Том 88, № 9 (2018)

The results of systematic studies demonstrated wide possibilities of the three-component Kabachnik–Fields and two-component Pudovik reactions catalyzed by metal phthalocyanines in the synthesis of structurally diverse α-aminophosphonates. Extension of this catalytic method to the synthesis α-aminophosphinates gave rise to a series of α-amino- and α-hydrazinophosphinates based on biogenic amino acids. A number of α-hydrazinophosphonates showed a good antioxidant activity.

A modified method for the preparation of 2,5-diamino-5,5-diphosphonovaleric acid (DADP5) has been developed in the search for new synthetically available organic ligands to produce ¹⁸⁸Re radiopharmaceuticals with an increased accumulation in the bone tissue. Interaction of the obtained acid with ¹⁸⁸Re was studied by radio-TLC. An optimal system for separating unbound ¹⁸⁸Re and labeled complex in a yield of at least 95% was found. The biological distribution of ¹⁸⁸Re-DADP5 was studied based on direct radiometric data. The osteotropicity of ¹⁸⁸Re-DADP5 and its increased accumulation in bone fracture sites, which represent oncological pathology models, was detected at a level comparable to known radiopharmaceuticals.

1-Hydroxy-3-(5,7-dimethyl-2-oxo-1,2-dihydro-1,8-naphthyridin-1-yl)propylidenebisphosphonic acid has been synthesized. The structure of the acid and its precursors synthesized for the first time, 3-(5,7-dimethyl-2-oxo-1,2-dihydro-1,8-naphthyridin-1-yl)propionic acid and the corresponding methyl ester, in the solid state and in the DMSO solution has been elucidated by means of vibrational (IR and Raman) and multinuclear (¹H, ¹³C, and ³¹P) NMR spectroscopy.

A mild and efficient method for the synthesis of new tetrahydroxy-1,1′-binaphthyls containing a halogen atom in the position 3 of the naphthalene moiety was developed. The structure of the tetrahydroxy-1,1′-binaphthyls complexes with the corresponding phosphine oxides was established by NMR spectroscopy.

Reactions of pyridoxal hydrochloride with 5-pyrazolone derivatives in alcohol medium in the presence of concentrated hydrochloric acid led to the formation of new pyrazolones with pyridoxal fragments in the molecule. The corresponding diarylmethanes were formed when using pyridoxal and pyrazolone in a 1: 2 ratio.

A possibility to use pyridoxal as an alkylating agent in the reactions of electrophilic mono-, di-, and trisubstitution in the aromatic core of various phenols and polyphenols was demonstrated for the first time. New types of hydroxyl-containing aromatic aldehydes containing vitamin B6 fragment were obtained, and the conditions for their synthesis were optimized.

A convenient method for preparation of phosphorus-containing podands R₂P(O)CH₂OCH₂X, where X = C(O)NBu₂; P(O)R′₂, R = R′ = Ph, Bu, R = Ph, R′ = Bu via OH-alkylation of phosphorylmethanols under the phase transfer conditions in the presence of Cs₂CO₃ was developed. Carbamoyl-substituted dimethyl ethers were synthesized via transformation of phosphorylmethanols to phosphorylmethoxyacetic acids, followed by amidation. Symmetrical bisphosphoryl substituted dimethyl ethers were obtained by reaction of phosphorylmethanols with tosyl chloride in the presence of Cs₂CO₃. The synthesis of unsymmetrical substituted ether in the presence of Cs₂CO₃ was complicated by transesterification of phosphorylmethyl tosylate resulting in the formation of symmetrical dimethyl ethers as byproducts.

О′,О′-Diethyl-[2-(3,4-dicyanophenoxy)phenyl]phosphonate has been synthesized for the first time and introduced in template condensation on lithium and zinc cations to prepare a series of new neutral and acidic phthalocyanines containing four fragments of 2-oxyphenylphosphonic acid. A scheme of modification of the peripheral substituents at the phosphoryl group was developed allowing a targeted synthesis of phthalocyanine ligands and complexes soluble in organic solvents or aqueous media.

The structure and ion-selective properties of some 2-phosphorylphenols were studied. It was shown that, irrespective of the nature of the substituents on the benzene ring and on the phosphorus atom, these compounds exhibit potentiometric selectivity to cesium cation. The crystal structures of 2-(diphenylphosphoryl)-4-ethylphenol and 2-[(diphenylphosphoryl)methyl]phenol were established.

The interaction of dimethyl phosphite with hexacarbonyls of the chromium group metals in a nonpolar solvent has afforded metal(0) σ⁴,λ⁴-(dimethyl phosphite)pentacarbonyls containing a hydroxy tautomeric form of dimethyl phosphite in the coordination sphere. Hydrogen of the phosphite OH group in the metal(0) σ⁴,λ⁴-(dimethyl phosphite)pentacarbonyls exhibited a significant acidity, strongest for the chromium complexes. Due to the significant acidity of the phosphite hydroxyl, the metal(0) σ⁴,λ⁴-(dimethyl phosphite)-pentacarbonyls are intermediates in the electrophilic version of the Pudovik reaction.

One-pot, four component, green, and efficient synthesis of 3-amino-1-(5-nitro-1H-indol-2-yl)-5,10-dioxo-5,10-dihydro-1H-pyrazolo[1,2-b]phthalazine derivatives by reaction of phthalic anhydride with hydrazine hydrate, 5-nitro-1H-indole-3-carboxaldehyde–indole-3-carboxaldehydes and malononitrile–ethyl cyanoacetate in the presence of [DBUH][OAc] at 60–65°C is developed. The method is characterized by short reaction time, high yields, and purity of products formed.

A series of bis-isoxazoles blended chalcones 7a–7j are synthesized in high yields. The combination of three pharmacologically active moieties in a single scaffold results in the synergistic effect in their bioactivity. All the newly synthesized compounds are characterized by IR, NMR and Mass spectroscopy. The target compounds 7a–7j are assessed for their antimicrobial activity and these demonstrate high to excellent activity against tested bacterial and fungal strains. The products 7f, 7h, 7j, and 7i demonstrate potent antimicrobial activity at concentrations 75 and 100 μg/mL.

Changes in the chemical composition of the vacuum gas oil in a mixture with heavy coker gas oil in the presence of industrial and laboratory NiMoW/P₂O₅–Al₂O₃ catalyst were studied. The support used was γ-Al₂O₃, prepared from AlOOH powder TH-60 (Sasol), with the following textural characteristics: S_BET = 205 m²/g, V_pore = 0.682 cm³/g, R_eff = 48 Å. Alumina was modified with P₂O₅ by incipient wetness impregnation with a solution of phosphoric acid (reagent grade), followed by drying and calcination. The catalysts were prepared by incipient wetness impregnation with a combined solution of Mo, W, and Ni compounds. Before the catalytic test, the catalysts were subjected to sulfidation directly in the hydrotreating reactor of a laboratory setup in a stream of H₂S/H₂ = 70/30 vol %/vol % under 0.11 MPa pressure for 2 h at 500°C. The catalytic properties of the catalysts synthesized were examined under the following conditions: temperature of 360 and 390°C, hydrogen pressure of 5.0 MPa, liquid hourly space velocity of 1.0 h^–1, volume ratio of hydrogen to feed of 1000: 1 nL/L, catalyst loading (0.50–0.25 mm fraction) 27 cm³. The reactor temperature was controlled accurately to within 1°C, pressure, to within 0.1 MPa, feed rate, to within 0.2 mL/h, and hydrogen flow, to within 0.2 L/h. During the process the contents of sulfur and polycyclic aromatic hydrocarbons, as well as the hydrocarbon-type content and carbon content of the feed and the hydrogenates, were determined. After the tests the catalysts were studied by differential thermal analysis in combination with thermogravimetry (DTA-TGA).

The effect of the composition of the catalytic system (the nature and composition of the solvent, specifically, aqueous solutions of sodium hydroxide and their mixtures with aliphatic alcohols with the alcohol concentration of 0.11 mole fractions) and additions of a catalyst poison (sodium sulfide) on the catalytic activity of skeletal nickel in the liquid-phase hydrogenation of the carbon‒carbon double bond in sodium maleate was studied. The assumption was made on the decisive role of the solvent in changing the activity of skeletal nickel in the hydrogenation reaction of sodium maleate, which is primarily associated with the redistribution of individual forms of adsorbed hydrogen. In was found that in the water‒sodium hydroxide‒monohydric alcohol solvent skeletal nickel undergoes selective deactivation at the NaOH concentration of 0.01 M, antiselective deactivation at the NaOH concentration of 0.10 M, and variable deactivation at the NaOH concentration of 1.0 M. It is shown that in some cases sodium sulfide additions exert a promoting effect on skeletal nickel in the hydrogenation of sodium maleate.

Immobilization of tetra-tert-butylphthalocyanine and its copper complex on a chemically activated surface of nonwoven polypropylene and Dacron materials was studied with the aim of creating new materials with antimicrobial properties. A method of the chemical activation of the surface of the studied materials by aminolysis was developed. It was shown that chemical activation leads to a change in the roughness of the polymer surface and formation of nitrogen-containing surface functional groups, which increases the sorption capacity of the studied materials. The modified non-woven materials exhibit a sustained antimicrobial activity.

Synthesis and properties of 2,5-diamino-1,3,4-thiadiazole, 3,5-diamino-1,2,4-thiadiazole, 3,5-diamino-1H-1,2,4-triazole, 3N-alkyl-5-amino-3-imino-1,3,4-thiadiazolines, 2N-alkyl-5-amino-3-imino-1,2,4-thiadiazolines, and 1-alkyl-3,5-diamino-1,2,4-triazoles as building blocks of macroheterocycles compounds are reviewed.

Phthalonitriles with fragments of 4-hydroxy, 4-mercapto and 4-aminobenzoic acids were synthesized by nucleophilic substitution in 4-bromo-5-nitrophthalonitrile. The synthesized phthalonitriles were used to prepare octasubstituted cobalt phthalocyanines by template synthesis. The spectral properties of the products were studied.

The Kabachnik–Fields reaction in a ternary system of 4,4-diethoxybutylamine–dialkyl(tolyl)-phosphine acid–3,5-di-tert-butyl-4-hydroxybenzaldehyde (or paraformoldehyde) afforded new aminophosphine oxides containing 3,5-di-tert-butyl-4-hydroxyphenol moiety and an acetal group.

New nitrogen-containing derivatives of pyridoxal were obtained as a result of its reaction with various amines. The reactions with amines bearing a heterocyclic fragment (pyridine, pyrimidine, quinoline, piperidine) furnished the final products stabilized in an aminoacetal form. The product prepared from 2-aminomethylpiperidine has an imidazolidine fragment in the molecule.

A series of precursors of novel tripodal ligands (2-XCH₂CH₂CH₂OC₆H₄)₃PO, where X = AcO, HO, MeSO₂O, Br, N₃, were synthesized by the alkylation of the starting tris(2-hydroxyphenyl)phosphine oxide with 3-bromopropyl acetate followed by hydrolysis of the resulting triacetate to triol and conversion of the latter to trimesylate. Treratment of the resulting trimesylate with LiBr or NaN₃ was used to prepare the corresponding tribromo or triazido derivatives.

The reaction of 3-arylidene-1-pyrrolines with phenols yielded 2-arylpyrrolidines. The proposed method makes it possible to obtain pyrrolidines containing a phenol fragment in the position 2 in high yields and under mild conditions.

The reaction of 2-hydroxy-5,7,8-trimethyl-2-oxobenzo[e]-1,2-oxaphosphorine with thionyl chloride yielded the pyrophosphonate product, which was isolated and characterized for the first time. Subsequent treatment of it with phosphorus pentachloride led to the formation of new types of unsymmetrical cage phosphonates.

The action of sulfur diethylaminotrifluoride on 19β,28-epoxyoleanan-3-ol (allobetulin) causes dehydration of the terpenoid and isomerization of the ring A via its contraction to isopropylcyclopentene ring resulting in 19β,28-epoxy-A-neo-18α-olean-3(5)-ene (α-allobetulin) in a high yield.