Cationic polymerization of isoprene using the initiating systems consisting of organoaluminum compounds (OAC = AlEt3, AlEt2Cl, or AlEtCl2) and allyl chloride (ALC) is a new efficient method for the synthesis of completely soluble solid thermoplastic isoprene polymers characterized by reduced degree of unsaturation (44–50 mol.

A series of fatty aromatic adamantane-containing diamines based on acetylated aniline derivatives have been obtained using trifluoroacetic acid, which allows the target products to be obtained selectively with yields of up to 93 % and purities of up to 97,5 % without pretreatment. The pKa values and the charges on the nitrogen atom of the resulting diamines are determined. The synthesized compounds are potential monomers for transparent polyimide materials.

The features of thermal destruction of copolyimides based on pyromellite dianhydride, 4,4'-diaminodiphenyl ether and [2-(aminomethyl)bicyclo[2.2.1]hept-3-yl]anilines were studied. The effective activation energies of the thermal destruction process were determined. It has been shown that in the case of bicyclic polyimides, hydrolytic reactions have a lesser effect on the process of thermal destruction compared to fully aromatic polyimides.

The cationic polymerization of butadiene under the action of catalytic systems based on diethylaluminum chloride (AlEt2Cl) in combination with tertiary alkyl halides (AHs) such as tert-butyl chloride, tert-butyl bromide, and 2-chloro-2-methylbutane is found to be an efficient method for the preparation of fully soluble butadiene polymers at a technologically convenient process temperature of 20°C. It is shown that with an increase in the duration of butadiene polymerization process, the weight-average molecular weights and polydispersity of the polymer increase significantly with a simultaneous decrease in the unsaturation of polybutadiene, which is associated with the transfer reaction of the growing chain to the double bond of the polymer during polymerization. A 13C NMR spectral study showed that the macromolecules of polybutadiene synthesized on the AlEt2Cl–tert-butyl chloride catalytic system consist mainly of 1,4-trans units and contain two types of initial tert-butyl units and two types of end chlorine-containing units formed as a result of the transfer reaction of the growing chain to tert-butyl chloride. Based on the data of 13C NMR spectra of polybutadiene, a method for calculating butadiene conversion during polymerization is developed, and a mechanism of the process of cationic polymerization of butadiene is proposed. It is shown that the synthesized “cationic” polybutadiene is characterized by high film-forming properties and can be a promising component in the production of paints and varnishes.

An efficient approach to the synthesis of (+)-camphor and (–)-fenchone anils has been developed, which involves the reaction of the corresponding bicyclic monoterpenoid ketones with substituted anilines in the presence of in situ prepared ( i -PrO) 2 Ti(OTf) 2 ·( i -PrOH) 2 complex, as a homogeneous catalyst, and ( i- PrO) 4 Ti, as a dehydrating agent. The advantage of the suggested method lies not only in obtaining target products in good yield and high purity, but also in a simplified procedure for their isolation. These products are of interest as potential pharmacologically active compounds, antioxidants for rubber mixtures, and components of 3D-printing formulations.

An efficient approach to the synthesis of (+)-camphor and (–)‑fenchone anils has been developed, which consists in the interaction of the corresponding bicyclic monoterpenoid ketones with substituted anilines in the presence of the (i-PrO)2Ti(OTf)2·(i-PrOH)2 complex obtained in situ, as a homophasic catalyst, and (i‑PrO)4Ti, as a dehydrating agent. The advantage of the proposed method lies not only in obtaining target products with good yields and high purity, but also in a simplified procedure for isolating target substances, which, in turn, are of interest as pharmacologically active compounds, antioxidants for rubber compounds and components of compositions for 3D-print.

Pharmacological studies of the new fatty-aromatic amides, structural analogs of chlorobenzoylaminoadamantane (chlodantane), and non-covalent water-soluble complexes of chlodantane, adamantylbromophenylamine (bromantane) and ADC-918 were carried out. It was shown that complexation neutralized the actoprotective properties of the last three substances. The resulting complexes of arabinogalactan were inclusion compounds where the adaptogen molecule played the role of a guest; the arabinogalactan molecule, a host. Salt-like coordination complexes formed with glycyrrhizic acid. The new derivatives belonged to the third class of moderately toxic compounds. N-[(1R, 2RS)-Camphan-2-yl]-4-chlorobenzamide turned out to be the most promising compound in terms of the pharmacological profile and increased physical performance in the treadmill test by 23.22 – 25.20

The regularities of obtaining polyimides by high-temperature polycyclization in various solvents have been studied. It is shown that the use of sulfolane as a solvent makes it possible to obtain polymers with a higher reduced viscosity and, accordingly, a better potential set of characteristics. Polyimides based on vicinally substituted bicyclic diamines have a higher molecular weight compared to polyimides based on 9.9-bis-(4-aminophenyl) fluorene.

Various methods for the reduction of (het)arylimines of cage-structured monoterpenoid ketones, l-fenchone and d-camphor, were explored. The best results were achieved using the NaBH4-NiCl2 • 6H2O system in 95% ethanol. The exception is halogenated aniline derivatives, in the case of which the reduction of the C-N bond is accompanied with the hydrogenolysis of the C-Hal bond.

For the first time, a study of the reaction of pyromellitic dianhydride with [3-(aminomethyl)bicyclo[2.2.1]hept-2-yl]anilines by the calorimetric method was carried out. The enthalpies, rate constants and activation energies of the reaction were determined. It was found that the reactivity in the reactions of the formation of polyamide acids, [3-(aminomethyl)bicyclo[2.2.1]hept-2-yl]anilines are significantly superior to aromatic diamines. It was shown that in the case of 3-[3-(aminomethyl)bicyclo[2.2.1]hept-2-yl]aniline pK(a) values do not fully take into account steric factors and, therefore, are not a sufficiently sensitive measure of the reactivity of [3-(aminomethyl)bicyclo[2.2.1]hept-2-yl]anilines in the reactions of polyamide acids formation.

В рамках выполнения работ по направленному конструированию новых структурных аналогов синтетического адаптогена -Бромантана, с прицелом на снижение гепатотоксических свойств прототипа, был предложен новый подход [1, 2] к получению ключевых интермедиатов синтеза -аниловтерпеноидных кетонов.В основе данного подхода лежит реакция конденсации соответствующего кетона -камфоры или фенхона, с соответствующим ариламином в присутствии (i-PrO) 4 Ti и комплексного катализатора

The thermal and thermomechanical properties of copolyimides based on pyromellitic dianhydride, 4,4'-diaminodiphenyloxide and [2-(aminomethyl)bicyclo [2.2.1]hept-3-yl]anilines in an inert medium have been studied for the first time. It is shown that the introduction into the structure of aromatic polyimides up to 20 mol %. asymmetric vicinally substituted bicyclic diamines allows to obtain materials with increased hydrolytic stability in comparison with fully aromatic polyimides while maintaining a high level of thermomechanical characteristics.

For the first time, the influence of the structure of vicinally substituted bicyclo [2.2.1] heptanes on the yield of hydrogenation products under the Schwenk-Papa reaction conditions was studied. It has been shown that the Schwenk-Papa reaction allows one-step reduction of multiple bonds of the bicyclic fragment, double bonds of side alkyl substituents, as well as nitro- cyano- and oxime groups with their joint presence. At the same time, carboxyl and amide groups are not reduced under these conditions.

The reduction of cage ketoximes under Schwenk–Papa reaction conditions was studied to establish that the d,l, d- and l-camphor oximes are smoothly reduced to the corresponding amines in high yields. At the same time, d,l-norcamphor and adamantan-2-one oximes undergo partial catalytic deoximation to form a mixture of the corresponding amines and alcohols.

A significant effect of the steric factor on the activity of 3,5-dimethyl-1H-pyrazolide as an acylating agent has been found using the example of acylation of camphane-type monoamines. The predominant contribution of the catalytic hydrogenation as a component of the Schwenk-Papa reaction has been confirmed by the synthesis of 4-chlorobenzoyl derivatives.