Мақалада лупинин алкалоидының екіорынбасылған 1Н-1,2,3-үшазол туындылары қатарының синтезі мен құрылымдық ерекшеліктері туралы зерттеулердің нәтижелері келтірілген. Лупинин алкалоидының химиялық трансформациясы хинолизин қаңқасының С-1 жағдайда орналасқан гидроксиметилен тобы бойынша жүзеге асырылды. Реакциялар үш кезеңде әр түрлі еріткіштерде жүргізілді. Лупининнің метансульфохлоридпен үшэтиламиннің қатысуымен өзара әрекеттесуі кезінде жоғары шығымдылықпен лупининнің мезилаты оңай түзілетіні көрсетілді. Осы қосылысты диметилформамид ерітіндісінде натрий азидімен ары қарай қыздырып өңдеу нәтижесінде жоғары шығыммен лупинин азидінің түзілуі жүреді. Жаңа азидтің мыс купоросының сулы және натрий аскорбаты қатысуымен диметилформамид ерітіндісінде әртүрлі сипаттағы функционалды орынбасылған ароматты алкиндермен өзара әрекеттесуі кезінде оларға сәйкес 4-алмастырылған лупининнің үшазолды туындыларының түзілуі мүмкін екендігі анықталды. Лупининнің үшазолды циклінің негізінде С-4 жағдайында орынбасылған ароматты жаңа туындылары синтезделді. Синтезделген үшазолдықосылыстардың құрылысы ЯМР 1Н және 13С спектрлерін талдау негізінде дәлелденілді. Жаңа заттардың ЯМР 13С спектрлеріндегі сигналдардың мультиплеттілігі J-модуляция режимінде (JMOD) жазылған спектрлер бойынша анықталды. Синтезделген қосылыстардың құрылысы сондай-ақ екі өлшемді COSY (1H-1H) және HMQC (1H-13C) спектрлерінің деректерімен зерттелген. ЯМР спектрлердегі химиялық ығысулардың мәндері 1Н және 13С сигналдарының мультиплеттілігі және интегралды қарқындылығы бір өлшемді ЯМР спектрлерімен анықталды.
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.
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 temperature dependences of the specific heat of nanoscale (nanocluster) cobaltite(nickelite)-cuprate-manganites LaSrCoCuMnO6 and LaSrNiCuMnO6 have been studied via experimental dynamic calorimetry in the range of 298.15–673 K. The temperature dependences of the specific heat $${C}_{p}^{\circ }$$ ~ f(T) of LaSrCoCuMnO6 (at 323 and 523 K) and LaSrNiCuMnO6 (at 348 K) exhibit anomalous jumps in the specific heat, which are likely due to the second-order phase transitions. Based on the experimental data on $${C}_{p}^{\circ }$$(T) and the calculated value of entropy S°(298.15), the temperature dependences of the specific heat and thermodynamic functions of the studied compounds are calculated in the temperature range of 298.15–673 K.
A crystalline compound is isolated from Digitalis lanata Ehrh. and its molecular and crystal structures are studied by single crystal X-ray diffraction. The X-ray diffraction results show that the crystal is mixed and consists of a crystalline hydrate of isomorphically substituted digitogenin and gitogenin molecules in the 38:62 ratio. The data on the mole ratio are confirmed by high-performance liquid chromatography.
Из наперстянки шерстистой (Digitalis lanata Ehrh.) выделено кристаллическое вещество, молекулярная и кристаллическая структура которого исследована рентгеноструктурным методом. Результаты рентгеноструктурного анализа показали, что кристалл смешанный, состоит из кристаллогидрата изоморфно замещенных молекул дигитогенина и гитогенина в соотношении 38:62. Данные по соотношению молекул подтверждены методом высокоэффективной жидкостной хроматографии.
2-Deoxyecdyzone (3β,14α,22R,25-tetraoxy-5β-cholest-7-en-6-one) has been isolated from Silene cretaceae Fisch. Caryophyllaceae. The compound structure has been elucidated by X-ray diffraction studies.
The studies were carried out to search for 20-hydroxyecdysone and its analogs among plants in the flora of Kazakhstan. There were determined their long-term sources which were families of Amaranthaceae Juss., Caryophyllaceae Juss., Chenopodiaceae Vent. and Asteraceae Dumort., genus Lychnis L., Silene L., Rhaponticum Adans, Serratula L., species of Lychnis chalcedonica L., Kochia prostrata L., Silene cretaceae Fisch., Serratula coronata L. and Silene wolgensis (Hornem) Bess.
The heats of solution of tigogenin C27H44O3 in dioxane at dilutions equal to 1: 9000, 1: 18 000, and 1: 36 000 (mol solute/mol solvent) have been studied by isothermal calorimetry. The standard enthalpy of C27H44O3 solution in dioxane at infinite dilution was derived by the mathematical processing of the calorimetric data. Dynamic calorimetry over the range 173–423 K has been used to study the heat capacity of tigogenin. The C p o ∼ f(T) plot has a jump at 298.15. K. The standard enthalpies of formation and combustion and the heat of melting of tigogenin have been indirectly calculated.
Tigogenin [(25R)-5α-spirostan-3β-o1] was isolated from Digitalis lanata Ehrh. , and its crystal and molecular structure was determined by single crystal X-ray diffraction.