dehydracetic acid, chalcones, alkylamino-β-ketoenols.

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The structure of alkylamino-β-ketoenols obtained by opening of the pyran cycle of chalcones based on dehydracetic acid was studied by X-ray diffraction, IR, 1H NMR spectroscopy and chromatography-mass spectrometry. The infrared spectra of the compounds appear to be typical of β-ketoenols. The crystalline structure (2Z,5Z,7E,9E)-6-hydroxy-2-(methylami-no)-10-phenylethoxy-2,5,7,9-tetraene-4-one was first determined. A comparative analysis of it with 2 pre-viously published structures has been carried out. All of these compounds are crystallized in the form of yellow plates in the monoclinic crystalline system (spatial group P21/n), they have a planar arrangement of the polyene chain and β-ketoenol fragment con-jugated to the aromatic ring. It has been established that the planar configuration of the β-ketoenol fragment is stabilized by hydrogen bonds between the hydroxy and keto group and the amino and keto group in the crystalline state. The length of the polymethine chain, the nature of the substituents in the aromatic and aliphatic part of the molecule do not significantly affect the size and geometry of the alkylamino-β-ketoenolate fragment. Approximately the same lengths of bonds, the distance between atoms and the corners indicate that all these com-pounds may have similar chelating properties. Ac-cording to 1H NMR spectroscopy in various deu-terated solvents (benzene, DMSO, chloroform, ace-tone, methanol and trifluoroacetic acid), most of the main signals of the obtained compounds have sa-tellites, which indicates the existence of several isomeric forms in solutions. The analysis of integral intensities of labile protons in 1H NMR spectra does not allow to obtain accurate results regarding the ratio of tautomers in a solution, but for a series of compounds their approximate ratio in chloroform, DMSO and trifluoroacetic acid have been established (from 70:30 in CDCl3 to 90:10 in DMSO and CF3CO2D). The stability of the tautomers in the solutions is confirmed by the data of chromatogra-phy-mass spectrometry.


1. Zucolotto Chalaça M., Figueroa-Villar J.D., El-lena J.A., Castellano E.E. Synthesis and struc-ture of cadmium and zinc complexes of dehyd-roacetic acid . Inorg. Chim. Acta. 2002. 328: 45.
2. Munde A., Shelke V., Jadhav S., Kirdant A., Vaidya S., Shankarwar S., Chondhekar T. Syn-thesis, Characterization and Antimicrobial Ac-tivities of some Transition Metal Complexes of Biologically Active Asymmetrical Tetradentate Ligands. Adv. Appl. Sci. Res. 2012. 3: 175.
3. Hsieh W.-Y., Zaleski C.M., Pecoraro V.L., Fan-wick P.E., Liu S. Mn(II) complexes of mono-anionic bidentate chelators: X-ray crystal struc-tures of Mn(dha)2(CH3OH)2 (Hdha = dehyd-roacetic acid) and [Mn(ema)2(H2O)]2·2H2O (Hema = 2-ethyl-3-hydroxy-4-pyrone). Inorg. Chim. Acta. 2006. 359: 228.
4. Chitrapriya N., Mahalingam V., Zeller M., Ja-yabalan R., Swaminathan K., Natarajan K. Syn-thesis, crystal structure and biological activities of dehydroacetic acid complexes of Ru(II) and Ru(III) containing PPh3/AsPh3. Polyhedron. 2008. 27: 939.
5. Maurya R.C., Malik B.A., Mir J.M., Vishwakar-ma P.K. Oxidovanadium (IV) complexes invol-ving dehydroacetic acid and β-diketones of bioinorganic and medicinal relevance: Their synthesis, characterization, thermal behavior and DFT aspects. J. Mol. Struct. 2015. 1083: 343.
6. Al Alousi A.S., Shehata M.R., Shoukry M.M., Hassan S.A., Mahmoud N. Coordination pro-perties of dehydroacetic acid – binary and ter-nary complexes. J. Coord. Chem. 2008. 61: 1906.
7. Chernii V.Ya., Dovbii Y.M., Tretyakova I.N., Severinovskaya O.V., Volkov S.V. Synthesis and properties of phthalocyanine complexes of zirconium and hafnium with dehydracetic acid. Ukr. Chem. Journ. 2015. 81(1): 3. [in Russian].
8. Edwards J.D., Page J.E., Pianka M. Dehydroa-cetic acid and its derivatives. J. Chem. Soc. 1964:5200.
9. Manku G.S., Sapral P.D. Dehydroacetic acid as a reagent for the separation and gravimetric determination of copper(II), aluminium and be-ryllium. Talanta. 1971. 18(10): 1079.
10. Bhat A.N., Jain B.D. Analytical applications of 3-acetyl-4-hydroxycoumarin. II: Spectro-photometric determination of iron II. Talanta. 1960. 5(3–4): 271.
11. Bhat A.N., Jain B.D. Separation and determi-nation of uranium and thorium with 3-ace-tyl-4-hydroxycoumarin.Talanta. 1960. 4(1):13.
12. Bhat A.N., Jain B.D. Gravimetric determination of cerium (IV) and its separation from rare earths using 3-acetyl-4-hydroxycoumarin. J. Less Common Metals. 1961. 3(3): 259.
13. Zouchoune F., Zendaoui S.-M., Bouchakri N., Djedouani A., Zouchoune B. Electronic struc-ture and vibrational frequencies in dehydro-acetic acid (DHA) transition-metal complexes: A DFT study. J. Molec. Struct. THEOCHEM. 2010. 945: 78.
14. Aït-Baziz N., Rachedi Y., Hamdi M., Silva A.M.S., Balegroune F., Thierry R., Sellier N. 4-hydroxy-6-methyl-3-5-phenyl-2E,4E-pentadi-en-1-oyl)-2H-pyran-2-one: Synthesis and reac-tivity with amines. J. Heterocyclic Chem. 2004. 41(4): 587.
15. Jilalat A.E., Al-Garadi W.H.A.H., Karrouchi K., Essassi E.M. Dehydroacetic acid (Part 1): chemical and pharmacological properties. J. Mar. Chim. Heterocycl. 2017. 16(1): 1.
16. Kotali A., Nasiopoulou D.A., Harris P.A.A novel and facile synthesis of 3,4-diacyl-2H-pyran-2-ones. New CC bond formation Tet-rahedron Lett. 2016. 57: 3488.
17. Walker G.N. Reduction of Enols. New Syn-thesis of Certain Methoxybenzsuberenes via Hydrogenation of Dehydroacetic Acids. J. Am. Chem. Soc. 1956. 78(13): 3201.
18. Pavlik J. W. Ervithayasuporn V., Tantayanon S. Synthesis of some pyrano[2,3-c]pyra-zoles. J. Heterocyclic Chem. 2011. 48: 710.
19. Prakash O., Kumar A., Kinger M., Singh S.P. Io-dine (III) mediated synthesis of new 5-aryl-3-(4-hydroxy-6-methyl-2H-pyran-2-oxo-3-yl)-l-phe-nylpyrazoles from dehydrogenation of 5-aryl-3-(4-hydroxy-6-methyl-2H-pyran-2-oxo-3-yl)-1-phe-nylpyrazolines. Indian J. Chem. 2006. 45B: 456.
20. Goto S., Iguchi S., Kono A., Utsunomiya H. Ki-netics of Reaction of Dehydroacetic Acid I: Reaction with Primary Amines I. J. Pharm. Sci. 1967. 56: 579.
21. Wang C.S., Easterly J.P., Skelly N.E. Reaction of dehydroacetic acid with ammonia. Tetrahed-ron. 1971. 27: 2581.
22. Mohmed J., Palreddy R.R., Boinala A., Narsim-ha N., Gunda S.K., Ch S.D. Synthesis, charac-terization, equilibrium and biological studies of novel 33-(1-(benzo[d]thiazol-2-ylimino)ethyl)-6-methyl-2h-pyran-2,4(3h)-dione and its Cu(II), Ni(II) and Hg(II) metal complexes: an experi-mental and theoretical approach. Int. J. Pharm. Sci. Res. 2016. 7: 1103.
23. Benosmane N., Boutemeur B., Hamdi S., Ham-di M. A convenient synthesis of pyrandione de-rivatives using P-toluenesulfonic acid as ca-talyst under ultrasound irradiation. J. Fundam. Appl. Sci. 2016. 8: 826.
24. Gelin S., Chantegrel B., Nadi A. I. Synthesis of 4-(acylacetyl)-1-phenyl-2-pyrazolin-5-ones from 3-acyl-2H-pyran-2,4(3H)-diones. Their syn-thetic applications to functionalized 4-oxopyra-no[2,3-c]pyrazole derivatives. J. Org. Chem. 1983. 48: 4078.
25. Rehse K., Rüther D. Einfluß der S-Oxidation auf anticoagulante Wirkungen bei 4-Hydroxy-cumarinen, 4-Hydroxy-2-pyronen und 1,3-Indan-dionen. Arc. Pharm. 1984. 317: 262.
26. Li L., Bender J.A., West F.G. Diastereocontrol in [4+4]-photocycloadditions of pyran-2-ones: effect of ring substituents and chiral ketal. Tetrahedron Lett. 2009. 50:1188.
27. Aït-Baziz N., Rachedi Y., Chemat F., Hamdi M. Solvent Free Microwave-Assisted Knoevena-gel Condensation of Dehydroacetic Acid with Benzaldehyde Derivatives. Asian Journ. Chem. 2008. 20: 2610.
28. Patange V., Arbad B. Synthesis, spectral, ther-mal and biological studies of transition metal complexes of 4-hydroxy-3-[3-(4-hydroxyphenyl)-acryloyl]-6-methyl-2H-pyran-2-one. J. Serb. Chem. Soc. 2011. 76: 1237.
29. Dovbii Ya.M., Chernii V.Ya., Tretyakova I.M., Gorski A.V., Starukhin A.S., Volkov S.V. Syn-thesis of dehydroacetic acid derivatives with chromophoric chains and their complexes with zirconium phthalocyanine. Ukr. Chem. Journ. 2015. 81(12): 79.
30. Chergui D., Hamdi M., Baboulene M., Spezi-pale V., Lattes A. Réactivité des cinnamoyl-3-pyrones-2 vis à vis des amines primaires. J. He-terocycl. Chem. 1986. 23: 1721.
31. Kovalska V., Chernii S., Losytskyy M., Dovbii Y., Tretyakova I., Czerwieniec R., Chernii V., Yarmoluk S., Volkov S. β-ketoenole dyes: Syn-thesis and study as fluorescent sensors for pro-tein amyloid aggregates. Dyes and Pigm. 2016. 132: 274.
32. Kovalska V., Chernii S., Losytskyy M., Tretya-kova I., Dovbii Y., Gorski A., Chernii V., Czer-wieniec R., Yarmoluk S. Design of functionali-zed β-ketoenole derivativesas efficient fluore- rescent dyes for detection of amyloid fibrils. New J. Chem. 2018. 42: 13308.
33. Forsen S., Nilsson M. The Chemistry of Carbo-nyl Group. (London: Interscience, 1970). 2. Ch. 3.


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