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Registration Number

0217U003098, 0115U003537 , R & D reports

Title

Stable carbenes of a new generation. Synthesis and properties

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Head

Korotkikh Nikolai Ivanovich, Доктор хімічних наук

Registration Date

18-01-2017

Organization

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

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The object of the study is new types of stable carbenes on the basis of fused imidazol-2-ylidenes and their precarbene and carbenoid forms to obtain highly effective catalysts of organic reactions in homogenic and heterogenic processes. The goal of the work is synthesis of stable carbenes of new generation for using as catalysts of organic reactions (hydrodehalogenation of haloarenes, reduction of multiple bonds, transesterification, etc. Methods of the study are synthetic, spectroscopic (NMR spectroscopy), analytical (chromatography, elemental analysis), X-ray ana¬lysis. The results of the research involve synthesis of sterically shielded and sterically open derivatives of phenanthro[9,10-d]imidazol-2-ylidenes with adamantyl, methyl and 2,6-diisopropylphenyl substitutents starting from phenathrenequinone. Methyl derivatives of carbenoids were synthesized by the reaction of phenathrenequinone with ammonium acetate and formaldehyde followed by the subsequent methylation of the obtained phenanthro[9,10-d]imidazole with dimethyl carbonate in the presence of DABCO, methylation of the intermediate 1-methylphenanthro[9,10-d]imidazole with methyl iodide and generation of 1,3-dimethylphenanthro[9,10-d]imidazol-2-ylidene under the action of sodium tert-butoxide on the corresponding salt in the presence of copper iodide. Adamantylation of phenanthro[9,10-d]imidazole was carried out in dichlorobenzene in the presence of calcium hydride. Mono- and disubstituted derivatives of this system were prepared. Synthesis of benzimidazol-2-ylidene-based cyclic carbene complexes with copper(I) iodide was developed and highly efficient catalysis was observed for the reduction reaction of ketones by alcohols in alkali medium. The DFT calculations of singlet-triplet splittings were carried out for a series of carbenes and the most stable ones were defined. The resulting data have prospects for the development of preparative synthesis of stable carbenes, precarbenes and their derivatives, catalysis of organic reactions with the help of the indicated compounds. The area of the application is synthesis of stable carbenes and their derivatives, catalysis of organic reactions.

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Єня Василь Іванович
Дзюба Оксана Іванівна
Ковач Микола Анатолійович
Короткіх Владислав Миколайович
Короткіх Микола Іванович
Панкіна Ольга Юрієвна
Раєнко Генадій Федорович
Скоробогатова Зоя Михайлівна
Ткачук Юлія Валентинівна
Устілко Юлія Олександрівна
Швайка Олесь Павлович

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2020-04-02