vuzbiochemiИзвестия вузов. Прикладная химия и биотехнологияProceedings of Universities. Applied Chemistry and Biotechnology2227-29252500-1558ИРНИТУ10.21285/achb.1014RUQCNSvuzbiochemi-1578Research ArticleХИМИЧЕСКИЕ НАУКИCHEMICAL SCIENCESИзучение строения продуктов взаимодействия L-аскорбиновой кислоты с п-аминоацетанилидомStructural analysis of products arising from the interaction between L-ascorbic acid and p-aminoacetanilidehttps://orcid.org/0000-0002-0880-5474ЧерепановИ. С.CherepanovI. S.

Черепанов Игорь Сергеевич, к.х.н., доцент

426034, г. Ижевск, ул. Университетская, 1

Igor S. Cherepanov, Cand. Sci. (Chemistry), Associate Professor

1, Universitetskaya St., Izhevsk, 426034

cherchem@mail.ruhttps://orcid.org/0009-0005-4555-2196ТарасоваД. А.TarasovaD. A.

Тарасова Дарья Александровна, ассистент

426034, г. Ижевск, ул. Университетская, 1

Dar’ya A. Tarasova, Assistant

1, Universitetskaya St., Izhevsk, 426034

dashatarasova20@mail.ruhttps://orcid.org/0009-0002-6602-4008ЕгороваА. И.EgorovaA. I.

Егорова Алина Игоревна, ассистент

426034, г. Ижевск, ул. Университетская, 1

Alina I. Egorova, Assistant

1, Universitetskaya St., Izhevsk, 426034

ealiapril@gmail.comУдмуртский государственный университетРоссияUdmurt State UniversityRussian Federation202519122025154446455Copyright © Черепанов И.С., Тарасова Д.А., Егорова А.И., 20252025Черепанов И.С., Тарасова Д.А., Егорова А.И.Cherepanov I.S., Tarasova D.A., Egorova A.I.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://vuzbiochemi.elpub.ru/jour/article/view/1578

Продукты реакций L-аскорбиновой кислоты с различными азотсодержащими биологически активными веществами открывают пути к получению препаратов нового типа, перспективных к применению в фармацевтической, пищевой и косметической индустрии. В настоящей работе изучено взаимодействие L-аскорбиновой кислоты с п-аминоацетанилидом в этанольной среде при варьируемом (1:1 и 1:2) соотношении компонентов. Получение целевых продуктов проводили термостатированием водно-этанольных растворов, содержащих заданные количества компонентов (50 °С, 1 ч) с последующим медленным удалением растворителя в течение 24 ч. Непосредственно после термостатирования реакционные системы в виде тонких пленок на KBr-подложках исследовали методом колебательной спектроскопии. После медленного удаления растворителя промытые безводным эфиром и его смесью с этанолом твердые фазы изучали при помощи инфракрасной спектроскопии в KBr-матрице. Анализ колебательных спектров реакционной системы 1:1 показал, что в ходе термостатирования не происходит образования ионного ассоциата, последующее удаление растворителя приводит к выделению твердой фазы продукта сокристаллизации, формирование которого подтверждено анализом спектров средней и ближней инфракрасной области. Установлено, что в реакционной системе при соотношении компонентов 1:2 на стадии термостатирования происходит формирование основания Шиффа по С 3 -фрагменту аскорбиновой кислоты, перегруппировывающегося впоследствии при медленном удалении растворителя в 3-замещенное N-производное аскорбиновой кислоты (3-дезокси-3-(п-ацетамидофениламино)-L-аскорбиновую кислоту). Характер электронных спектров обеих реакционных систем указывает на незначительное протекание побочных процессов меланоидинообразования в выбранных условиях эксперимента. Структурные аналоги выделенных продуктов, согласно литературным данным, характеризуются достаточной в сравнении с алифатическими производными устойчивостью, а также заметными антиоксидантными свойствами, что предполагает актуальность их дальнейшего изучения.

Products of reactions between L-ascorbic acid and various nitrogen-containing biologically active substances can be used to develop new preparations with promising applications in the pharmaceutical, food, and cosmetic industries. The present study examined the interaction of L-ascorbic acid with p-aminoacetanilide in ethanol medium at component ratios of 1:1 and 1:2. The target products were obtained by controlling the temperature of aqueous ethanol solutions containing the specified amounts of components (50 °С, 1 h), which was followed by slow solvent removal for 24 h. Immediately after the temperature control stage, the reaction systems, in the form of thin films on KBr substrates, were analyzed via vibrational spectroscopy. Following slow solvent removal, the solid phases washed with anhydrous ether and its mixture with ethanol were studied in a KBr matrix using infrared spectroscopy. The vibrational spectra of the 1:1 reaction system revealed that no ionic associate is formed during the temperature control stage; subsequent solvent removal leads to the release of the solid phase of co-crystallization product, whose formation is confirmed by analysis of the mid- and near-infrared spectra. With the 1:2 component ratio, the reaction system was found to form a Schiff base at the C 3 of ascorbic acid during the temperature control stage, which subsequently rearranged during slow solvent removal into a 3-substituted N-derivative of ascorbic acid (3-deoxy-3-(p-acetamidophenylamino)-L-ascorbic acid). The electronic spectra of both reaction systems indicate insignificant side processes of melanoidin formation under the selected experimental conditions. According to published sources, the structural analogs of released products are characterized by sufficient stability compared to aliphatic derivatives, as well as notable antioxidant properties, which indicates the importance of their further study.

L-аскорбиновая кислотап-аминоацетанилидэлектронные спектрыИК-спектрысинтезантиоксидантная активностьL-ascorbic acidp-aminoacetanilideelectronic spectraIR spectrasynthesisantioxidant activityReferencesSpizzirri U., Garullo G., De Cicco L., Crispini A., Scarpelli F., Restuccia D., et al. Synthesis and characterization of a (+)-catechin and L(+)-ascorbic acid cocrystal as a new functional ingredient for tea drink // Heliyon. 2019. Vol. 5, no. 8. P. e02291. DOI: 10.1016/j.heliyon.2019.e02291.Spizzirri U., Garullo G., De Cicco L., Crispini A., Scarpelli F., Restuccia D., et al. Synthesis and characterization of a (+)-catechin and L(+)-ascorbic acid cocrystal as a new functional ingredient for tea drink. Heliyon. 2019;5(8):e02291. DOI: 10.1016/j.heliyon.2019.e02291.Levy R., Okun Z., Shpigelman A. The influence of chemical structure and the presents of ascorbic acid on anthocyanins stability and spectral properties in purified model systems // Foods. 2019. Vol. 8, no. 6. P. 207. DOI: 10.3390/foods8060207.Levy R., Okun Z., Shpigelman A. The influence of chemical structure and the presents of ascorbic acid on anthocyanins stability and spectral properties in purified model systems. Foods. 2019;8(6):207. DOI: 10.3390/foods8060207.Inoue Y., Horage M., Suzuki R., Niiyama D., Urano R., Ando S., et al. Study on complexation of ascorbic acid derivatives with γ-cyclodextrin // International Journal of Pharmacy. 2017. Vol. 7, no. 1. P. 9–21.Inoue Y., Horage M., Suzuki R., Niiyama D., Urano R., Ando S., et al. Study on complexation of ascorbic acid derivatives with γ-cyclodextrin. International Journal of Pharmacy. 2017;7(1):9-21.Chanphai P., Tajmir-Riahi H. Conjugation of vitamin C with serum proteins: a potential application for vitamin delivery // International Journal of Biological Macromolecules. 2019. Vol. 137. P. 966–972. DOI: 10.1016/j.ijbiomac.2019.07.059.Chanphai P., Tajmir-Riahi H. Conjugation of vitamin C with serum proteins: a potential application for vitamin delivery. International Journal of Biological Macromolecules. 2019;137:966-972. DOI: 10.1016/j.ijbiomac.2019.07.059.Palanisamy V., Sanphui P., Palanisamy K., Prakash M., Bansail A.K. Design of ascorbic acid eutectic mixtures with sugars to inhibit oxidative degradation // Frontiers in Chemistry. 2022. Vol. 10. P. 754269. DOI: 10.3389/fchem.2022.754269.Palanisamy V., Sanphui P., Palanisamy K., Prakash M., Bansail A.K. Design of ascorbic acid eutectic mixtures with sugars to inhibit oxidative degradation. Frontiers in Chemistry. 2022;10:754269. DOI: 10.3389/fchem.2022.754269.Zhang H., Zeng H., Li M., Song Y., Tian S., Xiong J., et al. Novel ascorbic acid co-crystal formulations for improved stability // Molecules. 2022. Vol. 27, no. 22. P. 7998. DOI: 10.3390/molecules27227998.Zhang H., Zeng H., Li M., Song Y., Tian S., Xiong J., et al. Novel ascorbic acid co-crystal formulations for improved stability. Molecules. 2022;27(22):7998. DOI: 10.3390/molecules27227998.Farias M.D.P., Albuquerque P.B.S., Soares P.A.G., de Sá D.M.A.T., Vicente A.A., Carneiro-da-Cunha M.G. Xyloglucan from Hymenaea courbaril var. courbaril seeds as encapsulating agent of L-ascorbic acid // International Journal of Biological Macromolecules. 2018. Vol. 107. P. 1559–1566. DOI: 10.1016/j.ijbiomac.2017.10.016.Farias M.D.P., Albuquerque P.B.S., Soares P.A.G., de Sá D.M.A.T., Vicente A.A., Carneiro-da-Cunha M.G. Xyloglucan from Hymenaea courbaril var. courbaril seeds as encapsulating agent of L-ascorbic acid. International Journal of Biological Macromolecules. 2018;107:1559-1566. DOI: 10.1016/j.ijbiomac.2017.10.016.Garnero C., Longhi M. Study of ascorbic acid interaction with hydroxypropyl-β-cyclodextrin and triethanolamine, separately and in combination // Journal of Pharmaceutical and Biomedical Analysis. 2007. Vol. 45, no. 4. P. 536–545. DOI: 10.1016/j.jpba.2007.07.030.Garnero C., Longhi M. Study of ascorbic acid interaction with hydroxypropyl-β-cyclodextrin and triethanolamine, separately and in combination. Journal of Pharmaceutical and Biomedical Analysis. 2007;45(4):536-545. DOI: 10.1016/j.jpba.2007.07.030.Xavier A., Raj M., Marie J. Synthesis and characterization of an aminoacetophenone-based Schiff base and its interaction studies with ascorbic acid // Journal of Chemical and Pharmaceutical Research. 2012. Vol. 4, no. 1. P. 669–672.Xavier A.J.M., Raj M.A., Marie J.M. Synthesis and spectral characterization of an aminoacetophenone-based Schiff base and its interaction studies with ascorbic acid. Journal of Chemical and Pharmaceutical Research. 2012;4(1):669-672.Сарыбаева Б.Д., Пищугин Ф.В., Тулебердиев И.Т. Кинетика и механизм взаимодействия L-аскорбиновой кислоты с азотсодержащими органическими соединениями // Научное обозрение. Международный научно-практический журнал. 2017. N 3. С. 12. EDN: ZGIVYP.Sarybayeva B.D, Pishchugin F.V, Tuleberdiev I.T. Kinetics and the mechanism of interaction of L-ascorbic acid with nitrogen-containing organic compounds. Nauchnoe obozrenie. Mezhdunarodnyi nauchno-prakticheskii zhurnal. 2017;3:66. (In Russian). EDN: ZGIVYP.Pischetsrieder M., Larisch B., Muller U., Severin T. Reaction of ascorbic acid with aliphatic amines // Journal of Agricultural and Food Chemistry. 1995. Vol. 43, no. 12. P. 3004–3006. DOI: 10.1021/jf00060a002.Pischetsrieder M., Larisch B., Muller U., Severin T. Reaction of ascorbic acid with aliphatic amines. Journal of Agricultural and Food Chemistry. 1995;43(12):3004-3006. DOI: 10.1021/jf00060a002.Dikusar E.A., Kozlov N.G., Mel’nichuk L.A. Salts of L-ascorbic acid with certain substituted amines and triphenylphosphine // Chemistry of Natural Compounds. 2004. Vol. 40. P. 406-407. DOI: 10.1023/B:CONC.0000048259.21776.2e.Dikusar E.A., Kozlov N.G., Mel’nichuk L.A. Salts of L-ascorbic acid with certain substituted amines and triphenylphosphine. Chemistry of Natural Compounds. 2004;40:406-407. DOI: 10.1023/B:CONC.0000048259.21776.2e.Малинкина О.Н., Провозина А.А., Шиповская А.Б. Оценка химического взаимодействия гидрохлорида хитозана с аскорбиновой кислотой методами ИК- и ЯМР-спектроскопии // Известия Саратовского университета. Новая серия. Серия «Химия. Биология. Экология». 2014. Т. 14. N 3. С. 20–24. EDN: SXUADF.Malinkina O.N., Provozina A.A., Shipovskaya A.B. Evaluation of the chemical interaction between chitosan hydrochloride and ascorbic acid by IR and NMR spectroscopy. Izvestiya of Saratov University. Chemistry. Biology. Ecology. 2014;14(3):20-24. (In Russian). EDN: SXUADF.Черепанов И.С. Синтез и антиокислительная активность продуктов конденсации D-глюкозы с п-аминоацетанилидом // Химия и технология органических веществ. 2020. N 3. С. 71–78. DOI: 10.54468/25876724_2020_3_71. EDN: ZFCPUG.Cherepanov I.S. Synthesis and antioxidative activity of D-glucose - p-aminoacetanilide condensation products. Chemistry and Technology of Organic Substances. 2020;3:71-78. (In Russian). DOI: 10.54468/25876724_2020_3_71. EDN: ZFCPUG.Abraham J.P., Sajan D., Hubert Joe I., Jayakumar J.S. Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of p-aminoacetanilide // Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2008. Vol. 71, no. 2. P. 355–367. DOI: 10.1016/j.saa.2008.01.010.Abraham J.P., Sajan D., Hubert Joe I., Jayakumar J.S. Molecular structure, spectroscopic studies and first-order molecular hyperpolarizabilities of p-aminoacetanilide. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy. 2008;71(2):355-367. DOI: 10.1016/j.saa.2008.01.010.Черепанов И.С., Корепанова Я.С. Поведение антиоксидантов ряда N-гликозиларилдиаминов в условиях окислительного стресса // Технология и товароведение инновационных пищевых продуктов. 2021. N 1. С. 3–7. DOI: 10.33979/2219-8466-2021-66-1-3-7. EDN: VIONRL.Cherepanov I.S., Korepanova Ya.S. Behavior of N-glycosylaryldiamine antioxidants under oxidative stress conditions. Technology and merchandising of the innovative foodstuff. 2021;1:3-7. (In Russian). DOI: 10.33979/2219-8466-2021-66-1-3-7. EDN: VIONRL.Пирниязов К.К., Анварова Г.К., Рашидова С.Ш. Влияние условий синтеза на комплексообразование хитозана с аскорбиновой кислотой // Известия Уфимского научного центра Российской академии наук. 2018. N 3. С. 72–74. EDN: XWQPKH.Pirniyazov K.K., Anvarova G.K., Rashidova S.Sh. Effect of synthesis conditions on the complexation of chitosan with ascorbic acid. Proceedings of the RAS Ufa Scientific Centre. 2018;3:72-74. (In Russian). EDN: XWQPKH.Casian T., Reznek A., Vonica-Gligor A.L., Van Renterghem J., De Beer T., Tomuță I. Development, validation and comparison of near infrared and Raman spectroscopic methods for fast characterization of tablets with amlodipine and valsartan // Talanta. 2017. Vol. 167. P. 333–343. DOI: 10.1016/j.talanta.2017.01.092.Casian T., Reznek A., Vonica-Gligor A.L., Van Renterghem J., De Beer T., Tomuță I. Development, validation and comparison of near infrared and Raman spectroscopic methods for fast characterization of tablets with amlodipine and valsartan. Talanta. 2017;167:333-343. DOI: 10.1016/j.talanta.2017.01.092.Dabbagh H.A., Azami F., Farrokhpour H., Chermahini N. UV-Vis, NMR and FTIR spectra of tautomers of vitamin C. Experimental and DFT calculation // Journal of the Chilean Chemical Society. 2014. Vol. 59, no. 3. P. 2248–2254. DOI: 10.4067/S0717-97072014000300013.Dabbagh H.A., Azami F., Farrokhpour H., Chermahini N. UV-Vis, NMR and FTIR spectra of tautomers of vitamin C. Experimental and DFT calculation. Journal of the Chilean Chemical Society. 2014;59(3):2248-2254. DOI: 10.4067/S0717-97072014000300013.Ferrer E., Williams P., Baran E. Interaction of vanadyl (IV) cation with L-ascorbic acid and related system // Zeitschrift für Naturforschung B. 1998. Vol. 53, no. 2. P. 256–262. DOI: 10.1515/znb-1998-0220.Ferrer E., Williams P., Baran E. Interaction of vanadyl (IV) cation with L-ascorbic acid and related system. Zeitschrift für Naturforschung B. 1998;53(2):256-262. DOI: 10.1515/znb-1998-0220.Lohmann W., Pagel D., Penka V. Structure of ascorbic acid and its biological activity. Determination of the conformation of ascorbic acid and isoascorbic acid by infrared and ultraviolet investigation // European Journal of Biochemistry. 1984. Vol. 138, no. 3. P. 479–480. DOI: 10.1111/j.1432-1033.1984.tb07941.x.Lohmann W., Pagel D., Penka V. Structure of ascorbic acid and its biological activity. Determination of the conformation of ascorbic acid and isoascorbic acid by infrared and ultraviolet investigation. European Journal of Biochemistry. 1984;138(3):479-480. DOI: 10.1111/j.1432-1033.1984.tb07941.x.Saleh T.A.-K., Al-Samarrai R.R.H., Abdul-Razzaq N.E. The antioxidant and antimicrobial activity for some new synthesized Schiff base derived from ascorbic acid // International Journal of Research in Pharmaceutical Sciences. 2019. Vol. 10, no. 2. P. 1510–1515. DOI: 10.26452/ijrps.v10i2.730.Saleh T.A.-K., Al-Samarrai R.R.H., Abdul-Razzaq N.E. The antioxidant and antimicrobial activity for some new synthesized Schiff base derived from ascorbic acid. International Journal of Research in Pharmaceutical Sciences. 2019;10(2):1510-1515. DOI: 10.26452/ijrps.v10i2.730.Tajmir-Riahi H.A. Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution // Journal of Inorganic Biochemistry. 1990. Vol. 40, no. 2. P. 181–188. DOI: 10.1016/0162-0134(90)80051-x.Tajmir-Riahi H.A. Coordination chemistry of vitamin C. Part I. Interaction of L-ascorbic acid with alkaline earth metal ions in the crystalline solid and aqueous solution. Journal of Inorganic Biochemistry. 1990;40(2):181-188. DOI: 10.1016/0162-0134(90)80051-x.Onoda H., Inoue Y., Ezawa T., Murata I., Chantadee T., Limmatvapirat S., et al. Preparation and characterization of triamterene complex with ascorbic acid derivatives // Drug Development and Industrial Pharmacy. 2020. Vol. 46, no. 12. P. 2032–2040. DOI: 10.1080/03639045.2020.1842439.Onoda H., Inoue Y., Ezawa T., Murata I., Chantadee T., Limmatvapirat S., et al. Preparation and characterization of triamterene complex with ascorbic acid derivatives. Drug Development and Industrial Pharmacy. 2020;46(12):2032-2040. DOI: 10.1080/03639045.2020.1842439.Wang L., Choi W.M., Chung J.S., Hur S.H. Multicolor emitting N-doped carbon dotes derived from ascorbic acid and phenylenediamine precursors // Nanoscale Research Letters. 2020. Vol. 15. P. 222. DOI: 10.1186/s11671-020-03453-3.Wang L., Choi W.M., Chung J.S., Hur S.H. Multicolor emitting N-doped carbon dotes derived from ascorbic acid and phenylenediamine precursors. Nanoscale Research Letters. 2020;15:222. DOI: 10.1186/s11671-020-03453-3.Wang P., Wang Y., Sun Y., Cao Z., Zhu W., Wang H. Thermal and spectroscopic studies of the thermal-oxidation stabilities of lubricants // Journal of Applied Spectroscopy. 2021. Vol. 88. P. 847–854. DOI: 10.1007/s10812-021-01249-6.Wang P., Wang Y., Sun Y., Cao Z., Zhu W., Wang H. Thermal and spectroscopic studies of the thermal-oxidation stabilities of lubricants. Journal of Applied Spectroscopy. 2021;88:847-854. DOI: 10.1007/s10812-021-01249-6.

The authors declare that there are no conflicts of interest present.