Vol 87, No 9 (2017)

Phosphorylation of a naphthol hydroxy group of thiophosphorylated thiourea obtained by reaction of diethyl thiophosphoryl isothiocyanate with 1-(α-aminobenzyl)-2-naphthol (Betti base) afforded a number of chiral bisphosphorylated thioureas. Molecular structure of the obtained compounds was studied by single crystal X-ray diffraction. The capacity of the studied compounds for dimerization due to the intermolecular N–H···S hydrogen bonding was revealed.

Reactions of dialkyl [(3,5-di-tert-butyl-4-oxocyclohexa-2,5-dien-1-ylidene)methyl]phosphonates with butyl, benzyl and propargyl alcohols in the presence of catalytic amounts of trifluoromethanesulfonic acid resulted in the formation of nucleophilic 1,6-addition products. Azide-alkyne cycloaddition reaction of dimethyl (3,5-di-tert-butyl-4-hydroxyphenyl)(prop-2-ynyloxy)methylphosphonate with benzyl azide and 1,3-bis-(2-azidoethoxy)benzene in the presence of copper sulfate and sodium ascorbate afforded 1,2,3-triazoles with sterically hindered phenol fragments.

Reaction of benzoxazole-2-thione with 3,5-di-tert-butyl-4-hydroxybenzylacetate in methanol affords S-(3,5-di-tert-butyl-4-hydroxybenzyl)-2-mercaptobenzoxazole as the major product. Antiradical activity of S- and N-3,5-di-tert-butyl-4-hydroxybenzyl derivatives of benzothiazole(oxazole, imidazole)-2-thione with respect to 2,2-diphenyl-1-picrylhydrazyl is varies widely. S-Benzyl derivatives exhibit higher reactivity at 30°C.

A novel approach has been proposed to the synthesis of phosphonium salts containing a 1,4-dihydroxybenzo fragment via reaction of 2-methyl-1,4-benzoquinone or 2-isopropyl-5-methyl-1,4-benzoquinone with PH-phosphonium salts generated in situ from triphenylphosphine and trifluoromethanesulfonic or trifluoroacetic acid. The structure of the synthesized phosphonium salts was determined by NMR spectroscopy and X-ray analysis.

Successive functionalization of p-tert-butylcalix[4]arene afforded a bifunctional derivative containing photopolymerizable pentacosa-10,12-diynoic acid fragments on the upper rim and propargyl groups on the lower rim of the macrocycle having a cone structure. The functionalization can be readily accomplished via copper-catalyzed azide–alkyne cycloaddition under mild conditions.

Novel bis- and tetra-1,3-diketo derivatives of calix[4]arene with nonyl substituents at the lower rim have been synthesized. Their conformational and tautomeric composition have been determined; spectral parameters and complex formation properties with Tb³⁺ have been studied. Substitution of two 1,3-diketo groups with bromine under going from tetra- to bis 1,3-diketone derivatives was resulted in twofold increase luminescence intensity in their terbium complexes. Lifetime of the excited state of the terbium luminescence of the corresponding complexes as well as lifetime of excited triplet level of the 1,3-diketonate ligands have been determined.

Supramolecular systems based on a novel tetracationic amphiphilic multiheterocycle have been studied by tensiometry, conductometry, pH-metry, spectrophotometry, and dynamic and electrophoretic light scattering. The critical micelle concentration of the system has been determined (0.4 mM), and the possibility of open and closed association models realization has been demonstrated. A high solubilizing ability of the aggregates toward hydrophobic guest species has been revealed. Micellar catalysts based on the new multiheterocycle have shown substrate specificity in the hydrolysis of phosphonates possessing different hydrophobicities.

Novel polydentate ligands on the basis of second- and third-generation hyperbranched polyesters containing terminal poly[3-(morpholin-4-yl)propionate] groups and their 6 : 1 and 13 : 1 polynuclear copper(II) complexes were synthesized. The degree of functionalization of the polyesters with morpholine increases in going from the second (56%) to third generation (68%). According to IR and electronic spectroscopy data, each coordination entity in the complexes is an isolated paramagnetic center of the formula CuN₂O₂Solv₂ (Solv = H₂O, DMSO).

A series of novel 9-{2-[(1H-1,2,3-triazol-4-yl)methoxy]phenyl}-3,3,6,6-tetramethyl-3,4,5,6,7,9-hexahydro-1H-xanthene-1,8(2H)-dione derivatives were synthesized by a click chemistry approach. The structures of all the newly synthesized compounds were characterized by IR, MASS, ¹H and ¹³C NMR spectral data. The final analogues showed good to excellent antibacterial and antifungal activities in an agar well diffusion assay. Compounds 6i and 6f were the most active against all the test bacterial and fungal strains.

Acetyl benzofurans 1a, 1b reacted with isatins 2a–2f in the presence of pyridine to give corresponding 3-[2-(1-benzofuran-2-yl)-2-oxoethyl]-3-hydroxy-1,3-dihydro-2H-indol-2-one derivatives 3a–3l. Dehydration of the latter in acidic media led to the corresponding α,β-unsaturated ketones 4a–4l. The structures of newly synthesized compounds 3a–3l and 4a–4l were established on the basis of analytical and spectral data. The synthesized compounds were screened for their antibacterial and antifungal activities. Compounds 5d, 5f, and 5h displayed excellent antimicrobial activity. The synthesized compounds were studied for docking on the enzyme, Glucosamine-6-phosphate Synthase.

3,4-Dimethoxyphenylacetates of Mn(II), Co(II), Ni(II), Cu(II), and Zn(II) of general formula M(C₁₀H₁₁O₄)₂·nH₂O, where n = 1, 2 or 4 depending on M(II) ions, are obtained. The complexes crystallize in monoclinic or triclinic systems. The carboxylate groups act as bidentate chelating or bridging ligands. On heating in the air (293–1173 K) they decompose in three steps finally forming oxides of the corresponding metals(II) or their mixtures. Magnetic moments of compounds were determined in the ranges of 76–303 and 4–300 K.

Quinazolinylbenzoic acid 1 was used as a precursor for synthesis of many heterocyclic systems. Ethyl 4-[4-oxo-2-phenylquinazolin-3(4H)-yl]benzoate 2 upon reaction with hydrazine hydrate gave 4-[4-oxo-2-phenylquinazolin-3(4H)-yl]benzoate benzoylhydrazide 3. Compound 3 on treatment with 3-nitrobenzaldehyde, acetyl acetone, ethyl acetoacetate, and ammonium thiocyanate yielded compounds 4–8, respectively. Isothiocyanate 8 was used for the synthesis of other quinazoline derivatives 9–16 via the reactions with various reagents. All newly synthesized quinazolinone derivatives have been characterized by ¹H NMR, IR, and mass spectroscopy. Most of the synthesized products were evaluated for their antibacterial and antifungal activities and some of those demonstrated high activity.

Some novel (E)-2-cyano-3-(substituted phenyl/dimethylamino)-N′-[1-(pyren-3-yl)]acrylohydrazides and benzochromenone-2-carbohydrazide derivatives were synthesized by reaction of (E)-2-cyano-N′-[1-(pyren-3-yl)ethylidene]acetohydrazide with several reagents. Chemical structures of the newly obtained products were determined by elemental and spectroscopic analysis.

Dialkyl [2-(piperazin-1-yl)ethyl]phosphonates were obtained by the reactions of piperazine with dialkyl vinylphosphonates. The addition of 2-(piperazin-1-yl)ethanamine to diethyl vinylphosphonate involves the primary exocyclic amino group of the heterocyclic compound.

N,N′-Bis(dihexylphosphorylmethyl)-1,4-diaminobutane has been obtained via the Kabachnik–Fields reaction. Crystal structure of its salt with nitric acid (bisphosphoryldiammonium dinitrate) has been studied.

Depending on the structure of the substituent at the nitrogen atom of the heterocycle, reaction of isoindigo derivatives with hydrazine hydrate leads to the formation of either oxindole derivatives, or to a substituted isatin-3-hydrazone.

Novel calix[4]resorcinols modified by sulfamide fragments were synthesized via acid-catalyzed opening of the pyrrolidine ring in 1-sulfonyl-2-naphthylpyrrolidines in the presence of pyrogallol. A possibility of synthesis of calix[4]resorsinols without isolation of the intermediate naphthalene-2-ylpyrrolidines was demonstrated.

The reactions of p-tert-butylthiacalix[4]arenes containing phthalimide fragments with diethyl-[(p-toluenesulfonyl)oxymethyl)]phosphonate were used to synthesize new phosphonate derivatives in the 1,3-alternate configuration. Hydrolysis and hydrazinolysis of the products gave the corresponding amido- and aminophosphonate thiacalixarene derivatives. ¹H–¹H NOESY NMR spectroscopy established a 1,3-alternate configuration of the synthesized macrocycles with spatially separated phosphoryl and amino groups.

Polarity of diselenophosphinates in benzene solution has been determined by second Debye method. We suggest that these compounds exist as a mixture of several conformers with cis and gauche arrangement of substituents at the phosphorus atom with respect to the P=Se bond.

The interaction between bisthiophosphorylated thiourea with nickel(II) nitrate in the presence of potassium tert-butylate has afforded NiL₂ complex with square-planar configuration of the nickel(II) ion and the 1,3-N,S-coordination of the trans-positioned similar heteroatoms.

Factors responsible for the polypropylene consumption growth in the post-crisis period were analyzed, and the world’s largest polypropylene manufacturers and leading polypropylene-producing countries were listed. Preferential growth of polypropylene production in Asia and the Middle East and the specific features of development of the raw material base of polypropylene under the Russian market conditions were demonstrated. The key polypropylene consumption areas in North America, Europe, and the Russian Federation were identified as follows: films, packaging materials, components for automotive industry, plastic pipes, fibers and fibrous materials, sheets, plastic furniture, and construction elements.

Processability of present-day highly filled ballistite-type compositions on regular equipment is a real-time issue in the production of powders and propellants. This poses a number of difficulties, in the wringing phase in particular. In this context, wringing the powder mass containing a hydrophilic filler, lead-nickel complex of phthalic acid (LNP), as burning modifier was considered. The main factors responsible for low water permeability of the powder mass and the major relationships in the filtration process were examined. An approach was proposed for improving the water permeability of the composition mass through the use of polyacrylamide (PAM) type water-soluble flocculants and hydrophobization of LNP with organosilicon compounds from among aryl-substituted orthosilicic esters.

The effect exerted by PAM of different grades with methyltriethoxysilane as hydrophobizer on the water permeability of the composition containing 5–10% LNP was examined. The method based on using PAM was shown to be the most preferable, with Praestol 650 BC cation-active polyacrylamide being the most efficient flocculant. An indisputable advantages of the approach proposed is that is allows improving the water permeability of a powder mass through using a small amount of the flocculant without affecting the main properties of the composition.

Methods were developed for the synthesis of nitro derivatives of 5,15-diphenyl-3,7,13,17-tetramethyl-2,8,12,18-tetraethylporphyrin containing nitro groups at the meso positions of the porphyrin core and at the para positions of the phenyl substituents. The formation kinetics of the zinc, copper, and cobalt complexes of the resultant porphyrins in pyridine and in an acetic acid–benzene (7 : 3) mixed solvent was studied. It was found that the properties of the porphyrin ligands are determined both by the electronic effect of the nitro groups and by the effects of spatial distortion of the porphyrin core.

Publications dedicated to cyclic oligoesters based on cyclic butylene terephthalate were analyzed and summarized. The features of their preparation and structure and their properties were considered with a special focus on advantages and disadvantages of the methods of their preparation: polycondensation at high dilution and depolymerization. The prospects of application of cyclic butylene terephthalate for polymer nanocomposite production were demonstrated. A development strategy for this research area was suggested.

The thermal behavior of compounds with the general formula [MA₆]_x[Fe(CN)₆]_y (M = Со, Cu, Ni, A = NH₃, 1/2 C₃H₁₀N₂) in air, argon, nitrogen, and hydrogen at temperatures between 20 to 1000°C was studied. The study involved measurement of TG–DSC–DTG curves and analysis of solid and gaseous thermolysis products. It was found that the process is not affected by the nature of the atmosphere up to about 200°C. The coordinated cyanide ion partially releases as hydrogen cyanide. The destruction of diamines forms NH₃, and a large amount of carbon remains in the solid phase.

The influence of the composition of the methanol—acetonitrile (MeOH—AN) solvent on the solvation of 18-crown-6 ether (18C6) has been studied. Increasing fraction of AN in the binary solvent stabilizes the 18C6 solvation complex by increasing the exothermicity of 18C6 solvation. Analysis of the solvation contributions of the reagents to the enthalpies of complex formation of silver(I) ion with 18C6 in MeOH—AN mixtures has been performed to establish that the decrease in the exothermicity of complex formation in going from MeOH to AN is mostly associated with the solvation contribution of Ag(I).

Blending of polymers is a method for obtaining new materials with improved properties. Numerous studies have been carried out to characterize the structure, morphology, mechanical, thermal, and rheological behavior of polypropylene blends. The main ways to increasing the compatibility of polymer blends containing polypropylene as one of the components are considered. An important role of polymer compatibilization with the use of a third component is underlined. This article is a review of research on polypropylene blends.