SPECTRAL-LUMINESCENT PROPERTIES OF SOME NEW DIHYDROXY-2H-1-BENZOPYRAN-2-ONES SYNTHESIZED BASED ON 2,4,6-TRIHYDROXYTOLUENE

Keywords: 2,4,6-trihydroxytoluene, methylphloroglucinol, 2H-1-benzopyrans, luminescence

Abstract

2,4,6-trihydroxytoluene (methylphloroglucinol) is a promising reagent in organic synthesis, after development out getting it from 2,4,6-trinitrotoluene. We previously synthesized of derivatives of 5,7-dihydroxy-2H-1-benzopyran-2-ones by the interaction of 2,4,6-trihydroxytoluene and 2,4,6 -trihydroxy-3-methylbenzoic acid with polyfunctional carbonyl compounds. The first time, a detailed analysis of the electronic absorption and fluorescence spectra of derivatives of 5,7-dihydroxy-2H-1-benzopyran-2-ones is carried out. In the electronic absorption spectra of the studied compounds, the absorption in the long-wavelength region of the spectrum is determined by electronic transitions with intramolecular charge carry. The possibility of controlling the bathochromic or hypsochromic shift of the long-wavelength absorption band by introducing substituents of various electronic nature into the molecule has been revealed. It was shown that some of the studied compounds have pronounced luminescence in the blue-green region of the spectrum (390–508 nm) with a quantum yield of 9–40%. The highest quantum yield (38%) was achieved when the 5,7-dihydroxy-2H-1-benzopyran-2-one carboxyl group was introduced into position 6. The bromination of this compound leads to a decrease in the quantum yield to 9.5 % The introduction into the 3 position of 5,7-dihydroxy-4,8-dimethylchromen-2-one phenyl substituted fragment along with O-acylation leads to a sharp decrease in the quantum yield. It is concluded that the studied objects are promising as basic structures for the search for new biosensors.

References

Kashaev V.A., Khisamutdinov G.Kh., Shevelev S.A., Valeshnii S.I., Shakhnes A.Kh., Bavrina A.P. Preparation of 2,4,6-triaminotoluene and its salts with inorganic acids from 2,4,6-trinitrotoluene. Theor. Found. Chem. Eng. 2008. V. 42. N 5. P. 650–656. DOI: 10.1134/S004057950805028X.

Kobrakov K.I., Kuznetsov D.N., Ruchkina A.G., Sharpar N.M. Synthesis and properties azocompounds based on nitroanilines - derivatives of 2,4,6-trinitrotoluene and 1,3,5-trinitrobenzene. Khim. Tekhnol. 2019. V. 20. N 10. P. 440-444 (in Russian). DOI: 10.31044/1684-5811-2019-20-10-440-444.

Ushkarov V.I., Kobrakov K.I., Alafinov A.I., Shevelev S.A., Shakhnes A.Kh. Methylphloroglucinol as an available semiproduct for azo dye synthesis. Theor. Found. Chem. Eng. 2007. V. 41. N 5. P. 671-674. DOI: 10.1134/S0040579507050375.

Kobrakov K.I., Alafinov A.I., Stankevich G.S., Ruchkina A.G., Volyansky O.V., Kovalchukova O.V. A new inter-mediate product for perspective azo-dyes on the basis of 2,4,6-trinitrotoluene. Izv. Vyssh. Uchebn. Zaved. Teknol. Tekstil. Prom-ti. 2012. V. 339. N 3. P. 142-144 (in Russian).

Alafinov A.I., Kobrakov K.I., Kuznetsov D.N., Dmitrieva M.B. Synthesis of new nitrogen of methyl phluoroglucinol – potential dyes and pigments for textiles. Butlerov. Soobshch. 2013. V. 34. N 3. P. 93-97 (in Russian).

Bobylev S.S., Kobrakov K.I., Kuznetsov D.N., Ruchkina A.G., Shevelev S.A., Shakhnes A.Kh., Fakhrutdinov A.N. Synthesis and transformations of dihydroxy-2H-1-benzo-pyran-2-ones. Russ. Chem. Bull. 2015. V. 64. N 1. P. 154-160. DOI: 10.1134/S1070428015110093.

Bobylev S.S., Kuznetsov D.N., Kobrakov K.I., Ruchkina A.G., Fakhrutdinov A.N. Synthesis and transformations of dihydroxy-2H-1-benzopyran-2-ones. Russ. J. Org. Chem. 2015. V. 51. N 11. P. 1572–1577. DOI: 10.1134/S1070428015110093.

Shubin D.A., Bobylev S.S., Kuznetsov D.N., Ruchkina A.G., Kobrakov K.I. Synthesis and some properties of 2,4,6-trihydroxy-3-methylbenzoic acid. Russ. Chem. Bull. 2019. V. 68. N 1. P. 74–78. DOI: 10.1007/s11172-019-2418-2.

Melyshenkova V.V., Kuznetsov D.N., Ruchkina A.G., Kobrakov K.I. Synthesis of new acridine-9-carboxylic acid derivatives. Russ. Chem. Bull. 2018. V. 67. N 5. P. 878-883. DOI: 10.1007/s11172-018-2152-1.

Wilze K., Johnson A. Handbook of Detergents, Chemistry, Production, and Application of Fluorescent Whitening Agents, Part F. Boca Raton: Taylor & Francis. CRC Press. 2007. 593 p.

Yan L., Li R., Shen W., Qi Z. Multiple-color AIE coumarin-based Schiff bases and potential application in yellow OLEDs. J. Lumin. 2018. V. 194. P. 151–155. DOI: 10.1016/j.jlumin.2017.10.032.

Chang C., Cheng H., Lu Y., Tien K., Lin H., Lin C., Yang C., Wu C. Enhancing color gamut of white OLED displays by using microcavity green pixels. Org. Electron. 2010.

V. 11. N 2. P. 247-254. DOI: 10.1016/j.orgel.2009.11.002.

Yu T., Zhang P., Zhao Y., Zhang H., Meng J., Fan D. Synthesis, characterization and high-efficiency blue electroluminescence based on coumarin derivatives of 7-diethylamino-coumarin-3-carboxamide. Org. Electron. 2009. V. 10. N 4.

P. 653-660 DOI: 10.1016/j.orgel.2009.02.026.

Dsouza R.N., Pischel U., Nau W.M. Fluorescent dyes and their supramolecular host/guest complexes with macrocycles in aqueous solution. Chem. Rev. 2011. V. 111. N 12. P. 7941–7980. DOI: 10.1021/cr200213s.

Murphree S.S. Heterocyclic dyes: Preparation, properties, and applications. Prog. Heterocycl. Chem. 2011. V. 22. P. 21-58. DOI: 10.1016/S0959-6380(11)22002-6.

Wagner B.D. The Use of coumarins as environmentally-sensitive fluorescent probes of heterogeneous inclusion sys-tems. Molecules. 2009. V. 14. P. 210–237. DOI: 10.3390/molecules14010210.

Sameiro M., Gonçalves T. Fluorescent labeling of biomole-cules with organic probes. Chem. Rev. 2009. V. 109. N 1. P. 190–212. DOI: 10.1021/cr0783840.

Cao D., Liu Z., Verwilst P., Koo S., Jangjili P., Kim J-S., Lin W. Coumarin-based small-molecule fluorescent chemosensors. Chem. Rev. 2019. V. 119. N 18. P. 10403–10519. DOI: 10.1021/acs.chemrev.9b00640.

Antina E.V., Berezin M.B., Guseva G.B., Ksenofontov A.A., V’yugin A.I. Zinc(II) bis(dipyrrometenate)s as new fluores-cent chemosensors of N-and O-containing analytes. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. 2016. V. 59. N 6. P. 22-27. DOI: 10.6060/tcct.20165906.5398k

Kuznetsova N.A., Kalia O.L. The photochemistry of cou-marins. Russ. Chem. Rev. 1992. V. 61. N 7. P. 1243-1267. DOI: 10.1070/RC1992v061n07ABEH000992.

Martynov V.I., Pakhomov A.A., Popova N.V., Deyev I.E., Petrenko A.G. Synthetic fluorophores for visualizing bio-molecules in living systems. Acta Naturae. 2016. V. 8. N 4. P. 33–46. DOI: 10.32607/20758251-2016-8-4-33-46.

Published
2020-07-27
How to Cite
Kuznetsov, D., Kobrakov, K., & Bobylev, S. (2020). SPECTRAL-LUMINESCENT PROPERTIES OF SOME NEW DIHYDROXY-2H-1-BENZOPYRAN-2-ONES SYNTHESIZED BASED ON 2,4,6-TRIHYDROXYTOLUENE. ChemChemTech, 63(9), 37-42. https://doi.org/10.6060/ivkkt.20206309.6226
Section
CHEMISTRY (inorganic, organic, analytical, physical, colloid and high-molecular compounds)