SYNTHESIS AND PROPERTIES OF CHALCONES BASED ON DEHYDROACETIC ACID
№1

Keywords

dehydroacetic acid, Knoevenagel condensation, chalcones.

How to Cite

Tretyakova, I., Chernii, V., Fedosova, N., Denisenko, I., Dovbii, Y., Kovalska, V., Chernii, S., Pekhnyo, V., & Starukhin, A. (2021). SYNTHESIS AND PROPERTIES OF CHALCONES BASED ON DEHYDROACETIC ACID. Ukrainian Chemistry Journal, 87(5), 3-14. https://doi.org/10.33609/2708-129X.87.05.2021.3-14

Abstract

The Knoevenagel condensation reaction between dehydracetic acid and aromatic aldehydes is described in this work. The reaction is carried out directly between dehydroacetic acid and aromatic aldehydes in the presence of organic bases. The optimal conditions for the Knoevenagel reaction based on dehydroacetic acid and various aldehydes were determined. Twenty-one chalcones with substituents of different nature were synthesized. The composition and structure of the obtained compounds were determined. All characteristic signals of chalcones are present in the 1H NMR spectra of the obtained compounds registered in CDCl3 and DMSO-d6: OH groups in the range of 18.7–16.5 ppm, CH proton – 6.3–5.9 ppm, and methyl group of the pyran cycle 2.3–2.2 ppm. The corresponding signals of methine protons and aryl substituents are also present in the spectra. The most sensitive to solvent changes is the OH proton bound by an intramolecular hydrogen bond to the carbonyl group of the pyran ring. Signals in DMSO are usually shifted by 0.1–1.0 ppm in a stronger field compared to CDCl3 for dehydroacetic acid and chalcones based on it. CH proton signals are shifted by approximately 0.3 ppm in a weaker field, and the signals of the protons of the methyl group are almost insensitive to the solvent. The optical properties of obtained compounds were investigated in DMF, MeOH, MeCN. The synthesized chalcones absorb light in the visible range 330–490 nm with molar extinction coefficients of 3.5–4.5. The solvatochromic effects for most of them are weak – the position of the maximum changes by less than 10 nm. The electron-donor substituents in the phenyl ring (-NMe2 and -NEt2) shift the absorption ma­ximum bathochromically by almost 100 nm compared to others in all investigated solvents.

https://doi.org/10.33609/2708-129X.87.05.2021.3-14
№1

References

Hale William J. The constitution of dehydroacetic acid. J. Am. Chem. Soc. 1911. 33(7): 1119–1135. https://doi.org/10.1021/ja02220a015

Bhat A.N., Jain B.D. Separation and de­ter­mination of uranium and thorium with 3-acetyl-4-hydroxy-coumarin. Talanta. 1960. 4: 13–16. https://doi.org/10.1016/ 0039-9140(60)80066-5

Dovbii Ya.M., Chernii V.Ya., Tretyako­va I.M., Gorski A.V., Starukhin A.S., Vol­kov S.V. Synthesis of dehydroacetic acid deri­vatives with chromophoric chain and their complexes with zirconium phthalocyanine. Ukr. Chem. Journ. 2015. 81(12): 79–82.

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: 259–261.

Bhat A.N., Jain B.D. Spectrophotometric studies of uranium (VI)-3-acetyl-4-hydroxycoumarin complex in ethanol. J. Inorg. Nucl. Chem. 1961. 23: 136–139. https://doi.org/10.1016/0022-1902(61)80095-X

Hsieh W.Y., Zaleski C.M.. Pecoraro V.L., Liu S. Mn(II) Complexes of Monoanio­nic Bidentate Chelators: The x-ray Crystal Structures of Mn(DHA)2(CH3OH)2 (DHA=Dehydroacetic Acid) and [Mn(ema)2 (H2O)]2 2H2O (Hema= 2-Ethyl-3-Hydroxy-4-Pyrone). Inorg. Chim. Acta. 2006. 359: 228–236. https://doi.org/10.1016/j.ica.

09.025

Chalaca M.Z., Figueroa-Villar J.D., Ellena J.A., Castellano E.E. Synthesis and structure of cadmium and zinc complexes of dehydroacetic acid. Inorg. Chim. Acta. 2002. 328: 45–52. https://doi.org/10.1016/S0020-1693(01)00672-7

Jilalat A., Al-Garadi W., Karrouchi K., Essassi E. Dehydroacetic acid (part 1): chemical and pharmacological properties. J. Mar. Chim. Heterocycl. 2017. 16: 1–47. https://doi.org/10.48369/IMIST.PRSM/jmch-v16i1.8199

Walker G. N. Reduction of Enols. New Synthesis of Certain Methoxybenzsuberenes via Hydrogenation of Dehydroacetic Acids. Journal of the American Chemical Society. 1956. 78: 3201–3205. https://doi.org/10.1021/ja01594a062

Rehse K., Rüther D. Einfluß der S-Oxidation auf anticoagulante Wirkungen bei 4-Hydroxycumarinen, 4-Hydroxy-2-pyronen und 1,3-Indandionen. Archiv der Pharmazie, 1984. 317: 262–267. https://doi.org/10.1002/ardp.19843170313

Yi Y. Y., He J. J., Su J. Q., Kong S. Z., Su J. Y., Li Y. C., Huang S. H., Li C. W., Lai X. P., Su Z. R. Synthesis and antimicrobial evaluation of pogostone and its analogues. Fitoterapia, 2013. 84: 135–139. https://doi.org/10.1016/j.fitote.2012.11.005

Aït-Baziz N., Rachedi Y., Chemat F., Hamdi M. Solvent Free Microwave-Assisted Knoevenagel Condensation of De­hydroacetic Acid with Benzaldehyde Derivatives. Asian Journal of Chemistry. 2008. 20: 2610–2622.

Rachedi Y., Hamdi M., Spéziale V. Synthesis of 4-Hydroxy 6-Methyl 3-β-Arylpropionyl 2-Pyrones by Selective Cata­lytic Hydrogenation of 3-Cinnamoyl 4-Hyd­roxy 6-Methyl 2-Pyrones. Synthetic Commun. 1989. 19: 3437–3442. https://doi.org/10.1080/00397918908052752

Sundar P. S., Gunasheela D. Synthesis, characterization and determination of antimicrobial activity of novel chalcones of 3-acetyl 4-hydroxy-6-methyl-2hpyran-2-one. Europ. J. Pharm. Med. Research. 2016. 3(7): 381–384.

Patange V., Arbad B. Synthesis, spectral, thermal and biological studies of transition metal complexes of 4-hydroxy-3-[3-(4-hydroxyphenyl)-acryloyl]-6-methyl-pyran-2-one. J. Serb. Chem. Soc. 2011. 76: 1237–1246. doi: 10.2298/JSC100531108P

Tambov K. V., Voevodina I. V., Mana­ev A. V., Ivanenkov Y. A.. Neamati N., Traven V. F. Structures and biological acti­vity of cinnamoyl derivatives of coumarins and dehydroacetic acid and their boron difluoride complexes. Russ. Chem. Bul. 2012. 61: 78–90. https://doi.org/10.1007/s11172-012-0012-y

Hanuza J., Ptak M., Lisiecki R., Janczak J., Kwocz A., Kucharska E., Roszak S., Ryba-Romanowski W., Mączka M., Hermanowicz K., Macalik L. Spectral and energetic transformation of femtosecond light impulses in the Eu3+ complex with dehydroacetic acid. J. Lumines. 2018. 198: 471–481. https://doi.org/10.1016/j.jlumin. 2018.02.067

Wu B., Wang Y., Chen S., Wang M., Ma M., Shi Y., Wang X. Stability, mechanism and unique “zinc burning” inhibition synergistic effect of zinc dehydroacetate as thermal stabilizer for poly(vinyl chloride). Polymer Degradation and Stability. 2018. 152: 228–234. DOI: 10.1016/j.polymdegradstab.2018.04.025

Malik B.A., Mir J.M. Synthesis, characterization and DFT aspects of some oxovanadium(IV) and manganese(II) complexes involving dehydroacetic acid and β-diketones. J.Coord. Chem. 2018. 71: 104–119. https://doi.org/10.1080/00958972.2018.1429600

Vashisht D., Sharma S., Kumar R., Saini V., Saini V., Ibhadon A., Sahoo S.C., Sharma S., Mehta, S.K., Kataria, R. Dehydroacetic acid derived Schiff base as selective and sensitive colorimetric chemosensor for the detection of Cu(II) ions in aqueous medium. Microchemical Journal. 2020. 155: 1–10. https://doi.org/10.1016/j.microc.2020.104705

Chen K.-H., Lin T.-H., Hsu T.-E., Li Y.-J., Chen G.-H., Leu W.-J., Guh J.-H., Lin C.-H., Huang J.-H. Ruthenium (II) complexes containing dehydroacetic acid and its imine derivative ligands. Synthesis, characterization and cancer cell growth anti-proli­feration activity (GI50) study. J. Organometall. Chem. 2018. 871: 150–158. https://doi.org/10.1016/j.jorganchem.2018.07.014

Kendur U., Chimmalagi G.H., Patil S.M., Gudasi K.B., Frampton C.S. Synthesis, structural characterization and biological evaluation of mononuclear transition metal complexes of zwitterionic dehydroacetic acid N aroylhydrazone ligand. Appl. Organometall. Chem. 2018. 32: 1–21. https://doi.org/10.1002/aoc.4278

Emam S.M., El-Tabl A.S., Ahmed H.M., Emad E.A. Synthesis, structural characterization, electrochemical and biological studies on divalent metal chelates of a new ligand derived from pharmaceutical preservative, dehydroacetic acid, with 1,4-diaminobenzene. Arabian J. Chem. 2017. 10: S3816 – S3825. DOI: 10.1016/j.ara­bjc.2014.05.019

Devi J., Devi S., Kumar A. Synthesis, spectral, and in vitro antimicrobial studies of organosilicon(IV) complexes with Schiff bases derived from dehydroacetic acid. Monatshefte fur Chemie. 2016. 147: 2195–2207. https://doi.org/10.1007/s00706-016-1720-z

Benferrah N., Hammadi M., Philouze C., Berthiol F., Thomas F. Copper(II) complex of a Schiff base of dehydroacetic acid: Characterization and aerobic oxidation of benzyl alcohol. Inorg. Chem. Commun. 2016. 72: 17–22. https://doi.org/10.1016/j.inoche.2016.07.020

Mir J.M., Rajak D.K., Maurya R.C. Oxo­vanadium(IV) complex of 8 hydroxy qui­no­line and 3-acetyl-6-methyl-2H-pyran-2,4(3H)-dione: Experimental, theoretical and antibacterial evaluation. Journal of King Saud University – Science. 2019. 31: 1034–1041. https://doi.org/10.1016/j.jksus.2018.03.023

Sarhan A.M., Elsayed S.A., Mashaly M.M., El-Hendawy A.M. Oxovanadium(IV) and ruthenium(II) carbonyl complexes of ONS-donor ligands derived from dehydroacetic acid and dithiocarbazate: Synthesis, characterization, antioxidant activity, DNA binding and in vitro cytotoxicity. Appl. Organometall. Chem. 2019. 33: 1–16. № e4655. https://doi.org/10.1002/aoc.4655

Saini S., Pal R., Gupta A.K., Beniwal V. Synthesis, characterization, DNA photocleavage and antibacterial study of a no­vel dehydroacetic acid based hydrazone Schiff’s base transition metal complexes. Res. J. Chem. Environ. 2017. 21: 49–57.

Nechak R., Bouzroura S. A., Benmalek Y., Salhi L., Martini S. P., Morizur V., Du­nach, E., Kolli, B. N. Synthesis and Antimicrobial Activity Evaluation of Novel 4-Thiazolidinones Containing a Pyrone Moiety. Synthetic Commun. 2015. 45: 262–272. https://doi.org/10.1080/00397911.2014.970278

Swamy P. G., Sri B. R., Giles D., Shashid­har B., Das A. K., Agasimundin Y. Synthesis, anticancer, and molecular docking studies of pyranone derivatives. Med. Chem. Research. 2013. 22: 4909–4919. https://doi.org/10.1007/s00044-013-0478-7

Kashar T. I., El-Sehli A. H. Synthesis, cha­racterization, antimicrobial and anticancer activity of Zn(II), Pd(II) and Ru(III) complexes of dehydroacetic acid hydrazine. Journal of Chemical and Pharmaceutical Research. 2013. 5(11): 474–483.

Thaisrivongs S., Romero D. L., Tommasi R. A., Janakiraman M. N., Stroh­bach J. W., Turner S. R., Biles C., Morge R. R., Johnson P. D., Aristoff P. A., Tomich P. K., Lynn J. C., Horng M. M., Chong K. T., Hinshaw R. R., Howe W. J., Finzel B. C., Watenpaugh K. D. Structure-Based Design of HIV Protease Inhi­bitors: 5,6-Dihydro-4-hydroxy-2-pyrones as Effective, Nonpeptidic Inhibitors. J. Med. Chem. 1996. 39: 4630–4642. doi: 10.1021/jm960228q.

Defant A., Mancini I., Tomazzolli R., Balzarini J. Design, Synthesis, and Biological Evaluation of Novel 2H-Pyran-2-one Derivatives as Potential HIV-1 Reverse Transcriptase Inhibitors. Archiv Der Pharmazie. 2014. 348: 23–33. https://doi.org/10.1002/ardp.201400235

Kovalska V., Chernii S., Losytskyy M., Dovbii Y., Tretyakova I., Czerwieniec R., Chernii V., Yarmoluk S., Volkov S. β-ketoenole dyes: Synthesis and study as fluorescent sensors for protein amyloid aggregates. Dyes and Pigments. 2016. 132: 274–281. DOI: 10.1016/j.dyepig.2016.04.053

Kovalska V., Chernii S., Losytskyy M., Tretyakova I., Dovbii Y., Gorski A., Chernii V., Czerwieniec R., Yarmoluk S. Design of functionalized β-ketoenole derivatives as efficient fluorescent dyes for detection of amyloid fibrils. New Journal of Chemistry. 2018. 42 (16): 13308-13318. DOI: 10.1039/c8nj01020j

Moshynets O., Chernii S., Chernii V., Losytskyy M., Karakhim S., Czerwieniec R., Pekhnyo V., Yarmoluk S., Kovalska V. Flu­orescent β-ketoenole AmyGreen dye for visualization of amyloid components of bacterial biofilms. Methods and Applications in Fluorescence. 2020. 8 (3): 035006. DOI: 10.1088/2050-6120/ab90e0

Downloads

Download data is not yet available.