The reactions of lupinine alkaloid and its chlorine derivative with cinnamoyl chloride and 2-K-isoindole-1,3-dione were investigated to obtain 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester and 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione, respectively. The optimal conditions for carrying out the aforementioned reactions were determined, taking into account the nature of the solvent and medium. It was established that acylation of the molecule in a benzene medium, in the presence of trimethylamine, resulted in the formation of 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester, with an 82% yield. It was demonstrated that the interaction of chlorolupinine with 2-K-isoindole-1,3-dione under Gabriel reaction conditions resulted in the formation of 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione. The conformer with an axial orientation of the isoindole-1,3-dione substituent was observed to exhibit greater stability than the conformer with an equatorial orientation. The structure of the synthesized compounds was investigated by IR, 1H, and 13C NMR spectroscopy. The use of two-dimensional spectra in COSY (1H-1H) and HMQC (1H-13C) formats enabled the establishment of homo- and heteronuclear interactions, thereby confirming the structure of the compounds under investigation. The values of chemical shifts, multiplet and integrated intensity of 1H and 13C signals in one-dimensional NMR spectra of the novel compounds were determined. The crystal structures of 3-phenylacrylic acid octahydroquinolizin-1-ylmethyl ester and 2-(octahydroquinolizin-1-ylmethyl)isoindole-1,3-dione were elucidated through X-ray analysis.

В результате изучения химического состава эндемичного вида Казахстана танацетопсиса Пятаевой (Tanacetopsis Pjataevae (Kovalevsk.) Karmyscheva) впервые выделены сесквитерпеновые γ-лактоны гваянового ряда арглабин, β-изоэпоксиэстафиатин, новый гваянолид 3-кето-10β-гидрокси-5,7α,4,6β(Н)-гвай-1,11(13)-диен-6,12-олид. Пространственное строение соединений установлено рентгенодифракционным методом.

As a result of studying the chemical composition of the Kazakhstan endemic species Tanacetopsis Pjataevae ( Tanacetopsis Pjataevae (Kovalevsk.) Karmyscheva), the following guaianolide-type γ-lactones are isolated: arglabin, β-isoepoxyestafiatin, and a new 3-keto-10β-hydroxy-5,7α,4,6β(H)-gvai-1,11(13)-diene-6,12-olide guaianolide. The structure of these compounds is established by X-ray diffraction.

An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The article presents results on the synthesis and investigation of the structural features of a number of 1,4-disubstituted 1H-1,2,3-triazole derivatives of the alkaloid lupinine. Lupinine modification reactions have been carried out at the hydroxymethylene group in the C-1 position of the quinolysine backbone. It has been shown that (octahydro-2H-quinolysine-1-ylmethyl)methanesulfonate in high yield (93%) is formed by the in-teraction of lupinine with methanesulfonyl chloride in methylene chloride. Subsequent treatment of this com-pound with sodium azide in dimethylformamide on heating leads to the formation of 1-(azidomethyl)octahydro-2H-quinolysine in 61% yield. It has been found that the reaction of a new azide with terminal alkynes of various nature in the presence of aqueous СuSO4 and sodium ascorbate in dimethylfor-mamide can form the corresponding 4-substituted (1S,9aR)-1-[(1,2,3-triazol-1-yl)methyl]octahydro-1H-quinolysines. New 1,2,3-triazole derivatives of lupinine containing various aryl substituents at the C-4 posi-tion of the triazole ring have been obtained. The high selectivity of the reaction is explained by the action mechanism of the Sharpless catalyst. The spatial structure of the molecules of lupinine methanesulfonate, 4-aryltriazolylmethyl-octahydroquinolysines has been established by X-ray diffraction analysis. X-ray structur-al analysis data of new compounds have been deposited in the form of CIF files at the Cambridge Crystallo-graphic Data Center

The article presents the results of a chemical study of Tanacetopsis pjataevae, which is an endemic plant in Kazakhstan. The number of extractive substances was obtained by extraction with chloroform from the air-dry crushed above-ground part of the plant collected in the flowering phase. Isolation of compounds was carried out by column chromatography on a column of silica gel brand KSK at a ratio of sum - carrier = 1:20. A colorless crystalline substance of the composition C15H18O4 with m.p. 189-191 degrees C (recrystallized from diethyl ether) was found when the column was eluted with a mixture of petroleum ether-ethyl acetate (87.5:12.5). The structure of the obtained new compound (3-oxo-10 beta-hydroxy-5,7 alpha(H),6 beta(H)-guai-1,11(13)-diene-6,12-olide) was established based on IR, NMR analysis and mass spectra. The spatial structure was determined by the X-ray diffraction method. It was established that the 3-oxo-10 beta-hydroxy-5,7 alpha(H),6 beta(H)-guai-1,11(13)-diene-6,12-olide molecule in the crystal is disordered over two conformational states in the 6 :4 ratio. The stability of these conformers was confirmed by semi-empirical quantum-chemical calculations. It was established that the difference in the heat of formation of two conformers was 6.3 kJ/mol for a free molecule.

A three-component reaction of 3,5-diacetyl-2,6-dimethylpyridine, p-N-dimethylaminobenzaldehyde and phenylhydrazine in the presence of KOH in ethanol gave the condensation product of two p-N-dimethylaminobenzaldehyde and phenylhydrazine molecules, namely bis(biarylhydrazone). Structure of the obtained derivative was proved by the 1H and 13C NMR spectroscopy and X-ray diffraction analysis data. It was shown that the bis(biarylhydrazone) derivative has high antiradical and cytoprotective activity.

The article presents the results of a chemical study of Tanacetopsis pjataevae, which is an endemic plant in Kazakhstan. The number of extractive substances was obtained by extraction with chloroform from the air-dry crushed above-ground part of the plant collected in the flowering phase. Isolation of compounds was carried out by column chromatography on a column of silica gel brand KSK at a ratio of sum - carrier = 1:20. A colorless crystalline substance of the composition C15H18O4 with m.p. 189–191°C (recrystallized from diethyl ether) was found when the column was eluted with a mixture of petroleum ether-ethyl acetate (87.5:12.5). The structure of the obtained new compound (3-oxo-10β-hydroxy-5,7α(Н),6β(Н)-guai-1,11(13)-diene-6,12-olide) was established based on IR, NMR analysis and mass spectra. The spatial structure was determined by the X-ray diffraction method. It was established that the 3-oxo-10β-hydroxy-5,7α(Н),6β(Н)-guai-1,11(13)-diene-6,12-olide molecule in the crystal is disordered over two conformational states in the 6 :4 ratio. The stability of these conformers was confirmed by semi-empirical quantum-chemical calculations. It was established that the difference in the heat of formation of two conformers was 6.3 kJ/mol for a free molecule.

Based on (–)-cytisine alkaloid and ethyl isothiocyanate, N-ethyl-N-cytisinocarbothioamide is synthesized and its structure is proved by 1H NMR spectroscopy and single crystal X-ray diffraction. The mesomeric effect is shown in the carbothioamide group formed. It is found that π-conjugation between nitrogen atoms and the thiocarbonyl group is weakened due to the steric hindrance between hydrogen atoms of the piperidine ring and the thioamide group.

As a result of studying the interaction of chlorolupinine with potassium phthalimide, the optimal synthesis conditions for N-lupinylphthalimide by the Gabriel method are identified. The crystal structure of N-lupinylphthalimide is determined for the first time by single crystal XRD. The energy characteristics are calculated using the quantum chemical method. It is found that the conformer with the chair conformation of the cycles with the axial orientation of the phthalimide substituent is more stable than that with the equatorial orientation.

В результате изучения химического состава казахстанского эндемика — полыни полусухой (Artemisia semiarida (Krasch. Et Lavr) Filat.) — впервые выделены сесквитерпеновые γ-лактоны эвдесманового ряда таурин: 8α-ацетокситаурин и 8α-гидрокситаурин. Рентгенодифракционным методом установлено их пространственное строение. Также выделен новый эвдесманолид, названный 8α-ацетокси-2-ен-таурином. На основании данных рентгеноструктурного анализа ему приписано строение 1-кето-8α-ацетокси-7α,6,11β(Н)-эвдесм-2,4-диен-6,12-олид.

As a result of studying the chemical composition of the Kazakh endemic Artemisia semiarida ((Krasch. Et Lavr.) Filat.), sesquiterpene γ-lactones of the eudesman type are isolated for the first time: taurine, 8α-acetoxytaurine, and 8α-hydroxytaurine. Their spatial structures are determined by Xray diffraction (XRD). New eudesmanolide named 8α-acetoxy-2-en-taurine is also isolated. Based on the single crystal XRD data, its structure is 1-keto-8α-acetoxy-7α,6,11β(H)-eudesm-2,4-diene-6,12-olide.

The synthesis of some cytisine derivatives was carried out in the work. The article provides the data of quantum-chemical calculation and virtual screening of the alkaloid cytisine derivatives synthesized. At the same time, the reaction centers of the cytisine derivatives molecules were determined. In order to study the reactivity of the derivatives obtained (namely cinnamoylcytisine, lipoylcytisine, and cytisinylisoalantholactone) the quantum-chemical calculations were conducted to determine the energy and charge characteristics of the molecules. The results indicate a sufficient thermodynamic stability of the cinnamoylcytisine and lipoylcytisine molecules. The cytisinylisoalantholactone molecule is not stable according to the results of quantum chemical calculations. The data on the energy values of the frontier molecular orbitals show that, in general, all molecules exhibit electrophilic properties. A bioprediction was implemented using PASS (Prediction of Activity Spectra for Substances) as one of the most efficient and well-known computer program with the aim of detailed study and the probable establishment of the biological activity of the synthesized cytisine derivatives. Based on the results of virtual screening, promising types of alkaloid cytisine derivatives were identified, which are potential sources of original drugs.

Проведена реакция ангидрида фталевой кислоты с изоникотиноилгидразидом в жестких условиях с образованием циклического имида фталевой кислоты — N-изоникотиноил­фталимида. Строение соединения установлено методами 1Н и 13С ЯМР спектроскопии, а также по данным двумерных спектров COSY (1H—1H) и HMQC (1H—13C). РСА и полуэмпирическим методом квантовой химии исследовано пространственное строение и конформация N-изоникотиноилфталимида. Установлено, что π-сопряжение между фенильной и карбонильной группами в свободной молекуле N-изоникотиноилфталимида практически отсутствует, и разворот пиридинового цикла относительно амидной группы в кристалле определяется π—π-взаимодействием между пиридиновыми циклами.

На основе алкалоида (–)-цитизина и этилизотиоцианата синтезирован N-этил-N-цитизинокарботиоамид, строение которого доказано методами 1Н ЯМР спектроскопии и рентгеноструктурного анализа. Показано, что наблюдается мезомерный эффект в образованной карботиоамидной группе. Установлено, что π-сопряжение между атомами азота и тиокарбонильной группой ослаблено вследствие возникающего стерического напряжения между атомами водорода пиперидинового цикла и тиоамидной группы.

The germacrane-type sesquiterpene lactones tatridin A and B were isolated for the first time during chemical studies of the extract of Lepidolopha karatavica. The structures of the compounds were elucidated using spectral data and X-ray crystal structure analyses (XSAs). Correlations of the XSAs and CD spectra defined the absolute configurations of the molecules. Possible conformational states of 3,8-deoxytatridin A and B were calculated by a quantum chemical method.

The crystal structure of crystalline hydrates of dimethylaminoarglabine hydrochloride and dimethylaminoarglabine hydronitrate is determined by single crystal X-ray diffraction. It is established that in a crystal, water breaks the hydrogen bond between the anion and the cation in dimethylaminoarglabin hydrochloride and weakens it in dimethylaminoarglabin hydronitrate, which improves the solubility of salts in water.

В результате изучения взаимодействия хлорлупинина с фталимидом калия найдены оптимальные условия синтеза N-лупинилфталимида в рамках метода Габриэля. Для N-лупинилфталимида методом РСА впервые определена кристаллическая структура. Методом квантовой химии рассчитаны энергетические характеристики. Установлено, что конформер с конформациями кресло циклов с аксиальной ориентацией фталимидного заместителя более устойчив, чем с экваториальной.

Методом РСА определена кристаллическая структура кристаллогидратов гидрохлорида диметиламиноарглабина и гидронитрата диметиламиноарглабина. Установлено, что в кристалле вода разрывает водородную связь между анионом и катионом в гидрохлориде диметиламиноарглабина и ослабляет в гидронитрате диметиламиноарглабина, что способствует улучшению растворимости солей в воде.

For the first time, synthesis of 8-formylharmine by the Vilsmeier reaction was carried out. 8-Formylharmine was obtained by treating alkaloid harmine with dichloromethoxymethane in the presence of SnCl4.The yield of the target product was 64 %. The structure of the obtained compound was established on the basis of 1H and 13C NMR spectroscopy as well as mass-spectrometry data. The crystalline structure of 8-formylharmine was determined by X-ray diffraction. It has been shown that the replacement of the hydrogen atom in the harmine molecule with a formyl group occurs at the C8 atom. It was revealed that the methoxy group at the C7 atom changes its orientation to the opposite one as compared to the orientation in the harmine molecule and its salts due to the mutual Van der Waals repulsion of the methoxy and formyl groups. A weak intramolecular hydrogen bond was found in the crystal between the O2 atom of the formyl group and the hydrogen atom of the secondary amino group. It was shown that molecules in the crystal form an intermolecular hydrogen bond between the same atoms (О2 and НN9A), as a result of which dimers are formed.