It was shown for the first time that diaryl(hetaryl)ketones are capable of directly phosphorylating with red phosphorus in the superbase suspension KOH/DMSO(H2O) at 85 °C for 1.5 h to afford potassium bis(diaryl(hetaryl)methyl)phosphates that were earlier inaccessible in a yield of up to 45%. The ESR data demonstrate that unlike previously published phosphorylation with elemental phosphorus, this new phosphorylation reaction proceeds via a single electron transfer from polyphospide anions to diaryl(hetaryl)ketones. This is the first example of the C-O-P bond generation during the phosphorylation with elemental phosphorus in strongly basic media, which usually provides C-P bond formation.

With the expansion of the scope of lubricant oils and fuels, the requirements for their performance properties are increasing. One of the performance characteristics of these petroleum products is their oxidation resistance. It is known that as a result of oxidation, their performance properties deteriorate. Antioxidant stabilizers are used to increase the resistance of organic materials against oxidation. The study of the mechanism of action of oxidation inhibitors is one of the most important tasks in this field, the solution of which is the creation of a theoretically substantiated approach to the targeted synthesis of more effective antioxidants. To create the theoretical and practical foundations of solving this problem was to find novel classes of effective additives of multivalent activity, particularly antioxidants, a series of recently synthesized nitrogen, sulfur, selenium and phosphorus polyfunctional compounds, including pyrroledithioates, 6,8-bicycloctanes, aminopyrimidine, tris(2-pyridyl)phosphinesulfide and -selenide have been investigated using model oxidative reactions. The compounds studied appear to be perspective inhibitors of hydrocarbon oxidation. Some of them are antioxidants of combined action, breaking the chains of the oxidative reactions with cumene peroxide radicals and catalytically decomposing cumene hydroperoxide.

Recent publications on direct reactions of elemental phosphorus with organic halides (alkyl bromides, aryl (and hetaryl) halides, and aryl (and hetaryl) methyl halides) in the presence of superbasic and micellar catalysts are considered. The development of effective, technologically and environmentally acceptable methods for obtaining alkyl(and benzyl)- H -phosphinic and alkylphosphonic acids, triaryl(and hetaryl)phosphines and hetarylmethylphosphine oxides based on the above reactions is analyzed.

3-Bromo- and 6-chloroquinolines or 2-bromo-1-methylbenzimidazole react with red phosphorus in the KOH/DMSO (Н2О) system on heating (100–120°C, 3 h) to form in high yield the products of selective reduction (with retention of the aromatic heterocycle): quinoline or 1-methylbenzimidazole, respectively.

Triton-X-100, a polyethylene glycol 4-(tert-octyl)phenyl ether, has been found to be an active micellar organic catalyst for the one-pot selective synthesis of arylmethyl-H-phosphinic acids in up to 65% yields by the direct phosphinylation of arylmethyl halides with red phosphorus in the KOH/H2O/toluene multiphase superbase system. The catalyst demonstrates a good recyclability. As a result, an expeditious method for the chemoselective synthesis of arylmethyl-H-phosphinic acids-versatile sought-after organophosphorus compounds-has been developed. The synthesis is implemented via direct alkylation/oxidation of red phosphorus with arylmethyl halides, promoted by superbase hydroxide anions using Triton-X-100 (a commercial off-the-shelf organic recyclable micellar catalyst). The reaction comprises the hydroxide anions-assisted disassembly of P-red 3D polymer molecules triggered by the separation from the potassium cation in ordinary crown-like micelles to produce polyphosphide anions in aqueous phase. Further, polyphosphide anions are alkylated with arylmethyl halides in organic phase in the presence of the catalytic Triton-X-100 reverse micelles and alkylated polyphosphide species undergo the double hydroxylation. The advantages of the strategy developed include chemoselectivity, benign and accessible starting reagents, catalyst recyclability, and facile one-pot implementation.

Tertiary phosphine oxides, phosphine sulfides, and phosphine selenides containing pyridine, imidazole, and pyrazole groups have been synthesized via the reaction of elemental phosphorus or secondary phosphine oxides with functional pyridines, imidazoles, and pyrazoles. Alkyl tris(2-pyridylethyl)phosphonium iodide and bromide are also obtained by quaternization of the corresponding phosphine. Antimicrobial activity of the synthesized compounds, including nitrogen-containing heterocycles, phosphorus, selenium, and sulfur, with respect to Enterococcus durans, Bacillus subtilis, Escherichia coli, Pseudomonas aeruginosa microorganisms is evaluated. It is found that phosphine chalcogenides bearing imidazole (14, 19), pyrazole (13), and pyridine fragments (5, 9) and phosphonium salts (11, 12) can be considered as new promising antibacterial agents. For some synthesized compounds, LC50 is determined. Phosphine oxide with methylpyrazole fragments (13) and phosphonium salts (11, 12) show strong profile of antimicrobial activity, and cytotoxic effect of phosphonium bromide having a long chain radical (12) is by order of magnitude higher than that of cisplatin. We believe that the results obtained may contribute to the development of highly effective agents for the treatment and prevention of bacterial infections and cancers.

Tris(hetaryl)substituted phosphines and their chalcogenides are promising polydentate ligands for the design of metal complexes. An experimental and theoretical conformational analysis of tris[2-(4-pyridyl)ethyl]phosphine, tris[2-(2-pyridyl)ethyl]phosphine, and their chalcogenides was carried out by the methods of dipole moments, IR spectroscopy and DFT B3PW91/6-311++G(df,p) calculations. In solution, these compounds exist as an equilibrium of mainly non-eclipsed (synclinal or antiperiplanar) forms with a predominance of a symmetrical conformer having a gauche-orientation of the Csp3–Csp3 bonds of pyridylethyl substituents relative to the P=X bond (X = lone pair, O, S, Se) and a gauche-orientation of the pyridyl rings relative to the zigzag ethylene bridges. Regardless of the presence and nature of the chalcogen atom (oxygen, sulfur, or selenium) in the studied molecules with many axes of internal rotation, steric factors—the different position of the nitrogen atoms in the pyridyl rings and the configuration of ethylene bridges—determine the realization and spatial structure of preferred conformers.

Tertiary phosphine oxides have been synthesized by the reaction of secondary phosphine oxides with diverse hetarylmethylchlorides (pyridines, imidazoles, pyrazole) in the superbasic systems CsF/NaOH/DMF/4 angstrom MS or NaOH/DMSO/4 angstrom MS at 23-25 degrees C. It is found that a tertiary phosphine oxide bearing the imidazole fragment possess the pronounced antimicrobial activity.

Polyfluoroalkyl dichlorophosphites reacted with propargyl alcohol in Et3N/hexane to give di(2-propynyl) polyfluoroalkyl phosphites, which are transformed into polyfluoroalkyl 2-propynyl allenylphosphonates and isomeric (1-propynyl)phosphonates upon storage.

Alkylphosphinic acids, including long-chain ones, were synthesized in up to 76% yields from red phosphorus and n-AlkBr (Alk = C4–C14) under micellar catalysis conditions. The reaction proceeds efficiently and chemoselectively upon heating (85–90°C, 6 h) in a KOH/H2O/toluene/cetyltrimethylammonium bromide system.

In this study, a series of nitrogen-based novel heterocyclic compounds were synthesized and characterized by elemental analysis, IR and NMR spectra. The novel synthesized nitrogen-based novel heterocyclic compounds were evaluated against the acetylcholinesterase (AChE) and alpha-glycosidase enzymes. These compounds showed IC50 values in range of 0.76-28.04 mu M against AChE as a cholinergic enzyme, and 26.10-82.17 mu M against alpha-glycosidase as a hydrolytic enzyme. On the other hand, they demonstrated K(i )values between 1.25 +/- 0.22-25.36 +/- 4.72 mu M against AChE, and 25.07 +/- 4.57-78.55 +/- 17.04 mu M against alpha-glycosidase enzymes. The synthesized nitrogen-based novel heterocyclic compounds exhibited effective inhibition profiles against both indicated metabolic enzymes. These results may contribute to the development of new drugs particularly to treat some disorders, which widespread display in the world including Alzheimer's disease and diabetes. Furthermore, molecular docking calculations were made to compare the theoretical biological activities of nitrogen-based novel heterocyclic compounds against proteins including enzymes. After these calculations, ADME/T analysis was performed to examine the drug properties of nitrogen-based novel heterocyclic compounds.

Alkyl-H-phosphinic acid alkyl esters are synthesized in 65–71% yield via chemoselective reaction of alkyl bromides with available alkyl-H-phosphinic acids (60–65 °C, Et3N). The latter are prepared, in turn, by direct phosphorylation of alkyl bromides with red phosphorus under phase-transfer conditions.

Long-chain n-Alkylphosphonic acids, AlkP(O)(OH)(2), are synthesized in up to 91 % yield (mostly 40-60 %) by straightforward phosphonylation of alkyl bromides (AlkBr, Alk=C-4-C-18) with red phosphorus (P-n) in the multiphase KOH/H2O/toluene system in the presence of 2-10 mol % of cetyltrimethylammonium bromide (CTAB), acting as a micellar/phase transfer catalyst and as a generator/transporter of superbasic hydroxide anions, the intermediate potassium phosphinates being in situ oxidized/neutralized by nitric acid. The key steps of the phosphonylation mechanism are the P-P bond cleavage of P-n polymeric molecules by superbasic -OH anions, dissolved in the CTAB micelles, and phase transfer of polyphosphide anions to the organic phase and their alkylation with AlkBr.

The polarity and structure of tri(1- or 2-naphthyl)phosphines and their chalcogenides were determined by the methods of dipole moments, IR spectroscopy, and DFT quantum-chemical calculations at the B3PW91/6-311++G(df,p) level of theory. In solution, tri(1-naphthyl)phosphine prefers a single conformer with a gauche,gauche,gauche orientation of the substituents at the phosphorus. Tri(2-naphthyl)phosphine, as well as both phosphine chalcogenides exist as equilibrium mixtures of several forms with a propeller arrangement of the substituents and a cis or gauche orientation of the Csp2‒Csp2 and P=X (X = LEP, O, S, Se) bonds.

The reaction of [Mo3S4(Tu)8(H2O)]Cl4·4H2O (Tu is thiourea) with (PhCH2CH2)2-PCH2CH2SeC5H11) (PSe) followed by purification on a chromatographic column packed with silica gel using a saturated solution of KPF6 in acetone as an eluent results in the formation of [Mo3S4Cl3(PSe)3]PF6 (I) in a yield of 44%. Compound I is characterized by X-ray diffraction analysis, 1H, 31P{1H}, and 77Se NMR spectroscopy, IR spectroscopy, UV-Vis spectroscopy, cyclic voltammetry, and electrospray ionization mass spectrometry. Several species differed in the coordination mode of three PSe ligands, which can bind to molybdenum via one (phosphorus) or two (phosphorus and selenium) donor atoms, are formed in a solution of compound I at room temperature. This behavior is not observed for the compounds similar in structure with PS ligands of an analogous type. Complex I demonstrates a higher catalytic activity than its analogue with the PS ligand in the reduction of nitrobenzene to aniline under the action of diphenylsilane.

Long-chain n-alkyl-H-phosphinic acids (Alk = C4-C18) are chemoselectively synthesized in yields up to 90% via the direct one-pot alkylation/oxidation of red phosphorus (Pn) in the multi-phase alkyl bromide/KOH/H2O/toluene system with alkyl-PEG recyclable micellar catalysts, which demonstrate good recyclability.

In order to protect polymer materials in particular polyurethanes and similar materials from biodeterioration by microscopic fungi, seven fungicidal compounds of the guanidine series were synthesized and their effectiveness was investigated in various concentrations. Among the tested compounds, the most effective is the first fraction of polyhexamethylene guanidine n-octylphosphonate (code B1), which completely suppresses the growth of all studied micromycetes at a minimum concentration of 0.01 % by weight. At a lower concentration of 0.001 % by weight, compound the first fraction of polyhexamethylene guanidine n-octylphosphonate inhibits the growth of most of the studied micromycetes, with the exception of the Aspergillus niger culture.