ON REDUCTION OF N (β CYANOETHYL)BENZOMORPHOLINE AND N (β CYANOETHYL)PHENOTHIAZINE

DOI: 10.6060/tcct.20165911.5274
Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2016. V. 59. N 11. P. 40-45

The article is devoted to the reduction of products of the phenothiazine and benzo-morpholine cyanoethylation reaction by sodium borohydride, lithium aluminum hydride and hydrazine monoformiate in diverse conditions. Morpholine cyanoethylation reaction was studied as a model one, as well as benzomorpholine and phenothiazine ones were studied as well. Special attention was paid to the reaction of further reduction of the corresponding ni-triles. The article considers the solution of several synthetic problems: synthesis of the initial heterocycles; cyanoethylation of morpholine by acrylonitrile and selection of the conditions for this reaction (temperature, reaction time, concentrations, catalyst, solvents); cyanoethyla-tion of benzomorpholine and phenothiazine by acrylonitrile in the selected conditions; reduc-tion obtained nitriles by the different reduction systems. It was stated, that adherence of acry-lonitrile to morpholine is more effective when basic phase transfer catalyst was used. Carry-ing out cyanoethylation under phase transfer catalysis conditions (acrylonitrile as a one phase and substrate as a second ones) using tetrabutylammonium hydroxide as a catalyst yielded N (β cyanoethyl)benzomorpholine of 69% and N (β cyanoethyl)phenothiazine of 64% yields. Potassium hydroxide in the polar and nonpolar solvents and copper (II) acetate were also tested as catalysts of cyanoethylation by acrylonitrile. Different reduction systems, such as sodium borohydride / cobalt chloride (II) in methanol, sodium borohydride / cobalt chloride (II) in tetrahydrofuran-water mixture (2:1), lithium aluminum hydride in diethyl ether, lithium aluminum hydride in tetrahydrofuran, hydrazine monoformiate on nickel Raney were tested for the reduction reaction of the obtained nitriles. It was stated that N (β cyanoethyl)benzomorpholine is reduced well to N (3 aminopropyl)benzomorpholine with 70% yield by NaBH4 / CoCl2 system in methanol. His reduction by the other reagents proceeds worse. Attempts to reduce N (β cyanoethyl)phenothiazine failed in any systems be-ing used. Destruction of N (β cyanoethyl)phenothiazine increases with the growth of the basic properties of a reducing system occurred: phenothiazine and diphenylamine were the general products of this reaction. Phenothiazine formation can be explained by reversibility of the re-action of cyanoethylation and elimination of β-cyanoethyl-fragment under the bases influ-ence. The diphenylamine appearance among reaction products in some cases indicates that the substrate reductive desulfurization reaction occurred.

Key words: phenothiazine, benzomorpholine, nitriles reduction

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2016, Т. 59, № 11, Стр. 40-45

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