Search academic texts

Registration Number

0215U004330, 0114U003224 , R & D reports

Title

Inverse transphase catalysis of condensation reactions of bifunctional chloro anhydrides and phenols

popup.stage_title

Head

Rybachenko Volodymyr Ivanovych, Доктор хімічних наук

Registration Date

04-03-2015

Organization

The L.M.Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry

popup.description2

Objects of research - phosphoryl chlorides, phenols, pyridine N- oxides, hymatomelanic acids, gossypol imino-derivatives. Purpose - to develop methods of condensation of bifunctional reactants (dichlorides of carboxylic, sulfonic and phosphoric acids and polyphenols) in two-phase systems water-organic solvent, the study of the interaction of bifunctional acid chlorides with transphase catalysts (N-oxides of pyridine), phenols and polyphenols, the study of the structure and physical-chemical properties of the compounds, the synthesis of the corresponding ethers and polymer compounds oligoesters (polycarbonates, polysulfonates, polyphosphonates), including copolymers ( polycondensation products of acid chlorides with various polyphenols). Research methods - infrared spectroscopy, nuclear magnetic resonance, gas volumetric method, elemental analysis, quantum-chemical calculations. Were studied inversion transphase catalysis (CTI) reactions of phosphorylation of phenols. It is shown that the use of CTI allows monophenols phosphorylation reaction under mild conditions. The influence of the initial concentration of the catalyst in the aqueous phase on the rate of reaction and product yield. Determined that the most efficient catalyst among subjects for the phosphorylation reaction is a 4-dimethylaminopyridine-N-oxide. By IR and NMR spectroscopy and DFT were studied structures of six organic phosphates - 4-metoxyphenyl-, 4-methylphenyl, phenyl, 4-chlorophenyl, 4-nitrophenyl and 4-propionylphenyl diphenyl phosphates. The influence of the nature of the substituent at the para-position on the spectral characteristics of the compound. It was found that the method of using special IGLO basis sets has the advantage of modeling accuracy 31P chemical shifts of GIAO method with an average basis 6-31G (2df, p) with equal expenditure of time. It was studied initiated liquid-phase oxidation of cumene and ethylbenzene by oxygen in the presence of humic (HA) and hymatomelanic (HMA) acids. It has been shown that the addition of HA and HMA in the model reaction mixture hydrocarbon-DMSO-initiator causes inhibition of the oxidation of the hydrocarbon substrate (cumene, ethylbenzene), where the observed effect is enhanced with increasing concentration of humic substances. Thus, HA and HMA from brown coal are effective inhibitors of radical-chain oxidation, i.e exhibit expressed antioxidant properties. Were synthesized imino derivatives of gossypol. By IR and NMR spectroscopy were studied their structure and tautomeric equilibrium. Novelty is in the development of environmentally friendly methods of phosphorylation of phenols. The scientific importance is in studying of the process mechanism and structure of the reaction products by methods of experimental and theoretical spectroscopy. The practical significance is to find effective antioxidants from natural renewable raw materials.

Product Description

popup.authors

Ількевич Наталія Сергіївна
Аніщенко Віктор Миколайович
Бережний Валентин Сергїйович
Гребенюк Людмила Володимирівна
Дикун Олексій Михайлович
Коваленко Віталій Вікторович
Корженевська Надія Галактіонівна
Макарова Раїса Олександрівна
Невечеря Оксана Іванівна
Редько Андрій Миколайович
Рибаченко Володимир Іванович
Романенко Наталія Олександрівна
Семенова Римма Григорівна
Таперко Галіна Вікторівна
Хилько Світлана Леонідівна
Чотій Костянтин Юрійович

popup.nrat_date

2020-04-02