REACTION OF 2-HETARYL-2-(DIHYDROFURAN-2(3H)-ILIDEN)ACETONITRILES WITH AROMATIC AMINES
DOI: https://doi.org/10.17721/1728-2209.2020.1(57).12
Keywords:
2-hetaryl-2-(furanyl-2-ylidene)acetonitriles, 2-hetaryl-2-(N-arylpyrrolidin-2-ylidene)acetonitriles, aromatic aminesAbstract
This article reports on the reaction of 2-hetaryl-2-(furanyl-2-ylidene)acetonitriles with aromatic amines as N-nucleophiles. 2-Hetaryl-2-(furanyl-2-ylidene)acetonitriles represent versatile building blocks in syntheses of ω-(N-aryl)alkyl substituted heterocycles due to the presence of 1,3-bielectrophilic acrylonitrile fragment functionalized with unsaturated heterocyclic ring and nucleophilic azaheterocyclic moiety. The carbonyl group masked within the N-arylpyrrolidinylidene fragment which undergoes a ring opening through the reaction with nucleophiles. So, a method for the synthesis of 2-hetaryl-6-hydroxy-3-(arylamino)hex-2-enenitriles and 2-hetaryl-2-(N-arylpyrrolidin-2-ylidene)acetonitriles has been developed by us. The proposed scheme is based on the available reagents using. As a result of Michael addition, the aromatic amines to 2-hetaryl-2-(furanyl-2-ylidene)acetonitriles followed by ring transformations has formed two types of products, depending on the reaction conditions. The reaction of substituted furanylylideneacetonitriles with aromatic amines proceeds in good to high yields affording the corresponding 3-(arylamino)hex-2-enenitriles and 2-(N-arylpyrrolidin-2-ylidene)acetonitriles derivatives. The stereochemistry of the ring-opening reaction follows the rules of a classical SN2 mechanism. The resulting linear products can be cyclized to 2-hetaryl-2-(furanyl-2-ylidene)acetonitriles in high yields by treatment with the catalytic amount of acid or the equimolar amount of aromatic amines. Under these conditions 2-hetaryl-6-hydroxy-3-(arylamino)hex-2-enenitriles arising from reaction gives the ring closure.
References
1. Furstner A. Platinum-catalyzed cycloisomerization reactions of enynes / A. Furstner, F. Stelzer, H. Szillat // J. Am. Chem. Soc. – 2001. – V. 123. – № 48. – Р. 11863–11869.
2. Volovenko Yu. M. Synthesis of Enamino Nitrile of a New Type, 2-Hetaryl-2-(2-pyrrolidinylidene)acetonitriles, and Their Tautomerism / Yu. Volovenko, A. Tverdokhlebov // Chem. Heterocycl. Compd. – 2000. – V. 36. – P. 1351–1352.
3. Шемеген Р. В. Реакції 2-гетарил-2-(тетрагідро-2-фураніліден)ацетонітрилів з ароматичними амінами / Р. В. Шемеген, О. В. Хиля, Ю. М. Воловенко // XVI Міжнарод. наук. конф. студентів та аспірантів "Сучасні проблеми хімії", 20–22 травня, 2015 : тези доп. / КНУ імені Тараса Шевченка. – К., 2015. – С. 69.
4. Synthesis of 2-(2-hetaryl)-6-hydroxy-3-(R-amino)-2-hexenenitriles / O. V. Khilya, T. A. Volovnenko, A. V. Turov, R. I. Zubatyuk, O. V. Shishkin, Yu. M. Volovenko // Chem. Heterocycl. Compd. – 2013. – V. 48. – P. 1770–1780.
5. Khilya O.V. Reaction of 2-hetaryl-2-(tetrahydro-2-furanylidene)acetonitriles with aldehydes / O. V. Khilya, Y. V. Baglay, Yu. M. Volovenko // Chem. Heterocycl. Compd. – 2010. – V. 46. – P. 934–937.
6. Reactions of 2-(2-Hetaryl)-2-(tetrahydrofuran-2-ylidene)acetonitriles with Tertiary Amines / D. S. Milokhov, O. V. Khilya, A. V. Turov, R. I. Zubatyuk, G. V. Palamarchuk, O. V. Shishkin, A. A. Chekotilo, Yu. M. Volovenko // Chem. Heterocycl. Compd. – 2013. – V. 48. – P. 1761–1769.
7. Michael J. Syntheses of alkyl (E)-(1-aryl-2-pyrrolidinylidene)acetates / J. Michael, G. Hosken, A. Howard // Tetrahedron. – 1988. – V. 44. – P. 3025–3036.
8. Reaction of dianions of acyclic β-enamino ketones with electrophiles. Part 2. Oxiranes: synthesis of γ′- and ω-hydroxy-β-enamino ketones and of α-tetrahydrofurylidene ketones / G. Bartoli, M. Bosco, C. Cimarelli, R. Dalpozzo, G. Palmieri // Chem. Soc., Perkin Trans. 1. – 1992. – V. 16. – P. 2095–2100.
9. Catalytic Hydrogenation of 5,6‐Dihydro‐4H‐1,2‐oxazines Bearing a Functionalized Methylene Group at C‐3 / A. Yu. Sukhorukov, A. V. Lesiv, O. L. Eliseev, Yu. A. Khomutova, S. L. Ioffe, A. O. Borissova // Eur. J. Org. Chem. – 2008. – V. 23. – P. 4025–4034.
10. Khilya O.V. Convenient method for the synthesis of 2-(4-oxo-3,4-dihydro-2-quinazolinyl)-2-(2-tetrahydrofuranylidene) acetonitriles / O. V. Khilya, Yu. M. Volovenko, T. A. Volovnenko // Chem. Heterocycl. Compd. – 2003. – V. 39. – P. 394–395.
11. Взаємодія 4-оксо-3,4-дигідрохіназоліл- та бензімідазолілацетонітри-лів з o-галогенбензальдегідами / Ю.М. Воловенко, О.В. Хиля, Т. А. Воловненко, А. В. Туров // Доповіді НАН України. – 2003. – № 4. – С. 128–133.
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