Vol 87, No 12 (2017)

It has been stated that immobilized nickel nanoparticles catalyze disproportionation and cross-coupling of amines. The influence of the support on the catalysis of these properties in the in plug-flow reactor has been studied. The use of active carbon as the support has been found advantageous for the cross-coupling of amines, whereas alumina was a better support for the disproportionation reaction.

H-Lithiation and Br-lithiation reactions of 1,3-thiazole were studied in order to obtain new thiazole derivatives. Four isomeric chloromethyl derivatives of 1,3-thiazole containing a protected aldehyde group like 2-(1,3-dioxolan-2-yl)-5-(chloromethyl)-1,3-thiazole, 5-(1,3-dioxolan-2-yl)-2-(chloromethyl)-1,3-thiazole, 4-(1,3-dioxolan-2-yl)-2-(chloromethyl)-1,3-thiazole, and 2-(1,3-dioxolan-2-yl)-4-(chloromethyl)-1,3-thiazole were synthesized. Their nucleophilic substitution reactions with dimethylamine and sodium methylthiolate were studied. New aldehydes of 1,3-thiazole series of low-molecular weight were obtained.

Reactions of 4-(dibromomethyl)benzaldehyde with trialkyl orthoformates in the presence of both Brønsted (H₂SO₄) and Lewis (ZnCl₂) acids involved acetalization of the aldehyde group. In the first case, the corresponding acetal is formed as the only product, whereas in the second case the reaction is accompanied by transformation of the dibromomethyl group to give terephthalaldehyde and its mono- and bis-acetals.

Thiosemicarbazides of diphenylphosphorylacetic acid and their cyclic derivatives have been synthesized. Functionalization of the obtained 1,2,4-triazole-3-thiones with ethyl 2-bromoacetate at the sulfur atom has been carried out, the obtained esters have been transformed into the corresponding hydrazides via hydrazinolysis. Preliminary pharmacological tests of the synthesized compounds have been performed.

New amination reactions of morpholine with a series of chloronitro-substituted benzofurazanes and -furoxanes were studied. The reactions of morpholine with 5,7-dichloro-4,6-dinitrobenzofuroxane and 4-chloro-5-nitro- and 5-chloro-4-nitrobenzofurazanes gave products of the aromatic nucleophilic substitution of the chlorine substituents in the nitrogenous heterocycles. The composition and structure of the products were established by chemical, physical, and physicochemical methods. The reaction of morpholine with 4,6-dinitrobenzofuroxane gave a stable Meisenheimer σ-complex, the structure of which was assessed by X-ray diffraction analysis. The synthesized compounds showed high antibacterial and antimycotic activities toward pathogenic human and animal microflora.

A complex of physicochemical methods was used to study the aggregation characteristics of an imidazolium-containing amphiphile and its ability for complex formation with bovine serum albumin (BSA). Tensiometry showed that adding BSA to the surfactant decreases the aggregation threshold of the system by a factor of 50. Dynamic light scattering established, that the size of the surfactant–BSA complexes depends on the size of the polypeptide (6–10 nm) and is independent on the concentrations of the surfactant and BSA. The Stern‒Volmer constants and surfactant‒protein binding constants were calculated from fluorescence spectroscopy data.

It has been shown for the first time that aqueous solutions of metaphos pesticide (1×10^–4–1×10^–17 mol/L) are disperse systems, the disperse phase undergoing rearrangement upon dilution. The relationship between nonmonotonic concentration dependences of the nanoassociate size, physico-chemical properties of the systems, and their action on higher plants and hydrocoles has been found.

Island copper-containing films consisting mainly of copper(I) oxide particles were obtained on a quartz surface by photochemical decomposition of copper(II) complex compounds with amino acids. The size and morphology of Cu₂O particles and their dependence on the photolysis duration and the amino acid nature contained in the complex were established. The films obtained by the complex [Cu(β-Ala)₂] photolysis have the highest photocatalytic activity in reactions of methyl orange photodecomposition.

Features of interphase distribution of scandium chloride in the systems containing tributyl phosphate and molecular iodine have been analyzed. Significant electrolytic dissociation of the formed complex scandium chloride with tributyl phosphate and iodine in the organic phase (almost complete at tributyl phosphate concentration 80–100%) has been observed. The increase in electroconductivity of the solutions of scandium chloride has been most prominent at the ratio of scandium chloride and iodine corresponding to the formation of monosolvate. Accounting for electrolytic dissociation in the organic phase allowed the description of the interphase extraction of scandium chloride in the studied systems.

Barium amidoborane was synthesized for the first time by the reaction of metal barium with ammonia borane. The compound was characterized by the methods of the solid-phase ¹¹B NMR and IR spectroscopy and elemental analysis. It was shown by simultaneous thermal analysis that hydrogen is the only volatile product of barium amidoborane decomposition in the temperature range 50–240°C.

A method for the synthesis of vinyl derivatives of the terpenols verbenol and fenchol by their reaction with calcium carbide was developed. It was found that addition of potassium fluoride affects the yield of nucleophilic addition of the corresponding alcoholate ions to acetylene.

Functionally substituted cyano carbonyl compounds have been synthesized by reactions of 1-chloro-oxiranecarbaldehyde acetals and α-chlorobenzyl diethoxymethyl ketones with potassium cyanide in DMF.

According to NMR data, diphenylphosphine reacted with two equivalents of 1,4-naphthoquinone under mild conditions to form betaine, 1',4'-dihydroxynaphth-2'-yl-diphenylphosphonium (1-hydroxynaphth-2-yl-4-ate), which was converted to bis(1,4-dihydroxynaphth-2-yl)diphenylphosphonium salts when treated with hydrogen bromide or trifluoracetic acid.

Secondary phosphine selenides reacted as selenating agents with benzoylphenylacetylene in wet acetonitrile (70–72°C) to give bis(2-benzoyl-1-phenylvinyl) selenide in up to 43% yield.

Protolytic properties of porphyrin complexes with Mg, analogs of the natural porphyrin chlorophyll, were investigated by the UV spectroscopy method with simultaneous potentiometric determination of pH of the medium with the aim to detect metalloporphyrin forms arising in a solution with changing its acidity. To consider interconversions in solutions, MCR-ALS soft modelling based on the chemometric analysis of spectrometric data was applied.

Previously published studies on imidazole derivative ligands suggested two main characteristic complex structures that are independent on the central metal ion. By the thermally induced decomposition behaviors, two different systematic decomposition trends were proposed. In this work, one of these characteristic decomposition mechanisms was again found for precipitated 2-(pyridin-2-yl)imidazole complexes. The final goal of these serial studies is to provide, by experimental evidences, a prediction model of thermal stability and typical decomposition behavior by comparing the structural characteristics of precipitated complexes. 2-(Pyridin-2-yl)imidazole complexes with transition metal ions of the general formula M(PyIm)₂(H₂O)₂ (where M = Cu, Fe, Ni, Pd, Pt, Zn) were synthesized, characterized, and studied by thermoanalytical techniques coupled to mass spectrometry, to suggest their decomposition mechanism by evolved gas analysis (EGA-MS). As experimentally demonstrated in previous works, these complexes can be precipitated with two methanol molecules in the structure. By differential scanning calorimetry it was shown that methanol molecules can be replaced by water molecules under controlled conditions.

A series of 1-(arylthio)naphthalen-2-ols have been synthesized by condensation of naphthalen-2-ol with 1,2-diaryldisulfanes in the presence of iodine under microwave irradiation and conventional heating methods. Structures of the products were elucidated from the spectral data (IR, ¹H, and ¹³C NMR, mass spectra) and elemental analysis. All products were tested for in vitro antibacterial and antifungal activities.

Six organotin(IV) complexes have been synthesized by refluxing sodium salt of 3-(1H-indol-3-yl)-propanoic acid with di- and triorganotin chlorides in 1: 1 and 2: 1 molar ratios, respectively. These complexes have been characterized by elemental analysis, IR, and ¹H, ¹³C, and ¹¹⁹Sn NMR spectral data. DNA binding studies were performed by viscometric measurements and UV-Vis spectroscopy. Both techniques indicated an intercalation mode of interaction. Cytotoxic activity of the ligand salt and organotin(IV) complexes 1–6 was tested against human ovarian cell line A2780. Results of bioassay revealed that organotin derivatives were more active than anticancer drug cis-platin. Triorganotin(IV) compounds had higher cytotoxic activity than corresponding diorganotin(IV) complexes.

New series of thiophenes 6a–6e and 1,3-thiazolidines 13a–13f and 15a–15e were synthesized starting from 2-(4-methoxybenzoyl)-3-(phenylamino)-3-thioxopropanoate 3. The reaction of 3 with 1-aryl-2-bromoethanones 4a–4e yielded thiophenes 6a–6e. The X-ray single crystal analysis data accumulated for 6c and its structural features can be extended to the analogues 6a, 6b and 6d, 6e. Treatment of 3 with ethyl 2-bromoacetate afforded 1,3-thiazolidinone 11 which upon treatment with aldehydes 12a-f or isatins 14a–4e gave 5-arylidene derivatives 13a–13f and 4-oxo-5(-2-oxoindolin)-3-ylidenes 15a–15e, respectively. The newly synthesized compounds were tested in vitro for their anti-cancer activity against two cell lines (HepG-2 and MCF-7) using MTT assay. Most of these compounds demonstrated a significant anticancer activity compared with that of doxorubicin. Isatin derivative 15a was the most potent compound against HepG-2 cancer cells whereas p-MeO substituted benzylidine 13b showed the highest anticancer activity against MCF-7 cancer cells. The fluoro substituted isatin 15d showed anticancer activity more potent than doxorubicin against both HepG-2 and MCF-7 cancer cells, respectively.

A group of new 2-alkyloxypyridine-3-carbonitriles linked pyrenyl-pyrazole functions has been obtained via reaction of 1-(3-chlorophenyl)-3-(pyren-1-yl)-1H-pyrazole-4-carbaldehyde with different methyl aryl ketones. The newly compounds were assured by spectroscopic and elemental analysis.

In the present study, a series of 1,4-naphthoquinone oxime derivatives has been synthesized. The structures were confirmed by spectroscopic methods. The newly synthesized compounds were evaluated for their in vitro cytotoxicity. Among those, the compounds 8c, 8d, 8e, 12a, and 12b demonstrated potent cytotoxic activity comparable with that of the reference drug 5-Fu.

Cytotoxic activity of the newly synthesized phosphinolinium-type bromide salts was evaluated against two cell lines of human origin: A549 lung adenocarcinoma and U251 glioblastoma using the sulforhodamine B assay. Compound with long alkyl chain demonstrate a stronger effect on viability of two cell lines than cysplatin.

An efficient, magnetically separable catalyst was synthesized by immobilization of Preyssler heteropoly acid (HPA) on Ni_0.5Zn_0.5Fe₂O₄ magnetite nanoparticles (MNPs) coated with hydroxyapatite (HA). The catalyst was characterized by scaning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray diffraction (XRD), FT-IR, energy dispersive spectroscopy (EDS), and TGA. Activity of this catalyst was tested in the synthesis of imidazole derivatives via one-pot three-component condensation of [9,10]-phenanthraquinone with aryl aldehydes and ammonium acetate at room temperature under solvent-free conditions.

A series of novel substituted bis-benzimidazole derivatives were synthesized by reaction of 5,5′-methylenebis(2-hydroxybenzaldehyde) with various substituted o-phenylenediamines in glacial acetic acid. The structure of the newly synthesized compounds was elucidated by ¹H and ¹³C NMR, FT-IR, and MS spectra, and their antimicrobial activity against gram positive and gram negative bacteria and antifungal activity were evaluated. The thienyl-substituted derivative showed significant activity against Bacillus licheniformis, Bacillus subtilis, Staphylococcus aureus, Klebsiella pneumonia (bacteria), and Fusarium solani (fungi). The activities of the fluoro-substituted substituted derivative against some bacterial strains and of the thienyl-substituted derivative against fungi were found to be similar to those of standard drugs.

A series of 1,4-bis(2,3-dihydro-5-oxopyrrol-4-yl)-1,3-butadienes were designed as inhibitors of checkpoint kinase 1 (Chk1), based on the structure‒activity relationships for known inhibitors through docking simulations. The docking results suggested that the title compounds were similar to known inhibitors in interaction with the catalytic site of Chk1. Twelve compounds were synthesized by a one-pot procedure from amines, dimethyl acetylenedicarboxylate, and glyoxal in water in the presence of catalytic amounts of γ-cyclodextrin. The inhibitory activities of the synthesized compounds were evaluated in vitro using EC9706 esophageal cancer cells. The results indicated that 1,4-bis(2,3-dihydro-5-oxopyrrol-4-yl)-1,3-butadienes significantly inhibited Chk1 (IC₅₀ 10.45 μM).

Two new Schiff bases derived from combination of 4-aminoantipyrine with ethylenediamine (L₁) or benzaldehyde (L₂), gave Au(III) complexes. Their structures were elucidated from microanalytical, magnetic, conductance, and FT-IR, UV-Vis, Mass, and ¹H and ¹³C NMR spectral data. High conductance values indicated electrolytic nature of the complexes. Magnetic moments and electronic spectral data indicated that two synthesized Au(III) Schiff base complexes had a square planar geometry. FT-IR spectroscopic data demonstrated that the Schiff bases were coordinated to Au(III) ions in a tetradentate manner with NNNN donor sites of two 4-amino antipyrine and two azomethine (L₁), while L₂ Schiff base ligand coordinated to Au(III) ions via its four azomethine nitrogen, which was further supported by the appearance of new bands in IR spectra due to ν(M–N). Activation thermodynamic parameters (E*, ΔH*, ΔS*, and ΔG*) were calculated on the basis of TG curves. Crystalline structures of Schiff bases and their Au(III) complexes were characterized by X-ray diffraction (XRD), their morphology was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The Schiff base ligands and their Au(III) chelates were screened for their antimicrobial activity. Cytotoxic activity of those was tested against the human breast cancer (MCF-7) and human hepatocellular carcinoma (HepG-2) tumor cell lines.

Magnesium complexes of tetraazaporphyrins containing different numbers of phenyl rings in the macrocycles were synthesized by template condensation of maleodinitrile and phenylmaleodinitrile in the presence of magnesium butoxide in butanol at the boiling point of the alcohol. Magnesium(II) 2-phenyltetraazaporphyrin was synthesized and characterized.

The paper presents the methods of synthesis of dimeric and trimeric compounds formed by donor–acceptor interactions of Zn^II, Mn^III, and Sn^IV porphyrin complexes. The structure of the porphyrin ensembles was determined by ¹H NMR spectroscopy. The extra coordination properties of the synthesized dimeric and trimeric supramolecular systems in relation to nitrogen-containing compounds were studied and the stability constants of the resulting porphyrin extra complexes were determined.

The rheological properties of nitrocellulose solutions in cyclohexanone in the presence of phthalic and 4-nitrophthalic diester plasticizers were studied by rotational viscometry to reveal a behavior similar to that of Newtonian fluids. The activation parameters of the viscous flow regime were calculated. An influence of nitroplasticizers and dibutyl phthalate on the rheology of nitrocellulose was established. The influence of plasticizers on the mechanical properties of nitrocellulose films was discussed.

The behavior of porphyrin polymers derived from polyvinyl alcohol in aqueous solutions was investigated by viscometry. It was found that increasing amount of porphyrin in the immobilizate increases the size of the macromolecular coil of polyvinyl alcohol due to the incorporation of the tetrapyrrole macroheterocycle into the polymer matrix. It was shown that the immobilized porphyrin structure does not affect the nature of the polymer‒solvent interaction.