Nahide Gulsah Deniz

Synthesis and Spectroscopic Properties of S-,O-Substituted Naphthoquinone Dyes

New S-,O-substituted naphthoquinone compounds (3a, 4b, 6, 7c, 9d, 10, 12, 13c, 14d, 15) were synthesized via vinilic substitution. 2,3-Dichloro-1,4-naphthoquinone gave 3a and 4b with 4,4′-thiobisbenzenethiol, respectively. Compounds 6 and 7c were obtained from the reaction of 2,3-dichloro-1,4-naphthoquinone with cyclohexylmercaptane. The compounds 9d and 10 were prepared from the reaction of 2,3-dichloro-1,4-naphthoquinone with 6-mercapto-1-hexanol. Compounds 12, 13c, 14d, and 15 were synthesized from the reaction of 2,3-dichloro-1,4-naphthoquinone with 1,6-hexanedithiol. Their structures were characterized by micro analysis, FT-IR, 1H NMR, 13C NMR, MS, UV-Vis, and fluorescence spectroscopy.

Iron(III), nickel(II) and zinc(II) complexes based on acetophenone-S-methyl-thiosemicarbazone: synthesis, characterization, thermogravimetry, and a structural study

New complexes, [Fe(L)Cl], [Ni(L)], and [Zn(L)C2H5OH] (1–3), were synthesized by template reaction of 2-hydroxy-acetophenone-S-methyl-thiosemicarbazone with 2-hydroxy-benzaldehyde. The compounds were characterized by elemental analysis, magnetic measurements, FT-IR, 1H NMR, UV–visible, and ESI–MS spectra. In these complexes, the ligand is coordinated to the metal ion as dinegatively charged tetradentate chelating agents via the N2O2 donor set. The iron(III) and zinc(II) complexes exhibit square pyramidal geometry whereas the nickel(II) complex has a square planar geometry. The crystal structure of 1, determined by X-ray diffraction method, indicates that 1 crystallizes in the monoclinic space group P21/c with Z = 4. Thermal decompositions of the compounds have been investigated using TGA in air.

Synthesis and investigation of antioxidant activity of the dithiocarbamate derivatives of 9,10-anthracenedione

A variety of new derivatives of 9,10-anthracenedione with mono- and bisdithiocarbamate moiety in the non-catalytic conditions have been synthesized. The obtained compounds were screened for their antioxidant capacity using the cupric-reducing antioxidant capacity (CUPRAC) method. Three of the compounds showed CUPRAC-Trolox equivalent antioxidant capacity (TEAC) coefficients higher than trolox. Scavenging effects on reactive oxygen species (ROS), hydroxyl radical scavenging (HRS), hydrogen peroxide scavenging (HPS), and superoxide anion radical scavenging (SARS) of all synthesized compounds were determined. It was established that the results of HRS-, HPS-, and SARS-CUPRAC methods for three compounds are in accordance with TEAC-CUPRAC assay data.Graphical abstract

Synthesis, characterization of N-, S-, O-substituted naphtho- and benzoquinones and a structural study

AbstractThe new series of N-, S-, O-substituted 1,4-naphthoquinone and S-, O-substituted 1,4-benzoquinone compounds were synthesized via vinylic substitution. Compounds 3 and 4 were synthesized from the reaction of 1 with 2. Compounds 6, 7 and 8 were synthesized from reaction of 1 with 5. Compounds 10 and 11 were obtained from the reaction of 1 with 9. Compounds 13 and 14 were synthesized from the reaction of 1 with 12. Compounds 16 and 17 were obtained from the reaction of 15 with 2. Photochemical and electrochemical properties of N-, S-, O-substituted quninone compounds were determined by using fluorescence spectroscopy and cyclic voltammetry. Crystal structure of 2-(7-sulphanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-1,4-naphthoquinone 13 was determined by X-ray diffraction method. Graphical AbstractThe new series of heteroatom substituted 1,4-naphtho- and 1,4-benzoquinone compounds were synthesized via vinylic substitution. Photo- and electrochemical properties of N-, S-, O-substituted quinone compounds were investigated by fluorescence spectroscopy and cyclic voltammetry. The structure of 2-(7-sulfanyl-4-methyl-coumarinyl)-3-(1-ethoxy)-1,4-naphthoquinone 13 was determined by X-ray diffraction method.

Synthesis of novel N-, S-substituted-polyhalo-1, 3-butadienes and crystal structure of dibutadienyl homopiperazine

AbstractPolyhalogenated-2-nitro-1, 3-butadienes are important synthetic precursors for a variety of polyfunctionalized bioactive heterocycles. Herein, we report the reactions of 1, 1, 3, 4, 4-pentachloro-2-nitro-1, 3-butadiene 1 and 4-bromo-1, 1, 3, 4-tetrachloro-2-nitro-1, 3-butadiene 2 with amino and thiol containing nucleophiles to obtain highly functionalized (E)-polyhalodiene-2-nitro-1, 3-butadiene derivatives. Most of these reactions were found to be highly selective resulting in good to high yields of the products. All new compounds have been characterized by nuclear magnetic resonance spectroscopy (NMR), mass spectrometry (MS) and Fourier transform infrared spectroscopy (FT-IR) spectroscopic data. Single crystal X-ray structure analysis of compound 8c is reported. Graphical AbstractPolyhalogenated-2-nitro-1,3-butadienes are important synthetic precursors for a variety of polyfunctionalized bioactive heterocycles.We report here the reactions of 1,1,3,4,4-pentachloro-2-nitro-1,3-butadiene and 4-bromo-1,1,3,4-tetrachloro-2-nitro-1,3-butadiene with amino and thiol containing nucleophiles to obtain highly functionalized (E)-polyhalodiene-2-nitro-1,3-butadiene derivatives. All new compounds have been characterized by NMR, Mass and FT-IR.

One-pot synthesis, characterization, and antioxidant capacity of sulfur- and oxygen-substituted 1,4-naphthoquinones and a structural study

AbstractIn the present study, we reported the one-pot synthesis of S,S- and S,O-substituted 1,4-naphthoquinones, their structural studies, and investigation of their antioxidant activity. The multicomponent reactions of 2,3-dichloro-1,4-naphthoquinone with sulfur- and oxygen-containing nucleophiles were investigated to obtain highly functionalized S,S- and S,O-substituted 1,4-naphthoquinone derivatives. All new compounds were characterized on the basis of 1H, 19F, and 13C nuclear magnetic resonance spectroscopy, mass spectrometry, and Fourier transform infrared spectroscopy. Crystal structure of 2,3-dihydro-2-(hydroxymethyl)naphtho[2,3-b]-1,4-oxathiin-5,10-dione was determined by X-ray diffraction method. The synthesized compounds were screened for their antioxidant capacity and free radical scavenging activity using the cupric reducing antioxidant capacity method and DPPH method, respectively. 3-Chloro-2-[3-(3-chloro-1,4-dihydro-1,4-dioxonaphthalen-2-yloxy)propylsulfanyl]-1,4-naphthoquinone shows the highest antioxidant capacity with 0.63 cupric reducing antioxidant capacity—trolox equivalent antioxidant capacity coefficient.Graphical abstract

Computer-aided prediction and cytotoxicity evaluation of dithiocarbamates of 9,10-anthracenedione as new anticancer agents

Abstract Anticancer activity as an associated action for a series of dithiocarbamates of 9,10-anthracenedione was predicted using the PASS computer program and analysed with PharmaExpert software. The predicted cytotoxic activity of the dithiocarbamate derivatives of 9,10-anthracenedione was evaluated in vitro on cancer cells of the human lung (A549), prostate (PC3), colon (HT29) and human breast (MCF7) using the sulforhodamine B (SRB) cell viability assay. Among these compounds, 9,10-dioxo-9,10-dihydroanthracen-1-yl pyrrolidin-1-carbodithioate and 9,10-dioxo-9,10-dihydroanthracen-2-yl pyrrolidin-1-carbodithioate were identified as the most potent anticancer agents with cytotoxic activity against the MCF-7 human breast cell line with GI50 values of 1.40 μM and 1.52 μM, whereas the GI50 value for the reference anticancer drug mitoxantrone was 3.93 μM. Thus, anticancer activity predicted by PASS with a probability Pa > 30% was confirmed by the experiment. Relatively small Pa values estimated by PASS indicated the novelty of the considered derivatives comparing to the compounds from the PASS training set.

Synthesis and investigation of antimicrobial and antioxidant activity of anthraquinonylhydrazones

The new anthraquinonylhydrazones were obtained by the interaction of 9,10-dioxoanthracene-1-diazonium sulfates with a number of α- and β-carbonyl-containing compounds under modified conditions of the Japp–Klingemann reaction, and a probable mechanism of the formation has been proposed. It was found that hydrazones, unsaturated in the second position of the anthraquinone ring, containing acetyl or ethoxycarbonyl moieties in the ylidene part of the molecule, are capable of eliminating these fragments. It has been experimentally established that hydrazones, free rotation around the N=C bond of which is possible, exist as one isomer due to the presence of an intramolecular hydrogen bond in the molecule. The anthraquinonylhydrazone of dimedone with action against the bacteria strains of Staphylococcus aureus 209-P, Mycobacterium luteum B-917, and fungus Candida tenuis VKM Y-70 was found. The hydrazones of dimedone and barbituric acid with a higher trolox equivalent antioxidant coefficients of antioxidant action were found using CUPRAC assay. In addition, the hydrazones of dimedone and barbituric acid exhibited better activity against catalase enzyme. Correlations between the structure of the synthesized hydrazones and their antioxidant activity have been defined.Graphical abstract

Synthesis of Tris(Arylthio)-1,3-Butadienes by Nucleophilic Vinylic Substitution of Polyhalogenated Nitrodienes and Structural Elucidation of the Products

GRAPHICAL ABSTRACT Abstract The reactions of polyhalo-2-nitro-1,3-butadiene with naphthalene-2-thiol and 4-methylbenzenethiol lead to highly functionalized poly(arylthio)-2-nitro-1,3-butadienes. The novel 4,4-dichloro-1,1,3-tris(2-naphthylthio)-2-nitro-1,3-butadiene (5a) and the known 4,4-dichloro-1,1,3-tris(4-methylphenylthio)-2-nitro-1,3-butadiene (5b) were synthesized by vinylic substitution of 1,1,3,4,4-pentachloro-2-nitro-1,3-butadiene with naphthalene-2-thiol and 4-methylbenzenethiol, respectively. X-ray crystal structure analyses of tris(arylthio)-2-nitro-1,3-butadienes are quite rare in the literature. Both 5a and 5b crystallize in the monoclinic space group P21/c with a = 10.5068(3) Å, b = 19.2468(7) Å, c = 15.0354(6) Å, Z = 4 for 5a and a = 10.7087(5) Å, b = 19.3315(7) Å, c = 12.8395(5) Å, Z = 4 for 5b. The structures have been solved by direct methods (SIR92) and refined to the residual index R1 = 0.053 for 5a and R1 = 0.048 for 5b. The structure of 5a was also characterized by NMR, mass and FTIR spectroscopy.

Synthesis and Characterization of S,S-, S,S,S-, and Thiomorpholinyl-Substituted Nitrodiene Compounds and a Structural Study

GRAPHICAL ABSTRACT Abstract S,S- and S,S,S-substituted nitrodienes 3a, 3b, and 4a were synthesized by reactions of 1,1,2,4,4-pentachloro-3-nitro-1,3-butadiene with some thiols 4-chlorobenzylmercaptan and 2-chlorobenzylmercaptan in ethanol in the presence of sodium hydroxide. Thiomorpholine ring substituted nitrodienes 6c and 6d and were obtained from the reactions of the mono(thio)substituted nitrodienes with thiomorpholine in dichloromethane. The single crystal X-ray structure of 4-(1-thiomorpholinyl)-4-(butylsulfanyl)-1,1,2-trichloro-3-nitro-1,3-butadiene (6c) is reported. In this present paper, the structures of new compounds were characterized by using nuclear magnetic resonance (NMR) spectroscopy, mass spectrometry (MS), and Fourier transform infrared (FTIR) spectroscopy spectroscopic data.