Лаборатория полинепредельных соединений (№ 7)

• Разработка новых методов направленного синтеза природных низкомолекулярных биорегуляторов отдельных классов (стробилуриновые антибиотики, простаноиды, стероидные сапонины, полипренолы, феромоны насекомых и др.), их модифицированных аналогов, а также полупродуктов и вспомогательных реагентов для их получения.

✓  A new chiral hydrogen-bonded organic framework (HOF) denoted as ZIOC-1 based on a l-prolineamide substituted diarylacetylene dicarboxylic acid (3,3′-ethyne-1,2-diylbis[6-(l-prolylamino)benzoic acid]) has been synthesized and structurally characterized. Crystal structures of two forms of ZIOC-1, i.e., anhydrous and dihydrate phases, were identified by powder X-ray analysis. It was found that the novel HOF material demonstrated a framework flexibility: its crystalline phases transform reversibly into each other by a change in either humidity or ambient temperature. This fact in conjunction with the retention of crystal identity to the temperature as high as 265 °C indicates a robustness of the framework formed by a hydrogen bonding system. The catalytic performance of the synthesized HOF was probed in aldol condensation and Michael reaction.

✓  A novel hybrid material was prepared by the direct growth technique starting from metal-organic framework HKUST-1 (Cu3(BTC)2, BTC = benzene-1,3,5-tricarboxylate) and mesoporous silica matrix (MMS). MMS acts as a structure-directing agent, which assists to the formation of very small HKUST-1 nanoparticles (4–8 nm) are dispersed homogeneously in the silica matrix. To evaluate the field of the potential exploitation of HKUST-1@MMS hybrid, it was examined as a heterogeneous catalyst with Lewis and Brønsted acid sites in demanding organic transformations widely used for fine chemicals production, i.e. in the Friedlӓnder reaction between 2-amino-5-chlorobenzophenone and acetylacetone and Henry reaction (nitroaldol condensation) between nitromethane and 4-nitrobenzaldehyde. The cooperative effect between Lewis acid sites as Cu2+ ions in the HKUST-1 framework and acid sites of MMs silica in the HKUST-1@MMS catalytic material relevant to the Henry reaction between 4-nitrobenzaldehyde and nitromethane was found for the first time. According to adsorption tests, the novel hybrid features an hierarchical micro-/mesoporous structure and can also find application as an adsorbent with molecular-sieving properties.

✓  The zinc imidazolate metal-organic framework ZIF-8 was prepared from Zn(NO3)2 and 2-methylimidazole using liquid NH3 as solvent and was found to exhibit similar properties to ZIF-8 prepared by lit. procedures. ZIF-8 acted as a recyclable catalyst for the Henry reactions of nitromethane with 2-nitrobenzaldehyde, 4-nitrobenzaldehyde, and 4-pentenal to yield nitro alcs.; 2-chlorobenzaldehyde, 4-bromobenzaldehyde, 4-methoxybenzaldehyde, and cyclohexanone did not react with nitromethane in the presence of ZIF-8.