chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2023-18-4-315-327chemicallytech-1988Research ArticleTHEORETICAL BASIS OF CHEMICAL TECHNOLOGYТЕОРЕТИЧЕСКИЕ ОСНОВЫ ХИМИЧЕСКОЙ ТЕХНОЛОГИИStructure of 2-nitro-2’-hydroxy-5’-methylazobenzene: Theoretical and spectroscopic studyСтруктура молекулы 2-нитро-2’-гидрокси-5’-метилазобензола: Теоретическое и спектральное исследованиеhttps://orcid.org/0000-0002-2878-0454ФедороваА. А.FedorovaA. A.

Федорова Анастасия Александровна, к.х.н., доцент кафедры Физической и коллоидной химии

153000, Иваново, Шереметевский пр., д. 7

Scopus Author ID 57206167763, ResearсherID AAE-9416-2019

Anastasiya A. Fedorova, Cand. Sci. (Chem.), Associate Professor, Department of Physical and ColloidalChemistry

7, pr. Sheremetevsky, Ivanovo, 153000

fedorova@isuct.ruhttps://orcid.org/0000-0001-8385-2732ЛефедоваО. В.LefedovaO. V.

Лефедова Ольга Валентиновна, д.х.н., профессор кафедры Физической и коллоидной химии

153000, Иваново, Шереметевский пр., д. 7

Scopus Author ID 6603866365, ResearсherID S-7806-2016

Olga V. Lefedova, Dr. Sci. (Chem.), Professor, Department of Physical and Colloidal Chemistry

7, pr. Sheremetevsky, Ivanovo, 153000

physchem.606@yandex.ruhttps://orcid.org/0000-0003-4433-3395ШлыковС. А.ShlykovS. A.

Шлыков Сергей Александрович, д.х.н., заведующий кафедрой Физической и коллоидной химии

153000, Россия, Иваново, Шереметевский пр., д. 7

Scopus Author ID 7004449118, ResearсherID W-2154-2017

Sergey A. Shlykov, Dr. Sci. (Chem.), Professor, Head of the Department of Physical and Colloidal Chemistry

7, pr. Sheremetevsky, Ivanovo, 153000

shlykov@isuct.ruИвановский государственный химико-технологический университетРоссияIvanovo State University of Chemistry and TechnologyRussian Federation202307102023184315327Copyright © Fedorova A.A., Lefedova O.V., Shlykov S.A., 20232023Федорова А.А., Лефедова О.В., Шлыков С.А.Fedorova A.A., Lefedova O.V., Shlykov S.A.Данная работа распространяется под лицензией Creative Commons Attribution 4.0.This work is licensed under a Creative Commons Attribution 4.0 License.https://www.finechem-mirea.ru/jour/article/view/1988Objectives

Objectives. 2-Hydroxy-nitroazobenzenes comprise reagents for the synthesis of heteroaromatic compounds, in the molecules of which the benzene and azole cycles are annulated. These reagents are widely used in the production of chemical products for various industries. In particular, 2-2’-hydroxy-5’-methylphenylbenzotriazole is used as an effective photo stabilizer for polystyrene and polyethylene. A promising method for its preparation is the liquid-phase catalytic hydrogenation of 2-nitro-2'-hydroxy-5'-methylazobenzene (2NAB). The aim of the present study was to establish the structure of 2NAB in solutions of different composition.

Methods

Methods. Theoretical calculations were carried out within the framework of the density functional theory at a temperature of 298.15 K for the gas phase at B3LYP/6-311++G(d, p) and M06-2X/6-311++G(d, p) levels; for hexane, 2-propanol, toluene at B3LYP/6-311++G(d, p) level using the conductor-like polarizable continuum model. An experimental study to determine the probable isomeric structure of 2NAB in various solvents, including sodium hydroxide (NaOH) and acetic acid (CH3COOH) additives, was carried out using infrared (IR) and ultraviolet (UV) spectroscopy.

Results

Results. The most probable structure of 2NAB isomers for the gas phase and a number of solvents was determined. Experimental and theoretical IR and UV spectra were obtained. The thermodynamic characteristics of the reaction of intramolecular proton transfer from –OH to –N=N– group in the gas phase were calculated.

Conclusions

Conclusions. A comparison of the experimental and calculated results supports the conclusion that the cis-isomer should be considered most probable for the gas phase. For the studied solutions, a trans-isomer of 2NAB with hydrogen bonds formed between the hydroxyl group hydrogen and the β-nitrogen atom of the azo group of dye molecule should be considered as the most likely structure. In the studied individual and binary solvents, prototropic equilibrium is shifted towards the azo form of the dye, while intramolecular proton transfer is possible only in aqueous diethylamine and dimethylformamide solutions with additions of NaOH. 

Цели

Цели. 2-Гидроксинитроазобензолы – реагенты синтеза гетероароматических соединений, в молекулах которых аннелированы бензольный и азольный циклы, широко использующиеся при производстве химических продуктов для различных областей промышленности. В частности, 2-2’-гидрокси-5’-метилфенилбензотриазол используется в качестве эффективного фотостабилизатора полистирола и полиэтилена. Перспективным методом его получения является жидкофазная каталитическая гидрогенизация 2-нитро-2’-гидрокси-5’-метилазобензола (2НАБ). Целью нашей работы стало установление структуры 2НАБ в растворах различного состава.

Методы

Методы. Теоретические расчеты проводились в рамках теории функционала плотности при температуре 298.15 К для газовой фазы на уровнях B3LYP/6-311++G(d, p) и M06-2X/6-311++G(d, p), для гексана, 2-пропанола, толуола на уровне B3LYP/6-311++G(d, p) с использованием континуальной модели сольватации. Экспериментальное изучение предполагаемого изомерного строения 2НАБ в различных растворителях, в том числе с добавками гидроксида натрия (NaOH) и уксусной кислоты (CH3COOH), проведено с помощью инфракрасной (ИК) и ультрафиолетовой (УФ) спектроскопии.

Результаты

Результаты. Определена наиболее вероятная структура изомеров 2НАБ для газовой фазы и ряда растворителей. Получены экспериментальные и теоретические ИК-, УФ-спектры исследуемых веществ. Рассчитаны термодинамические характеристики реакции внутримолекулярного переноса протона от –ОН к –N=N– группе в газовой фазе.

Выводы

Выводы. Сравнение экспериментальных и расчетных результатов позволило сделать заключение, что наиболее вероятным для газовой фазы следует считать цис-изомер, а для изученных растворов транс-изомер 2НАБ с водородными связями, образующимися между водородом гидроксигруппы и β-атомом азота азогруппы. В изученных индивидуальных и бинарных растворителях прототропное равновесие смещено в сторону азоформы красителя, а внутримолекулярный перенос протона возможен только в водных растворах диэтиламина и диметилформамила с добавками NaОН. 

2-нитро-2'-гидрокси-5'-метилазобензолвнутримолекулярный перенос протонаводородная связьИК-спектроскопияУФ-спектроскопияквантово-химические расчеты2-nitro-2'-hydroxy-5'-methylazobenzeneintramolecular proton transferhydrogen bondIR spectroscopyUV spectroscopyquantum chemical calculationsИсследование проведено с использованием ресурсов Центра коллективного пользования научным оборудованием Ивановского государственного химикотехнологического университета при поддержке Министерства науки и высшего образования Российской Федерации, соглашение № 075-15-2021-671.The study was carried out using the resources of the Center for Shared Use of Scientific Equipment of the Ivanovo State University of Chemistry and Technology with the support of the Ministry of Science and Higher Education of the Russian Federation, grant No. 075-15-2021-671.ReferencesGérardy R., Monbaliu J.C. Preparation, Reactivity, and Synthetic Utility of Simple Benzotriazole Derivatives. In: Monbaliu J.C. (Ed.). The Chemistry of Benzotriazole Derivatives. Topics in Heterocyclic Chemistry. Cham.: Springer; 2016. V. 43. P. 1–66. https://doi.org/10.1007/7081_2015_179Gérardy R., Monbaliu J.C. Preparation, Reactivity, and Synthetic Utility of Simple Benzotriazole Derivatives. In: Monbaliu J.C. (Ed.). The Chemistry of Benzotriazole Derivatives. Topics in Heterocyclic Chemistry. Cham.: Springer; 2016. V. 43. P. 1–66. https://doi.org/10.1007/7081_2015_179Preschel M., Roeder M., Schlifke-Poschalko A., Zhang K. Novel process: Pat. US2012/0302760A1 USA. Publ. 29.11.2012.Preschel M., Roeder M., Schlifke-Poschalko A., Zhang K. Novel process: Pat. US2012/0302760A1 USA. Publ. 29.11.2012.Wood M.G., Pastor S.D., Lau J., DiFazio M., Suhadolnik J. Benzotriazoles containing phenyl groups substituted by heteroatoms and compositions stabilized therewith: Pat. US6800676 B2 USA. Publ. 04.04.2013.Wood M.G., Pastor S.D., Lau J., DiFazio M., Suhadolnik J. Benzotriazoles containing phenyl groups substituted by heteroatoms and compositions stabilized therewith: Pat. US6800676 B2 USA. Publ. 04.04.2013.Bossert J., Daniel C. Trans–cis photoisomerization of the styrylpyridine ligand in [Re(CO)3 (2,2′-bipyridine) (t-4-styrylpyridine)]+: role of the metal-to-ligand chargetransfer excited states. Chem. Eur. J. 2006.12(18):4835–4843. https://doi.org/10.1002/chem.200501082Bossert J., Daniel C. Trans–cis photoisomerization of the styrylpyridine ligand in [Re(CO)3 (2,2′-bipyridine) (t-4-styrylpyridine)]+: role of the metal-to-ligand chargetransfer excited states. Chem. Eur. J. 2006.12(18):4835–4843. https://doi.org/10.1002/chem.200501082Rachwal S., Wang P., Rachwal B., Zhang H., Yamamoto M. Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency: Pat. WO2013/049062 A2 int. Publ. 04.04.2013.Rachwal S., Wang P., Rachwal B., Zhang H., Yamamoto M. Highly-fluorescent and photo-stable chromophores for enhanced solar harvesting efficiency: Pat. WO2013/049062 A2 int. Publ. 04.04.2013.Yokoyama N., Hayashi S., Kabasawa N., Taniguchi Y., Ichikawa M., Mochiduki S. Compound Having Benzotriazole Ring Structure and Organic Electrolumenescent Element: Pat. EP2409974 A1 Europe. Publ. 25.01.2012.Yokoyama N., Hayashi S., Kabasawa N., Taniguchi Y., Ichikawa M., Mochiduki S. Compound Having Benzotriazole Ring Structure and Organic Electrolumenescent Element: Pat. EP2409974 A1 Europe. Publ. 25.01.2012.Ciorba S., Bartocci G., Galazzo G., Mazzacato U., Spaletti A. Photoisomerization mechanism of the cis-isomers of 1,2-distyrylbenzene and two hetero-analogues. J. Photochem. Photobiol. A: Chemistry. 2008;195(3):301–306. https://doi.org/10.1016/j.jphotochem.2007.10.016Ciorba S., Bartocci G., Galazzo G., Mazzacato U., Spaletti A. Photoisomerization mechanism of the cis-isomers of 1,2-distyrylbenzene and two hetero-analogues. J. Photochem. Photobiol. A: Chemistry. 2008;195(3):301–306. https://doi.org/10.1016/j.jphotochem.2007.10.016Bajaj K., Sakhuja R. Benzotriazole: much more than just synthetic heterocyclic chemistry. In: Monbaliu J.C. (Ed.). The Chemistry of Benzotriazole Derivatives. Topics in Heterocyclic Chemistry. Cham.: Springer; 2016. V. 43. P. 235–284. https://doi.org/10.1007/7081_2015_198Bajaj K., Sakhuja R. Benzotriazole: much more than just synthetic heterocyclic chemistry. In: Monbaliu J.C. (Ed.). The Chemistry of Benzotriazole Derivatives. Topics in Heterocyclic Chemistry. Cham.: Springer; 2016. V. 43. P. 235–284. https://doi.org/10.1007/7081_2015_198Liu G.-B., Zhao H.-Y., Yang H.-J., Gao X., Li M.-K., Thiemann T. Preparation of 2-aryl-2H-benzotriazoles by zincmediated reductive cyclization o-nitrophenylazophenols in aqueous media without the use of organic solvents. Adv. Synt. Catalysis. 2007;349(10):1637–1640. https://doi.org/10.1002/adsc.200700018Liu G.-B., Zhao H.-Y., Yang H.-J., Gao X., Li M.-K., Thiemann T. Preparation of 2-aryl-2H-benzotriazoles by zincmediated reductive cyclization o-nitrophenylazophenols in aqueous media without the use of organic solvents. Adv. Synt. Catalysis. 2007;349(10):1637–1640. https://doi.org/10.1002/adsc.200700018Baik W., Yoo C.H., Koo S., Kim H., Hwang Y.H., Kim B.H., Lee S.W. Photostimulated reductive cyclization of o-nitrophenylazo dyes using sodium hydroxide in isopropyl alcohol, a new synthesis of 2-aryl-2H-benzotriazoles. Heterocycles.1999;51(8):1779–1783. https://doi.org/10.3987/COM-99-8597Baik W., Yoo C.H., Koo S., Kim H., Hwang Y.H., Kim B.H., Lee S.W. Photostimulated reductive cyclization of o-nitrophenylazo dyes using sodium hydroxide in isopropyl alcohol, a new synthesis of 2-aryl-2H-benzotriazoles. Heterocycles.1999;51(8):1779–1783. https://doi.org/10.3987/COM-99-8597Zollinger H. Diazo Chemistry. I. Aromatic and Heteroaromatic Compounds. Weinheim; New York; Basel; Cambridge; Tokyo: VCH; 1994. 453 p.Zollinger H. Diazo Chemistry. I. Aromatic and Heteroaromatic Compounds. Weinheim; New York; Basel; Cambridge; Tokyo: VCH; 1994. 453 p.Koutsimpelis A.G., Screttas C.G., IgglessiMarkopoulou O. Synthesis of new ultraviolet light absorbers based on 2-aryl-2H-benzotriazoles. Heterocycles. 2005;65(6):1393–1401. https://doi.org/10.3987/COM-04-10304Koutsimpelis A.G., Screttas C.G., IgglessiMarkopoulou O. Synthesis of new ultraviolet light absorbers based on 2-aryl-2H-benzotriazoles. Heterocycles. 2005;65(6):1393–1401. https://doi.org/10.3987/COM-04-10304Frisch M.J., Trucks G.W., Schlegelv H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Montgomery J.A. Jr., Vreven T., Kudin T.K.N., Burant J.C., Millam J.M., Iyengar S.S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N.G., Petersson A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., Naka iH., Klene M., Li X., Knox J.E., Hratchian H.P., Cross J.B., Adamo C., Jaramillo J., Gomperts R., Stratmann R.E., Yazyev O., Austin A.J., Cammi R., Pomelli C., Ochterski J.W., Ayala P.Y., Morokuma K., Voth G.A., Salvador P., Dannenberg J.J., Zakrzewski V.G., Dapprich S., Daniels A.D., Strain M.C., Farkas O., Malick D.K., Rabuck A.D., Raghavachari K., Foresman J.B., Ortiz J.V., Cui Q., Baboul A.G., Clifford S., Cioslowski J., Stefanov B.B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R.L., Fox D.J., Keith T., Al-Laham M.A., Peng C.Y., Nanayakkara A., Challacombe M., Gill P. M.W., Johnson B., Chen W., Wong M.W., Gonzalez C., Pople J.A. Gaussian 03. Pittsburgh PA: Gaussian Inc.; 2003.Frisch M.J., Trucks G.W., Schlegelv H.B., Scuseria G.E., Robb M.A., Cheeseman J.R., Montgomery J.A. Jr., Vreven T., Kudin T.K.N., Burant J.C., Millam J.M., Iyengar S.S., Tomasi J., Barone V., Mennucci B., Cossi M., Scalmani G., Rega N.G., Petersson A., Nakatsuji H., Hada M., Ehara M., Toyota K., Fukuda R., Hasegawa J., Ishida M., Nakajima T., Honda Y., Kitao O., NakaiH., Klene M., Li X., Knox J.E., Hratchian H.P., Cross J.B., Adamo C., Jaramillo J., Gomperts R., Stratmann R.E., Yazyev O., Austin A.J., Cammi R., Pomelli C., Ochterski J.W., Ayala P.Y., Morokuma K., Voth G.A., Salvador P., Dannenberg J.J., Zakrzewski V.G., Dapprich S., Daniels A.D., Strain M.C., Farkas O., Malick D.K., Rabuck A.D., Raghavachari K., Foresman J.B., Ortiz J.V., Cui Q., Baboul A.G., Clifford S., Cioslowski J., Stefanov B.B., Liu G., Liashenko A., Piskorz P., Komaromi I., Martin R.L., Fox D.J., Keith T., Al-Laham M.A., Peng C.Y., Nanayakkara A., Challacombe M., Gill P. M.W., Johnson B., Chen W., Wong M.W., Gonzalez C., Pople J.A. Gaussian 03. Pittsburgh PA: Gaussian Inc.; 2003.Akiyama T. Hydrogen-bond catalysis or brønstedacid catalysis? General considerations. In: Pihko P.M. (Ed.). Hydrogen Bonding in Organic Synthesis. Weinheim: VCH; 2009. P. 5–14. https://doi.org/10.1002/9783527627844.ch2Akiyama T. Hydrogen-bond catalysis or brønstedacid catalysis? General considerations. In: Pihko P.M. (Ed.). Hydrogen Bonding in Organic Synthesis. Weinheim: VCH; 2009. P. 5–14. https://doi.org/10.1002/9783527627844.ch2Zollinger H. Color Chemistry: Synthesis, Properties and Application of Organic Dyes and Pigments. 2nd rev. ed. Weinheim; New York: VCH.; 1991. 496 p.Zollinger H. Color Chemistry: Synthesis, Properties and Application of Organic Dyes and Pigments. 2nd rev. ed. Weinheim; New York: VCH.; 1991. 496 p.Kim H.-D., Ishida H. A study on hydrogen-bonded network structure of polybenzoxazines. J. Phys. Chem. A. 2002;106(14):3271–3280. https://doi.org/10.1021/jp010606pKim H.-D., Ishida H. A study on hydrogen-bonded network structure of polybenzoxazines. J. Phys. Chem. A. 2002;106(14):3271–3280. https://doi.org/10.1021/jp010606pÖzen A. S., Doruker P., Viyente V. Effect of cooperative hydrogen bonding in azo−hydrazone tautomerism of azo dyes. J. Phys. Chem. A. 2007;111(51):13506–13514. https://doi.org/10.1021/jp0755645Özen A. S., Doruker P., Viyente V. Effect of cooperative hydrogen bonding in azo−hydrazone tautomerism of azo dyes. J. Phys. Chem. A. 2007;111(51):13506–13514. https://doi.org/10.1021/jp0755645Lauwiner M., Roth R., Rys P. Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of an iron oxide/hydroxide catalyst. III. Selective reduction of nitro groups in aromatic azo compounds. Appl. Catal. A: Gen. 1999;177(1):9–14. https://doi.org/10.1016/S0926-860X(98)00247-6Lauwiner M., Roth R., Rys P. Reduction of aromatic nitro compounds with hydrazine hydrate in the presence of an iron oxide/hydroxide catalyst. III. Selective reduction of nitro groups in aromatic azo compounds. Appl. Catal. A: Gen. 1999;177(1):9–14. https://doi.org/10.1016/S0926-860X(98)00247-6Hoang A., Nemtseva M.P., Lefedova O.V. Effect of individual solvents on the rates of hydrogenization for substituted nitro-, azo-, and nitroazobenzenes on skeletal nickel. Rus. J. Phys. Chem. A. 2017;91(11):2279–2282. https://doi.org/10.1134/S0036024417110085Hoang A., Nemtseva M.P., Lefedova O.V. Effect of individual solvents on the rates of hydrogenization for substituted nitro-, azo-, and nitroazobenzenes on skeletal nickel. Rus. J. Phys. Chem. A. 2017;91(11):2279–2282. https://doi.org/10.1134/S0036024417110085Klopman G. Chemical Activity and Reaction Paths. New York: John Wiley & Sons Inc.; 1974. 369 p.Klopman G. Chemical Activity and Reaction Paths. New York: John Wiley & Sons Inc.; 1974. 369 p.Zuenko M.A., Nemtseva M.P., Lefedova O.V., Nikolaev V.N. Liquid-phase hydrogenation of 2-nitro2′-hydroxy-5′-methylazobenzene on raney nickel at low temperatures. Rus. J. Phys. Chem. A. 2004;78(6):877–881.Zuenko M.A., Nemtseva M.P., Lefedova O.V., Nikolaev V.N. Liquid-phase hydrogenation of 2-nitro2′-hydroxy-5′-methylazobenzene on raney nickel at low temperatures. Rus. J. Phys. Chem. A. 2004;78(6):877–881.Lefedova O. V., Hoang A., Filippov D.V. Hydrogen role in selectivity of substituted nitro-azobenenes hydrogenization on skeletal nickel in 2-propanol aqueous solutions. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. = Russ. J. Chem. & Chem. Tech. 2020;63(6):65–71. https://doi.org/10.6060/ivkkt.20206306.6057Lefedova O. V., Hoang A., Filippov D.V. Hydrogen role in selectivity of substituted nitro-azobenenes hydrogenization on skeletal nickel in 2-propanol aqueous solutions. Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol. = Russ. J. Chem. & Chem. Tech. 2020;63(6):65–71. https://doi.org/10.6060/ivkkt.20206306.6057

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