chemicallytechFine Chemical TechnologiesТонкие химические технологии2410-65932686-7575MIREA – Russian Technological University (RTU MIREA).10.32362/2410-6593-2023-18-1-29-37chemicallytech-1930Research ArticleCHEMISTRY AND TECHNOLOGY OF ORGANIC SUBSTANCESХИМИЯ И ТЕХНОЛОГИЯ ОРГАНИЧЕСКИХ ВЕЩЕСТВCombined process of cyclohexyl cyclohexanecarboxylate synthesis from cyclohexanol and CO catalyzed by the Pd(OAc)2–PPh3–p-toluenesulfonic acid systemСовмещенный процесс синтеза циклогексилциклогексанкарбоксилата из циклогексанола и CO, катализируемый системой Pd(OAc)2–PPh3–п-толуолсульфокислотаhttps://orcid.org/0000-0002-3499-2226СевостьяноваН. Т.SevostyanovaN. T.

Севостьянова Надежда Тенгизовна, к.х.н., доцент, старший научный сотрудник, руководитель научно- производственного центра «Химреактивдиагностика»

300026, г. Тула, пр-т Ленина, д. 125

Scopus Author ID 25643582900, ResearсherID M-8567-2014

Nadezhda T. Sevostyanova, Cand. Sci. (Chem.), Associate Professor, Senior Researcher, Head, Research and Production Center “Himreaktivdiagnostika,”

125, Leninа pr., Tula, 300026

Scopus Author ID 25643582900, ResearсherID M-8567-2014

sevostyanova.nt@gmail.comhttps://orcid.org/0000-0001-7537-7740БаташевС. А.BatashevS. A.

Баташев Сергей Александрович, к.х.н., доцент, старший научный сотрудник научно-производственного центра «Химреактивдиагностика»

300026, г. Тула, пр-т Ленина, д. 125

Scopus Author ID 14071256200, ResearсherID N-1405-2018

Sergey A. Batashev, Cand. Sci. (Chem.), Associate Professor, Senior Researcher, Research and Production Center “Himreaktivdiagnostika,”

125, Leninа pr., Tula, 300026

Scopus Author ID 14071256200, ResearсherID N-1405-2018

tulapharma@gmail.comhttps://orcid.org/0000-0002-0896-5208РодионоваА. С.RodionovaA. S.

Родионова Анастасия Сергеевна, исполнитель по гражданско-правовому договору реализации гранта Российского научного фонда

300026, г. Тула, пр-т Ленина, д. 125

Scopus Author ID 57189375048

Anastasia S. Rodionova, Researcher

125, Leninа pr., Tula, 300026

Scopus Author ID 57189375048

rodionova.nastia@ya.ruФГБОУ ВО «Тульский государственный педагогический университет им. Л.Н. Толстого»РоссияTula State Lev Tolstoy Pedagogical UniversityRussian Federation2023200320231812937Copyright © Sevostyanova N.T., Batashev S.A., Rodionova A.S., 20232023Севостьянова Н.Т., Баташев С.А., Родионова А.С.Sevostyanova N.T., Batashev S.A., Rodionova A.S.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/1930Objectives

Objectives. To study the possibility of combining acid-catalytic cyclohexanol dehydration and alkoxycarbonylation of the formed cyclohexene with cyclohexanol and carbon(II) oxide in a single reactor in order to achieve high yields of the target cyclohexyl cyclohexanecarboxylate product under mild conditions using the Pd(OAc)2–PPh3–p-toluenesulfonic acid catalytic system.Methods. The combined process took place in a toluene medium in a periodic steel reactor designed to operate at elevated pressure, equipped with a glass insert, a magnetic stirrer, and a sampler, as well as gas input and discharge devices. The reaction mass with the components of the catalytic system was placed in a glass reactor inside a steel autoclave. The reaction mass samples obtained during the combined process were analyzed by gas–liquid chromatography with a flame ionization detector.Results. The possibility of combining cyclohexanol dehydration catalyzed by p-toluenesulfonic acid monohydrate and formed cyclohexene alkoxycarbonylation with cyclohexanol and CO during catalysis by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system in a single reactor was demonstrated. Under mild conditions (temperature 110°C; CO pressure 2.1 MPa), the target product yield reached 64.8% in 5 h. However, the combined process is complicated by the formation of a cyclohexanecarboxylic acid by-product formed as a result of the cyclohexyl cyclohexanecarboxylate hydrolysis and the cyclohexene hydroxycarbonylation.

Conclusions

Conclusions. The reactions of intramolecular acid-catalytic cyclohexanol dehydration and formed cyclohexene alkoxycarbonylation catalyzed by the Pd(OAc)2–PPh3–p-toluenesulfonic acid system can be combined in a single reactor. p-Toluenesulfonic acid can simultaneously act as a catalyst for the cyclohexanol dehydration and a co-catalyst of the palladium–phosphine system of cyclohexene alkoxycarbonylation. The involvement of cyclohexene, representing a product of reversible cyclohexanol dehydration, in the alkoxycarbonylation reaction is a factor in shifting the dehydration reaction equilibrium towards the formation of cyclohexene. Cyclohexanecarboxylic acid is a by-product of the proposed combined process. A factor in the reduction of target product yield is water formed as a result of cyclohexanol dehydration due to the involvement of the latter in the hydrolysis reaction and the course of the cyclohexene hydroxycarbonylation.

Цели. Изучение возможности совмещения в одном реакторе реакций кислотнокаталитической дегидратации циклогексанола и алкоксикарбонилирования образующегося циклогексена циклогексанолом и оксидом углерода (II). Установление возможности достижения высоких выходов целевого продукта – циклогексилциклогексанкарбоксилата – в мягких условиях при катализе системой Pd(OAc)2–PPh3–п-толуолсульфокислота.Методы. Совмещенный процесс изучался в среде толуола в периодическом стальном реакторе, рассчитанном на работу при повышенном давлении, снабженном стеклянной вставкой, магнитной мешалкой, пробоотборником, устройствами ввода и сброса газов. Реакционная масса с компонентами каталитической системы помещалась в стеклянный реактор внутри стального автоклава. Отбираемые в ходе совмещенного процесса пробы реакционной массы анализировали методом газо-жидкостной хроматографии с пламенно-ионизационным детектором.Результаты. Показана возможность совмещения в одном реакторе дегидратации циклогексанола, катализируемой моногидратом п-толуолсульфокислоты, и алкоксикарбонилирования образующегося циклогексена циклогексанолом и СО при катализе системой Pd(OAc)2–PPh3–п-толуолсульфокислота. В мягких условиях (температура 110 °С, давление СО 2.1 МПа) выход целевого продукта достигал 64.8% за 5 ч. Установлено, что совмещенный процесс осложняется образованием побочного продукта – циклогексанкарбоновой кислоты – в результате гидролиза циклогексилового эфира циклогексанкарбоновой кислоты и гидроксикарбонилирования циклогексена.

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