From Chemistry Towards Technology Step-By-Step From Chemistry Towards Technology Step-By-Step От химии к технологии шаг за шагом 2782-1900 111880 10.52957/2782-1900-2025-6-4-117-125 Научные статьи Scientific articles Научные статьи Alternative method for synthesis of tetracarboxylic acids with cycloaliphatic fragments Alternative method for synthesis of tetracarboxylic acids with cycloaliphatic fragments Фирстова Анастасия Андреевна Firstova Anastasia Andreevna firstovaaa@ystu.ru

кандидат химических наук;

candidate of chemical sciences;

 Огородников Дмитрий Алексеевич Ogorodnikov Dmitry Alekseevich Юсифова Юлия Руслановна Yusifova Yulia Ruslanovna yuyusifova@yandex.ru Кофанов Евгений Романович Kofanov Evgeny Romanovich

доктор химических наук;

doctor of chemical sciences;

 Лебедев Антон Сергеевич Lebedev Anton Sergeevich

кандидат химических наук;

candidate of chemical sciences;

 Ярославский государственный технический университет Yaroslavl State Technical University Ярославский государственный университет им. П.Г. Демидова P.G. Demidov Yaroslavl State University 10 01 2026 10 01 2026 6 4 117 125 20 11 2025 20 12 2025 https://chemintech.ru/en/nauka/article/111880/view

The tetracarboxylic acids containing a cycloaliphatic fragment are promising monomers for semi-aromatic polymers of a series of polyimides, polyesters, and polyetherimides. An alternative method has been developed for their synthesis. The method demonstrates the possibility of performing alkylation and acylation reactions in sequence. The choice of the combination of methods for the oxidation of the acyl and methyl groups has been confirmed by quantum chemical calculations.

The tetracarboxylic acids containing a cycloaliphatic fragment are promising monomers for semi-aromatic polymers of a series of polyimides, polyesters, and polyetherimides. An alternative method has been developed for their synthesis. The method demonstrates the possibility of performing alkylation and acylation reactions in sequence. The choice of the combination of methods for the oxidation of the acyl and methyl groups has been confirmed by quantum chemical calculations.

 Friedel-Crafts alkylation tetracarboxylic acids cycloaliphatic fragment Friedel-Crafts alkylation tetracarboxylic acids cycloaliphatic fragment

Mi M.-C., Szu F.-E., Cheng Y.-C., Tsai C.-H., Chen J.-H., Huang, J.-H. Kuo, C.-C., Lin Y.-C., Leung M.-K., Chen W.-C. Semi-aromatic copolymers of poly (ether imide) with alicyclic diamines for obtaining low oxidation properties at a high frequency of 10-40 GHz. Appl. Polym. Mater., 2024, 6(18), 11137–11148. DOI: 10.1021/acsapm.4c01405 Mi M.-C., Szu F.-E., Cheng Y.-C., Tsai C.-H., Chen J.-H., Huang, J.-H. Kuo, C.-C., Lin Y.-C., Leung M.-K., Chen W.-C. Semi-aromatic copolymers of poly (ether imide) with alicyclic diamines for obtaining low oxidation properties at a high frequency of 10-40 GHz. Appl. Polym. Mater., 2024, 6(18), 11137–11148. DOI: 10.1021/acsapm.4c01405 Sachs J.D., Tonks I.A. Synthesis of poly(ether-ether) polymers by hydroesterification polymerization of α,ω enol esters. Macromolecules, 2022, 55(21), 9520–9526. DOI: 10.1021/acs.macromol.2c01935 Sachs J.D., Tonks I.A. Synthesis of poly(ether-ether) polymers by hydroesterification polymerization of α,ω enol esters. Macromolecules, 2022, 55(21), 9520–9526. DOI: 10.1021/acs.macromol.2c01935 Wang D.H., Lee K.M., Lee D.H., Bachkowski M., Park H., MccOnnie M.E., Tan L.-S. The role of alicyclic conformational isomerization in the photomechanical characteristics of crosslinked polyimides with azobenzene functional groups containing tetrasubstituted cyclohexane fragments. ACS Macro Letters, 2021, 10(2), 278–283. DOI: 10.1021/acsmacrolett.0c00903 Wang D.H., Lee K.M., Lee D.H., Bachkowski M., Park H., MccOnnie M.E., Tan L.-S. The role of alicyclic conformational isomerization in the photomechanical characteristics of crosslinked polyimides with azobenzene functional groups containing tetrasubstituted cyclohexane fragments. ACS Macro Letters, 2021, 10(2), 278–283. DOI: 10.1021/acsmacrolett.0c00903 Hosseini N.E., van Melis K.G.V., Vermeer T.J., Koning K.E., Duchateau R. Polymerization of cyclohexenoxide and anhydrides with alternating cycle opening: the effect of the catalyst, co-catalyst, and anhydride structure. Macromolecules, 2012, 45(4), 1770-1776. DOI: 10.1021/ma2025804 Hosseini N.E., van Melis K.G.V., Vermeer T.J., Koning K.E., Duchateau R. Polymerization of cyclohexenoxide and anhydrides with alternating cycle opening: the effect of the catalyst, co-catalyst, and anhydride structure. Macromolecules, 2012, 45(4), 1770-1776. DOI: 10.1021/ma2025804 Nagura M., Sakurazawa M., Suzuki R. Pat.US № 2015346390, 2015. Nagura M., Sakurazawa M., Suzuki R. Pat.US № 2015346390, 2015. Hatanaka T., Adachi I. Pat. KR № 20120000104, 2012. Hatanaka T., Adachi I. Pat. KR № 20120000104, 2012. Nakahata M. Pat. JP № 2011142393, 2011 Nakahata M. Pat. JP № 2011142393, 2011 Yang A., Xu C. Synthesis and Characterization of a Polyimide-Epoxy Composite for Dental Applications. Mech. Compos. Mater., 2018, 54(1), 71–78. DOI:10.1007/s11029-018-9719-7. Yang A., Xu C. Synthesis and Characterization of a Polyimide-Epoxy Composite for Dental Applications. Mech. Compos. Mater., 2018, 54(1), 71–78. DOI:10.1007/s11029-018-9719-7. Li H.T., Lin M.S., Chuang H.R. Wang, M.-W. Siloxane- and Imide-modified Epoxy Resin Cured with Siloxane-containing Dianhydride. J. Polym. Res., 2005, 12(5), 385–391. DOI: 10.1007/s10965-005-1766-9 Li H.T., Lin M.S., Chuang H.R. Wang, M.-W. Siloxane- and Imide-modified Epoxy Resin Cured with Siloxane-containing Dianhydride. J. Polym. Res., 2005, 12(5), 385–391. DOI: 10.1007/s10965-005-1766-9 Tachibana Y., Tsutsuba T., Sakata Ms., Kasuya K.-I. Disubstituted cyclohexane monomers as biodegradable building block: Evaluation of biodegradability of polyesters containing cyclohexane ring. Polym. Degrad. Stab., 2023, 217, 110516.DOI: 10.1016/j.polymdegradstab.2023.110516. Tachibana Y., Tsutsuba T., Sakata Ms., Kasuya K.-I. Disubstituted cyclohexane monomers as biodegradable building block: Evaluation of biodegradability of polyesters containing cyclohexane ring. Polym. Degrad. Stab., 2023, 217, 110516.DOI: 10.1016/j.polymdegradstab.2023.110516. Unoh Y., Satoh T., Hirano K., Miura M. Rhodium(III)-Catalyzed Direct Coupling of Arylphosphine Derivatives with Heterobicyclic Alkenes: A Concise Route to Biarylphosphines and Dibenzophosphole Derivatives. ACS Catalysis, 2015, 5, 6634–6639. DOI:10.1021/acscatal.5b01896 Unoh Y., Satoh T., Hirano K., Miura M. Rhodium(III)-Catalyzed Direct Coupling of Arylphosphine Derivatives with Heterobicyclic Alkenes: A Concise Route to Biarylphosphines and Dibenzophosphole Derivatives. ACS Catalysis, 2015, 5, 6634–6639. DOI:10.1021/acscatal.5b01896 Madan S., Cheng C.H. Nickel-catalyzed synthesis of benzocoumarins: application to the total synthesis of arnottin I. J. Org. Chem., 2006,71(21), 8312-5. DOI: 10.1021/jo061477h. Madan S., Cheng C.H. Nickel-catalyzed synthesis of benzocoumarins: application to the total synthesis of arnottin I. J. Org. Chem., 2006,71(21), 8312-5. DOI: 10.1021/jo061477h. Adak L., Jin M., Saito S., Kawabata T., Itoh T., Ito S., Sharma A.K., Gower N.J., Cogswell P., Geldsetzer J., Takaya H., Isozaki K., Nakamura M. Iron-catalysed enantioselective carbometalation of azabicycloalkenes. ChemCommun (Camb), 2021, 57(57), 6975-6978. DOI: 10.1039/d1cc02387j Adak L., Jin M., Saito S., Kawabata T., Itoh T., Ito S., Sharma A.K., Gower N.J., Cogswell P., Geldsetzer J., Takaya H., Isozaki K., Nakamura M. Iron-catalysed enantioselective carbometalation of azabicycloalkenes. ChemCommun (Camb), 2021, 57(57), 6975-6978. DOI: 10.1039/d1cc02387j Boon-Hong T. Cobalt-Catalyzed Addition of Arylzinc Reagents to Norbornene Derivatives through 1,4 Cobalt Migration.Org.Lett., 2014, 16(12), 3392–3393. DOI: 10.1021/ol501449j Boon-Hong T. Cobalt-Catalyzed Addition of Arylzinc Reagents to Norbornene Derivatives through 1,4 Cobalt Migration.Org.Lett., 2014, 16(12), 3392–3393. DOI: 10.1021/ol501449j Lin Q., Yang W., Yao Y., Chen S., Tan Y., Chen D., Yang D. Copper-Catalyzed Diastereoselective 1,2 Difunctionalization of Oxabenzonorbornadienes Leading to β-Thiocyanato Thioethers. Org Lett., 2019, 21(18), 7244-7247. DOI: 10.1021/acs.orglett.9b02452. Lin Q., Yang W., Yao Y., Chen S., Tan Y., Chen D., Yang D. Copper-Catalyzed Diastereoselective 1,2 Difunctionalization of Oxabenzonorbornadienes Leading to β-Thiocyanato Thioethers. Org Lett., 2019, 21(18), 7244-7247. DOI: 10.1021/acs.orglett.9b02452. Magnus R.A. Review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis. BeilsteinJ.Org. Chem., 2010, 6(6),6–11. DOI: 10.3762/bjoc.6.6 Magnus R.A. Review of new developments in the Friedel–Crafts alkylation – From green chemistry to asymmetric catalysis. BeilsteinJ.Org. Chem., 2010, 6(6),6–11. DOI: 10.3762/bjoc.6.6 Firstova A.A., KofanovE.R., Krasovskaya G.G., Danilova A.S. Simple and efficient synthesis of new tricarboxylic acids bearing cyclohexane and norbornane fragments. Russ. Chem. Bull., 2017, 66, 867–869. DOI: 10.1007/s11172-017-1820-x Firstova A.A., KofanovE.R., Krasovskaya G.G., Danilova A.S. Simple and efficient synthesis of new tricarboxylic acids bearing cyclohexane and norbornane fragments. Russ. Chem. Bull., 2017, 66, 867–869. DOI: 10.1007/s11172-017-1820-x Firstova A.A., Kofanov E.R. Synthesis of Phenylcycloalkanepolycarboxylic Acids. Russ. J. Org. Chem., 2023, 59, 820–825 DOI: 10.31857/S0514749223050129 Firstova A.A., Kofanov E.R. Synthesis of Phenylcycloalkanepolycarboxylic Acids. Russ. J. Org. Chem., 2023, 59, 820–825 DOI: 10.31857/S0514749223050129 Kamiya Y., Kashima M. The autoxidation of aromatic hydrocarbons catalyzed with cobaltic acetate in acetic acid solution: I. The oxidation of toluene. J. Catal., 1972, 25(3), 326-333.DOI:10.1016/0021-9517(72)90234-5 Kamiya Y., Kashima M. The autoxidation of aromatic hydrocarbons catalyzed with cobaltic acetate in acetic acid solution: I. The oxidation of toluene. J. Catal., 1972, 25(3), 326-333.DOI:10.1016/0021-9517(72)90234-5 Becke A.D. A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys.,1993,98, 1372 1377. DOI:10.1063/1.464304 Becke A.D. A new mixing of Hartree-Fock and local density-functional theories. J. Chem. Phys.,1993,98, 1372 1377. DOI:10.1063/1.464304 Flurry R.L. Quantum chemistry: An introduction. NJ: Prentice-Hall, Inc., 1983. 399pp. Flurry R.L. Quantum chemistry: An introduction. NJ: Prentice-Hall, Inc., 1983. 399pp. Parr R.G., Szentpalyand L.V., Liu S. Electrophilicity Index.J. Am. Chem. Soc., 1999, 121, 1922. DOI: 10.1021/ja983494x Parr R.G., Szentpalyand L.V., Liu S. Electrophilicity Index.J. Am. Chem. Soc., 1999, 121, 1922. DOI: 10.1021/ja983494x Ignatov S.K. Kvantovo-khimicheskoye modelirovaniye atomno-molekulyarnykh protsessov. Nizhniy Novgorod: NGU im. N. I. Lobachevskogo, 2019, 93 s. (in Russian). Ignatov S.K. Kvantovo-khimicheskoye modelirovaniye atomno-molekulyarnykh protsessov. Nizhniy Novgorod: NGU im. N. I. Lobachevskogo, 2019, 93 s. (in Russian). Plekhovich S.D., Zelentsov S.V. Raschet perekhodnykh sostoyaniy metodami kvantovoy khimii. Uchebno-metodicheskoye posobiye. Nizhniy Novgorod: Nizhegorodskiy gosuniversitet, 2015, 21 s. (in Russian). Plekhovich S.D., Zelentsov S.V. Raschet perekhodnykh sostoyaniy metodami kvantovoy khimii. Uchebno-metodicheskoye posobiye. Nizhniy Novgorod: Nizhegorodskiy gosuniversitet, 2015, 21 s. (in Russian).