Vol 67, No 5 (2018)

The data on the composition of ester products formed in the Baeyer–Villiger reaction in the liquid-phase oxidation of organic compounds with molecular oxygen, on production channel of peroxy acids, as well as on the influence of a carbonyl compound structure on its reactivity in reactions with peroxy acids have been classified and considered. The Baeyer–Villiger reaction was shown to be the main source of accessory primary alcohol esters and lactones in industrial processes of aerobic oxidation of cyclohexane and paraffin hydrocarbons.

A set of physicochemical methods was used to establish that aqueous solutions of chloracetophos fungicide and bactericide (1) in the range of calculated concentrations from 1•10^–18 to 1•10^–4 mol L^–1 are disperse systems in which a dispersed phase hundreds of nanometers in size is formed above and below a threshold concentration of 1•10^–9 mol L^–1. Upon dilution disperse systems 1 are capable of non-monotonic changing the physicochemical properties and changing the toxicity profile (inhibition–stimulation) when influencing the growth and development of unicellular algae Chlorella vulgaris. The formation of domains and nanoassociates is accompanied by the appearance in the UV spectrum of an absorption band at 210–300 nm with a maximum at ~220 nm (A₂₂₀). The interrelated concentration dependences of A₂₂₀, the size of the dispersed phase, and electrical conductivity indicates that the observed spectral features of systems 1 are caused by the properties of the domains and nanoassociates.

A method for the synthesis of a series of symmetric and asymmetric conformationally fixed tricarbocyanines was developed based on benzоindolenine containing ethyl phosphonate and diethyl phosphonate groups in the linker at the quaternary nitrogen atom of the indolenine fragment. The polymethine chain meso position was modified by nucleophilic substitution of chlorine with O- and N-nucleophiles. Their absorption and fluorescence spectra were recorded, the possibility of further use of phosphonate-substituted tricarbocyanines as biomarkers was demonstrated. The dark cytotoxicity of synthesized compounds was studied, the possibility of their accumulation in HCT116, MCF7 cancer cells was shown.

Analysis of reactions of 1,3,5-trinitrobenzene (TNB) with alcoholates of primary aliphatic alcohols (substitution of the nitro group or generation of σ^H-complexes at the unsubstituted position of TNB) leads to the conclusion that high basicity of alcoholates (MeONa, EtONa) of unsubstituted primary alcohols promotes formation of σ^H-complexes, thus preventing nucleophilic substitution of a nitro group. Introduction of electron-withdrawing substitutes (R = HC≡C, H₂C = CH, pyridyl) into the alcohol molecule (RCH₂OH) reduces the basicity of their alcoholates which makes substitution of nitro groups possible aff ording the corresponding 1-alkoxy-3,5-dinitrobenzenes in the presence of K₂CO₃ in N-methylpyrrolidone at 80 °C.

New ivermectin-4″,5-diyl[bis(N-methylcarbamate)] was synthesized by the MoO₂Cl₂(DMF)₂-catalyzed reaction of ivermectin with methyl isocyanate. The synthesized compound could find application as antiparasitic agent.

Preparative procedures for the synthesis of N¹,N¹,N³,N³-tetrasubstituted diethylenetriamines via aminoalkylation of N,N-disubstituted ethylenediamines with N,N-disubstituted 2-chloroethylamines were developed. Aminoalkylation of N,N-dimethylethylenediamine under heating gave simultaneously secondary N¹,N¹,N³,N³-tetrasubstituted diethylenetriamines and quaternary ammonium salts, N-(2-aminoethyl)-N-(2-dialkylaminoethyl)-N,N-dimethylammonium chlorides. Structures of the synthesized compounds were established by IR spectroscopy, ¹H and ¹³C NMR spectroscopy, and electrospray ionization mass spectrometry.

The dynamics of changes in the composition of the reaction mixture during the reaction of Na₂SeSO₃ and bromopropyl-substituted phenol in 50% aqueous ethanol and under the conditions of decreasing EtOH concentration in the reaction medium was studied. Convenient methods for the synthesis of 3-(4-hydroxyaryl)propyl selenosulfates and the corresponding diselenides were proposed. Symmetrical and unsymmetrical selenides (derivatives of alkylated phenols and pyrocatechol) were synthesized.

A series of 5-alkyl-3-pyridylisoxazoles was synthesized using the 3-(3-pyridyl)isoxazole scaff old. All compounds of the series possessed antiaggregatory activity in the concentration range of 6•10^–6–6•10^–4 mol L^–1. Analysis of the experimental data on the antiaggregatory activity revealed the presence of spatial constraints for the alkyl substituents in position 5 of the isoxazole ring. 5-Alkyl-3-(3-pyridyl)isoxazoles are rather selective for platelet membrane receptors.

The condensation reactions of β- and γ-amino alcohols containing phenyl or (η⁶-arene) tricarbonylchromium substituent with formaldehyde, acetaldehyde, benzaldehyde, and (η⁶-benzaldehyde)tricarbonylchromium were studied. The resulting 1,3-oxazolidine and 1,3-oxazinane products were isolated in a pure form and identified by different physicochemical methods. The effect of (η⁶-arene)tricarbonylchromium moiety on the reaction process was demonstrated.

5-Aminopyrido[3′,2′:4,5]thieno[3,2-c]isoquinolines were synthesized via alkylation of 3-cyanopyridine-2(1H)-thiones with 2-(chloromethyl)benzonitrile followed by treatment of the products with potassium tert-butoxide. The oxidation of the alkylated products to corresponding sulfoxides or sulfones followed by treatment with potassium tert-butoxide provided the corresponding 11-oxides or 11,11-dioxides.

P*-Chiral diamidophosphite ligand of a 1,3,2-diazaphopholidine series bearing the exocyclic pseudodipeptide fragment was synthesized. The possibility of its application in the palladium- and rhodium-catalyzed asymmetric transformations was demonstrated. This ligand provided up to 84% ee in the Pd-catalyzed alkylation of (E)-1,3-diphenylallyl acetate with dimethyl malonate, up to 56% ee in amination of this substrate with pyrrolidine, and up to 68% ee in alkylation of cinnamyl acetate with ethyl 2-oxocyclohexane-1-carboxylate. In the Rh-catalyzed hydrogenation of (Z)-methyl 2-acetamido-3-phenylacrylate mediated by this ligand, up to 53% ee was achieved.

Hydrogenation of butyl sorbate into butyl Z-hex-3-enoate in supercritical carbon dioxide proceeds at high conversion and selectivity of 93–96% under catalysis with chromium hexacarbonyl at 180 °C and on using (methyl benzoate)chromium tricarbonyl as a catalyst at 160 °C.