Исследовано влияние степени метаморфизма (СМ) угля (Сdaf = 80–95.2%) на выход и характеристики активированных углей (АУ), получаемых в условиях щелочной активации (800°С, 1 ч, Ar) при соотношениях КОН/уголь 1 г/г. В этих условиях способность углей образовывать пористый материал снижается в ряду метаморфизма. Максимальную активируемость проявляет уголь марки Д (Сdaf = 80%), образуя материал с SBET = 1560 м2/г, V = 0.71 см3/г, Vmi = 0.51 см3/г. Минимальная активируемость (в условиях эксперимента ) обнаружена у антрацита (Сdaf = 95.2%), образующего АУ с плохо развитой пористостью (SBET = 306 м2/г, V = 0.15 см3/г, Vmi = 0.11 см3/г).

Inverse phase transfer catalysis of phosphorylation of phenol was studied. Para- substituted (4-methyl, 4-methoxy-, 4-morpholino- and 4-dimethylamino-) pyridine-1-oxides were used as IPT catalysts. The reaction proceeds via the formation of an ionic intermediate in the organic phase – 1-(diphenoxyphosphoryl)oxypyridinium chloride. Effect of catalyst structure on activation energy and product yield was investigated on the phosphorylation of 4-nitrophenol. With increasing basicity of the catalyst a lower activation energy and higher product yield were reached. Moreover, decreasing of reaction temperature leads to increasing of product yield due to retarding of hydrolysis of ionic intermediate. The first stage of IPTC process was the reaction between diphenyl chlorophosphate and para-substituted pyridine-1-oxide and it was theoretically studied using quantum chemistry at the DFT level of theory. Influence of solvent was taken into account by adding one molecule of dichloromethane and COSMO model. It was shown that diphenyl chlorophosphate, transitional states and -(diphenoxyphosphoryl)oxypyridinium chloride could exist in several conformational forms. Spatial orientation of phenyl rings significantly influence reactivity of chlorophosphate. Good correlation between experimental activation energy and calculated free activation energy was obtained.

A dimeric (gemini) surfactant containing cleavable ester groups has been synthesized and studied. The new surfactant has a low critical micelle concentration (2.7∙10–5 mol/L) and Krafft temperature (≤0°C). Alkaline hydrolysis of 4-nitrophenyl diethyl phosphonate and 4-nitrophenyl diethyl phosphate in the presence of micelles of gemini surfactant I proceeds 30-144 times more rapidly than in water. Chemical cleavage of gemini surfactant I in an alkaline medium is achieved in 96 h.

The reaction of diphenyl chlorophosphate with the 4-nitrophenolate ion was studied in the presence of a series of para derivatives of pyridine 1-oxide under inverse phase transfer catalysis (IPTC) conditions. The reaction proceeds due to the formation of an ionic intermediate in the organic phase, namely, 1-(diphenoxyphosphoryl) oxypyridinium salts. This conclusion was indicated by both 1 H NMR and IR spectroscopy.

Transfer of acyl groups from N-acyloxypyridinium salts to pyridine N-oxides in acetonitrile was studied. The equilibrium constants of acyl exchange were determined. These quantities vary in the range covering eight orders of magnitude, depending on the structure of the reagents, and are independent of the structure of the acyl group.

The main properties of phenylhydrazines are governed by the p -character of the unshared electron pair of the nitrogen of imino group changing in keeping with sp 3 → sp 2 -regibridization of its atomic orbitals under the steric and electronic (- I effect of amino group) effect of substituents.

28 identical acyl exchange reactions R-CO-Nu+, X− + Nu between pyridine N-oxides in acetonitrile were studied. Here, X− = BPh 4 − and R = methyl, N,N-dimethylamino, N,N-diethylamino, 4-morpholino, 1-piperidino, N-methyl, N-phenylamino, or N,N-diphenylamino group. The IR and NMR spectroscopic characteristics of acyloxypyridinium salts were determined, and the quantum-chemical parameters of all reagents calculated. The results were subjected to correlation analysis. It was found that the rate of identical acyl transfer reactions was controlled by the interaction of frontier orbitals in the transition state.

Kinetic characteristics of 19 transfer reactions of benzoyl group from N-benzoyloxypyridinium salts to pyridine N-oxides and 4-dimethylaminopyridine were studied in acetonitrile by the stopped-flow method. The rate of an identical reaction for 4-methoxypyridine was measured by dynamic NMR spectroscopy. For 5 other identical reactions the rates were estimated from Bronsted correlations. Equilibrium constants were estimated with the use of UV spectrophotometry (6), IR spectroscopy (2), from kinetic data (K ij = k ij /k ji ) (2), and in one case as logK i−j = logK i−x − logK j−x . The second order rate constants (k ij ) varied in the range 102–105 l mol−1 s−1, the equilibrium constants (K ij ) in the range 102–10−2; the activation parameters (ΔH≠) were within 15–50 kJ mol−1, (−ΔS≠) −20–110 J mol−1 K−1. The reactions under study occur in a single stage following the concerted SN2 mechanism through an early associative transition state. The benzoyl groups exchange rate and equilibrium are well described by simplified Marcus equation (omitting the quadratic term).

The rate of formation of N- and O-acetyl and benzoyl salts of pyridines and pyridine N-oxides in acetonitrile and methylene chloride and equilibria therein were studied. The process occurs in one step following the SN2 mechanism with a small degree of bond rupture in the transition state.

We have studied the rate of 15 reactions of acyl transfer from O-acyl salts of 4-dimethylaminostyryl-4′-pyridine N-oxide to 4-morpholinopyridine and 4-dimethylaminopyridine N-oxides in acetonitrile solutions. Analysis of the results based on the Shaik – Pross approach and the Marcus equation shows that if the structure of the acyl group is varied, then the reactivity is determined by such parameters as the resonance interaction in the transition state (B) or the internal barrier (ΔG≠0) of the reaction.

22 Acetyl group exchange reactions between N-acetoxypyridinium salts and 4-dimethylaminopyridine, 4-morpholinopyridine, and N-methylimidazole in acetonitrile at 298 K have been studied. The rate constants varied from 10 5 to 10 −4 L/mol·s, and the equilibrium constants ranged from 10 9 to 10 −9 . The rates and equilibrium constants of these reactions did not comply with the Brönsted equation. The kinetics of the acetyl exchange reactions are well described by a correlation equation containing squared terms.