaldehyde thiosemicarbazone complexes (MeHNT) were synthesized and used as mimic-enzyme catalysts to mimic the active group of horseradish peroxidase (HRP). The results showed that Fe-HNT, Mo-HNT are effective catalysts, which have similar catalytic activity as HRP. The sequence of catalytic activities of tested biomimic peroxidas is Mo-HNT > Fe-HNT > Zn-HNT > Ni-HNT > Mn-HNT. Among them, Fe-HNT is used as a mimic-enzyme catalyst in determination of ascorbic acid and glucose by coupling the catalytic reaction of glucose oxidase.

Structure and Luminescence Property of a Hexanuclear Silver(I) Cluster Containing Pyridine-3-carboxaldehyde Thiosemicarbazone

A new hexanuclear silver（I） compound containing thiosemicarbazone with group of 3-pyridine was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound 3 crystallizes in monoclinic,space group C2/m with a = 18.6523（9）,b = 24.7519（11）,c = 22.4542（15） ,β = 93.4960（10）°,V = 10347.4（10）3,C68H104Ag6N30O8S6,Mr = 2309.39,Dc = 1.482g/cm3,μ（MoKα） = 1.293 mm-1,F（000） = 4656,Z = 4,the final R = 0.0544 and wR = 0.1580 for 6733 observed reflections（I 〉 2σ（I））.In the structure,two Ag6L36（L3 = pyridine-3-carboxaldehyde thiosemicarbazone） clusters are contained.In each cluster,the S atom of ligand L3 served as a triply bridged chelator to connect the six silver atoms into a Ag6L36 cluster.Luminescence investigation revealed that the band at 630 nm was attributed to cluster-centered（CC） electron transfer,and those at 493 and 530 nm to the LMCT and CC transitions,respectively.

Structure and Luminescence Property of a Hexanuclear Silver(Ⅰ) Cluster Containing Benzaldehyde Thiosemicarbazone

A new hexanuclear silver （I） compound 2 containing thiosemicarbazone with the group of benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in triclinic, space group P with a = 11.611（3）, b = 15.610（5）, c = 15.624（7） , α = 113.942（6）, β = 104.520（6）, γ = 104.230（4）°, V = 2304.1（14） 3, C60H77Ag6N22O4.5S6, Mr = 2018.02, Dc = 1.454 g/cm3, μ（MoKα） = 1.435 mm-1, F（000） = 1005, Z = 1, the final R = 0.0468 and wR = 0.1474 for 6608 observed reflections （I 2σ（I））. In the structure, the S atom of the ligand L2 （L2 = benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L26 cluster. The luminescence property of compound 2 was investigated at room temperature.

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver(I) Cluster

A new hexanuclear silver（I） compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound crystallizes in monoclinic, space group P21/c with a = 16.101（4）, b = 24.855（7）, c = 14.492（4） A, β = 109.730（5）, V = 5459（3） A3, C90H102Ag6N2406S6, Mr= 2455.54, Dc= 1.494 g/cm3,μ（MoKa） = 1.228 mm^-1, F（000） = 2472, Z = 2, the final R = 0.0761 and wR = 0.1507 for 5258 observed reflections （I〉 2α（I））. In the structure, the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag6L6 cluster. Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.

Antitumor Metallothiosemicarbazonate:Synthesis,Crystal Structure,Spectra and Antitumor Studies of Co(Ⅲ) Complex with Thiosemicarbazone Derivative of 2-Benzoylpyridine

The title complex [Co（L）2]Cl·4H2O I has been achieved via self-assembly by incorporating cobalt into 2-benzoylpyridine thiosemicarbazonate ligand, and characterized by elemental analysis, infrared spectra, mass spectra and single-crystal X-ray diffraction study. The crystal crystallizes in monoclinic, space group P2 1/n, with a = 10.227（3）, b = 17.363（4）, c = 17.459（4） A, β= 100.408（4）°, V= 3049.2（13） A^3, Z = 4, Mr = 677.08, Dc = 1.475 g/cm^3, μ（MoKα） = 0.834 mm^-1, F（000） = 1400, the final R = 0.0747 and wR = 0.0896 for 1663 observed reflections with I 〉 2σ（I）. The complex contains one six-coordinated cobalt ion connected by two thiosemicarbazone ligands which act as a tridentate ligand to coordinate with the center metal atoms via two pyridyl nitrogen atoms, two imine nitrogen atoms and two sulfur atoms giving rise to a mononuclear structure. Hydrogen bonds existing in the complex link the different components to stabilize the crystal structure. The antiturnor activity of the title complex was tested against A549 lung cancer cell line. Complex ! exhibits antitumor activity.

Crystal Structure of a Hexanuclear Silver（Ⅰ） Compound [Ag_6L^66]·4DMF and Luminescence Discussion of a Series of Silver（Ⅰ） Clusters

A new silver（Ⅰ） compound 6 （[Ag6L66]·4DMF） containing thiosemicarbazone with the group of 2-chloro-1-benzene was synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analysis and fluorescence spectrum. The title compound 6 crystallizes in monoclinic, space group C2/c with a = 26.9236（18）, b = 15.2553（8）, c = 24.6237（13） , β = 103.0680（10）°, V = 9851.7（10）3, C58H66Ag6Cl6N20O3S6, Mr = 2143.59, Dc = 1.445 g/cm3, μ（MoKα） = 1.503 mm-1, F（000） = 4232, Z = 4, the final R = 0.0565 and wR = 0.1654 for 5831 observed reflections （Ⅰ 〉 2σ（Ⅰ））. Similar to the structure of the compounds we have reported, compound 6 also exhibits a hexanuclear silver（Ⅰ） cluster. In the cluster, the S atom of ligand L6 （L6 = 2-chloro-1-benzaldehyde thiosemicarbazone） served as a triply bridged chelator to connect the six silver atoms into a Ag6L66 cluster. The luminescence property of compound 6 was investigated at room temperature and compared with other similar compounds in order to find the factors influencing their luminescent property.

Synthesis and Antioxidant Activity of(E)ω-Formylcamphene-Based Thiazole Hydrazone Derivatives

(E)ω-formylcamphene was synthesized fromα-pinene,the main component of turpentine,and then reacted with thiosemicarbazide to obtain(E)ω-formylcamphene thiosemicarbazide 3,which was reacted with 14α-bromoace-tophenone compounds to obtain 14(E)ω-formylcamphene thiazole hydrazone compounds 5a–5n;the yields were all above 80%.The structures of the target compounds were characterized by IR,^(1)H-NMR,^(13)C-NMR,and HR-MS analyses.Then,500,250,125,62.5,and 31.25 mg/L drug solutions were prepared.Free radical scavenging experi-ments of 1,1-diphenyl-2-picrylhydrazyl(DPPH)and 2,2-bis(3-ethyl-benzothiazole-6-sulfonic acid)diammonium salt(ABTS)were carried out with Trolox and L-ascorbic acid as the control samples.The scavenging rates of 14 compounds for DPPH and ABTS free radicals were obtained;the IC_(50) values of scavenging free radicals were fitted using SPSS software.The results show that 14(E)ω-formylcamphene-based thiazole hydrazone compounds exhibited good scavenging effects on the two free radicals,especially when the concentration of the drug solution was 125 and 62.5 mg/L;most compounds exceeded the scavenging efficiency of Trolox and L-ascorbic acid.