Registration Number
0216U001341,
0115U003537
, R & D reports
Title
Stable carbenes of a new generation. Synthesis and properties
popup.stage_title
Head
Korotkikh Nikolai Ivanovich, Доктор хімічних наук
Registration Date
08-02-2016
Organization
The L.M.Litvinenko Institute of Physical-Organic Chemistry and Coal Chemistry
popup.description2
The object of the study is new types of stable carbenes with steric protection of the carbene center and precarbene forms to create highly efficient catalysts for the reductive dehalogenation (hydrodehalogenation) of haloarenes in homogeneous and heterogeneous processes. The purpose of the work is the synthesis of stable carbenes of new generation with a view to their use for the synthesis of the catalysts for haloarene hydrodehalogenation. The research methods - synthetic, spectroscopic (NMR spectroscopy), analytical (chromatography, elemental analysis), X-ray analysis. The results of the research involve a high catalytic effect of dimeric complex of palladium iodide with 1,3-bis(2,6-diisopropylphenyl) substituted imidazole-2-ylidene in the reaction of oxidation of aromatic alcohols with haloarenes to form ketones (TON 1000, TOF 42 h-1 at room temperature), which exceeds that for the known level of the reaction catalysis. The synthesis of sterically branched derivative of imidazol-2-ylidene with 2,4,6-trisbenzhydrylphenyl substituents was carried out for the first time by four steps starting from aniline. The synthesis of individual 2,6-diisopropylphenyl substituted phenanthro[4,5-c]imidazol-2-ylidene was performed by three-step route from phenanthrenequinone. A new method for the synthesis of 1,3,4-triaryl substituted 1,2,4-triazol-5-ylidenes was developed starting from phenylhydrazine. These carbenes are promising ligands for the synthesis of highly efficient haloarene hydrodehalogenation catalysts and oxidation of alcohols by haloarenes. A search of the literature on the carbene subject was carried out resulting in a review on the chemistry of stable carbenes of the imidazole, triazole series and their fused analogues. The proton affinities of a large number of carbenes were defined by DFT calculations, and some boundary compounds were found in this series. An area of hyperbasic and hypernucleophilic carbenes was expanded on the structures, in which the conduct of electronic influence is fulfilled via the different types of atoms (carbon, nitrogen, oxygen, sulfur, phosphorus). The resulting data have prospects for the development of reductive haloarene dehalogenation catalysis and preparative synthesis of stable carbenes and their precursors. The area of the application is catalysis of the haloarene hydrodehalogenation reaction, synthesis of stable carbenes. In future it is predicted the synthesis and studies of new catalysts efficiencies for the reductive processes based on the carbenes synthesized.
Product Description
popup.authors
Єня Василь Іванович
Дзюба Оксана Іванівна
Ковач Микола Анатолійович
Короткіх Микола Іванович
Панкіна Ольга Юріївна
Раєнко Генадій Федорович
Скоробогатова Зоя Михайлівна
Устілко Юлія
Швайка Олесь Павлович
popup.nrat_date
2020-04-02
