The structure of 2-arylhydrazones 1R-3-(4-pyridinyl)-1,2,3-propanetrione

V. A. Kovtunenko, L. M. Potikha, T. S. Bulda, R. I. Zubatyuk, O. V. Shishkin

Abstract


For the first time 2-arylhydrazones of 1R-3-(4-pyridinyl)-1,2,3-propanetrion have been synthesized with the help of Japp-Klingemann reaction. They are characterized by the keto-hydrazone structure, but since the initial dicarbonyl compound is asymmetric, there is a real possibility of formation of two tautomer forms – form A (where the fragment with acetyl group acts as the acceptor of the hydrogen bond) and form B (where 4- the pyridoyl fragment acts as the acceptor of the hydrogen bond). In the solid state 2-arylhydrazones of 1R-3-(4-pyridinyl)-1,2,3-propanetriones exist in the form of tautomer A. In the solid state the structure of the initial 1R-3-(4-pyridinyl)-1,2,3-propanetriones, as well as the structure of 2-arylhydrazones of 1R-3-(4-pyridinyl)-1,2,3-propanetriones obtained from of them has been studied with the help of IR spectroscopy (in the range of 1500-1600 cm-1 where the intensive absorption is observed). In this part of the spectrum the hyrazones absorption differs from the initial compounds. Distinctive intensive bands appear in the ranges of 1508-1516 cm-1 and 1640-1665 cm-1. Besides, none of the carbonyl groups of 2-arylhydrazones of 1R-3-(4-pyridinyl)-1,2,3-propanetriones is enolized. Both forms (A and B) may exist in solu­tions. The proportion of forms is controlled by the nature of the solvent. In all compounds of CDCl3 the concentration of isomer A is higher than that of isomer B. In the spectrum of 1-(4-pyridinyl)-1,2,3-butantrion-2-[(4-methylphenyl) hydrazone) there are no signals, which could be attributed to isomer B. It testifies the predominant coordination of the hydrogen bond by the fragment with the acetyl group and formation of strong intramolecular hydrogen bonds. The ratio of isomers in solution of the polar solvent (DMSO-d6) changes in favour of accumulation of more polar minor tautomer B. Factors affecting the isomers equilibrium position have been evaluated together with determina­tion of the dependence between the electronic effect of the substituent in the para-position of the phenylhydrazone fragment and the ratio and characteristics of A and B isomers. The intramolecular hydrogen bond strengthens with the presence of electron-donating substituents, while the thermodynamic efficiency of tautomer A increases. Quaternization of 2-arylhydrazones of 1R-3-(4-pyridinyl)-1,2,3-propanetrion by iodic methyl occurs only by the pyridine atom of nitrogen, thus decreasing the content of compounds that are derivatives of minor tautomer B.


Keywords


azo coupling; 2-arylhydrazone of β-diketone; quaternization

References


Gilli P., Pretto L., Bertolasi V., Gilli G. Acc. Chem. Res., 2009, Vol. 11, pp.33-44.

Olivieri A.C., Wilson R.B., Paul I.C., Curtin D.Y. J. Am. Chem. Soc., 1989, Vol. 111, pp.5225-32.

Krugowski T.M., Wozniak K., Anulewics R. et al. J. Phys. Chem., 1997, Vol. 101, pp.9399-404.

Yaddib H.B., Issa Y.M., Mohamed W.S. Journal of Thermal Analysis and Calorimetry, 2008, Vol. 92, pp.775-82.

Aliyeva R.A., Chygarov F.M., Mahmudov K.T., Journal of Analytical Chemistry, 2005, Vol. 50, pp.137-40.

Chen Z.M., Huang F.X., Wu Y.Q. et al. Inorganic Chemistry Communications, 2006, Vol. 9, pp.21-4.

Contihno D.L.M., Fernandes P.C. Indian J. Heterocycl. Chem., 1991, Vol. 1, pp.109.

Kocyigit B.K., Rollas S. Il Farmaco, 2002, Vol. 57, pp.595.

Mishra L., Jha A., Yadaw A.K. Transition Met. Chem., 2007, Vol. 22, pp.406.

Pat. European 383 449; Сhem. Abstr., 1991, Vol. 114, p. 81895 t.

Pat. GB 2 228004; Сhem. Abstr., 1991, Vol. 114, p.228967 d.

Ковтуненко В.А., Потиха Л.М., Мищук А.А., Туров А.В. Khimiya geterocyclicheskikh soedinenij – Chemistry of Heterocyclic Compounds, 2008, Vol. 44, p.1412.

Щегольков Е.В., Бургарт Я.В., Худина Щ.Г., Салоутин В.И., Чупахин О.Н. Uspekhi khimii – Успехи химии, 2010, Vol. 79 (1), pp.33-64.

Bertolasi V., Pretto L., Ferretti V., Gilli P., Gilli G. Acta crystallographica. Section B, Structural science, 2006, Vol. 62, (Pt 6), pp.1112-20

.

Burgi H.-B., Dunitz J.D. Structure correlation. VCH. Weinheim., 1994, Vol. 2, pp.741-784.

Bertolasi V., Ferretti V., Gilli P., Gilli G., Issa Y.M., Sherif O.E. J. Chem. Soc., Perkin Trans., 1993, №2, pp.2223.

Электронная база данных Национального института передовых промышленных наук и технологий (Япония). Режим доступа: http://sdbs.riodb.aist.go.jp SDBS№ 5801 и 874.

Электронная база данных Национального института передовых промышленных наук и технологий (Япония). Режим доступа: http://sdbs.riodb.aist.go.jp SDBS№ 6316.

Mitchell A.D., Nonhebel D.C. Tetrahedron, 1979, Vol. 35, p.2013.

Bertolasi V., Gilli P., Ferretti V., Gilli G., Vaughan K. New J. Chem., 1999, Vol. 23, p.1261.

Hammett L.P. J. Am. Chem. Soc., 1937, Vol. 59, p.96.

Mitchell A.D., Nonhebel D.C. Tetrahedron Letters, 1975, pp. 3859-3862.

http://www.chemicalize.org/

В дейтерохлороформе образцы нерастворимы.

Vogel A.I. A Text Book of Practical Organic Chemistry, Third ed., 1961, p.865.

Ishidate; Yamane, Yakugaku Zasshi, 1957, 77, p.386,387.

Sheldrick G. Acta Cryst., Sect. A, 2008, Vol. 64, p.112.


GOST Style Citations






DOI: https://doi.org/10.24959/ophcj.14.795

Creative Commons License
This work is licensed under a Creative Commons Attribution 4.0 International License.

Abbreviated key title: Ž. org. farm. hìm.

ISSN 2518-1548 (Online), ISSN 2308-8303 (Print)