Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters
Objectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-he...
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MIREA - Russian Technological University
2024-07-01
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| Series: | Тонкие химические технологии |
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| Online Access: | https://www.finechem-mirea.ru/jour/article/view/2084 |
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| author | N. T. Sevostyanova S. A. Batashev A. S. Rodionova D. K. Kozlenko |
| author_facet | N. T. Sevostyanova S. A. Batashev A. S. Rodionova D. K. Kozlenko |
| author_sort | N. T. Sevostyanova |
| collection | DOAJ |
| description | Objectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-hexanol and isomerizing methoxycarbonylation of the resulting 2-hexene, in order to obtain methyl esters of C7 carboxylic acids. To investigate the effect of the concentrations of 2-hexanol and methanol on the rate of the one-pot synthesis.Methods. One-pot synthesis was studied in a toluene medium in a steel batch reactor designed to operate at elevated pressure and equipped with a glass insert, a magnetic stirrer, a sampler, and gas input and discharge devices. Samples of the reaction mass were taken during the combined process and were analyzed by means of gas–liquid chromatography with a flame ionization detector.Results. The possibility of one-pot combination was demonstrated for 2-hexanol dehydration catalyzed by methanesulfonic acid, as well as for the isomerizing alkoxycarbonylation of the resulting 2-hexene with 2-hexanol and CO, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system. The dependencies of the rates of the dehydration of 2-hexanol and the formation of esters of C7 carboxylic acids on the concentration of 2-hexanol were shown to pass through a maximum. The possibility of the one-pot process was proved for the synthesis of esters from 2-hexanol, methanol, and CO with the predominant formation of heptanoic acid esters in the presence of the above catalytic system. The rates of dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids were found to decrease with increasing the concentration of methanol in the reaction mass. Under mild conditions (temperature 115°C, CO pressure 3 MPa) with the addition of methanol, the total fraction of 2-hexyl and methyl heptanoic acid esters among C7 carboxylic acid esters was determined to be 85.5%.Conclusions. The reactions of intramolecular acid–catalytic dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system, can be performed as a one-pot process. Methanesulfonic acid simultaneously functions as a catalyst for the dehydration of 2-hexanol and a cocatalyst for the palladium–phosphine system for the alkoxycarbonylation of hexenes. In the presence of the Pd(PPh3) 2Cl2–XANTPHOS–methanesulfonic acid catalytic system, processes for the synthesis of heptanoic acid esters from 2-hexanol, methanol, and CO can be combined within one reactor. An increase in the methanol concentration negatively affects the rate of the dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids. A small amount of methanol in the reaction mass leads to an increase in the fraction of heptanoic acid esters among C7 carboxylic acid esters. |
| format | Article |
| id | doaj-art-f34ff11ef2b045fd9c13b9dd01ffb336 |
| institution | Kabale University |
| issn | 2410-6593 2686-7575 |
| language | Russian |
| publishDate | 2024-07-01 |
| publisher | MIREA - Russian Technological University |
| record_format | Article |
| series | Тонкие химические технологии |
| spelling | doaj-art-f34ff11ef2b045fd9c13b9dd01ffb3362025-08-20T03:56:32ZrusMIREA - Russian Technological UniversityТонкие химические технологии2410-65932686-75752024-07-0119319220110.32362/2410-6593-2024-19-3-192-2011759Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of estersN. T. Sevostyanova0S. A. Batashev1A. S. Rodionova2D. K. Kozlenko3Tula State Lev Tolstoy Pedagogical UniversityTula State Lev Tolstoy Pedagogical UniversityTula State Lev Tolstoy Pedagogical UniversityTula State Lev Tolstoy Pedagogical UniversityObjectives. To study the possibility of one-pot synthesis (combination of two processes in one reactor) for the following pairs of processes: (1) dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, in order to obtain 2-hexyl heptanoate, and (2) dehydration of 2-hexanol and isomerizing methoxycarbonylation of the resulting 2-hexene, in order to obtain methyl esters of C7 carboxylic acids. To investigate the effect of the concentrations of 2-hexanol and methanol on the rate of the one-pot synthesis.Methods. One-pot synthesis was studied in a toluene medium in a steel batch reactor designed to operate at elevated pressure and equipped with a glass insert, a magnetic stirrer, a sampler, and gas input and discharge devices. Samples of the reaction mass were taken during the combined process and were analyzed by means of gas–liquid chromatography with a flame ionization detector.Results. The possibility of one-pot combination was demonstrated for 2-hexanol dehydration catalyzed by methanesulfonic acid, as well as for the isomerizing alkoxycarbonylation of the resulting 2-hexene with 2-hexanol and CO, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system. The dependencies of the rates of the dehydration of 2-hexanol and the formation of esters of C7 carboxylic acids on the concentration of 2-hexanol were shown to pass through a maximum. The possibility of the one-pot process was proved for the synthesis of esters from 2-hexanol, methanol, and CO with the predominant formation of heptanoic acid esters in the presence of the above catalytic system. The rates of dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids were found to decrease with increasing the concentration of methanol in the reaction mass. Under mild conditions (temperature 115°C, CO pressure 3 MPa) with the addition of methanol, the total fraction of 2-hexyl and methyl heptanoic acid esters among C7 carboxylic acid esters was determined to be 85.5%.Conclusions. The reactions of intramolecular acid–catalytic dehydration of 2-hexanol and isomerizing alkoxycarbonylation of the resulting 2-hexene, catalyzed by the Pd(PPh3)2Cl2–XANTPHOS–methanesulfonic acid system, can be performed as a one-pot process. Methanesulfonic acid simultaneously functions as a catalyst for the dehydration of 2-hexanol and a cocatalyst for the palladium–phosphine system for the alkoxycarbonylation of hexenes. In the presence of the Pd(PPh3) 2Cl2–XANTPHOS–methanesulfonic acid catalytic system, processes for the synthesis of heptanoic acid esters from 2-hexanol, methanol, and CO can be combined within one reactor. An increase in the methanol concentration negatively affects the rate of the dehydration of 2-hexanol and the formation of 2-hexyl esters of C7 carboxylic acids. A small amount of methanol in the reaction mass leads to an increase in the fraction of heptanoic acid esters among C7 carboxylic acid esters.https://www.finechem-mirea.ru/jour/article/view/2084<i>one-pot</i> synthesisester synthesisalcohol dehydrationisomerizing alkoxycarbonylation2-hexanolmethanolpalladium catalystxantphos diphosphinemethanesulfonic acid |
| spellingShingle | N. T. Sevostyanova S. A. Batashev A. S. Rodionova D. K. Kozlenko Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters Тонкие химические технологии <i>one-pot</i> synthesis ester synthesis alcohol dehydration isomerizing alkoxycarbonylation 2-hexanol methanol palladium catalyst xantphos diphosphine methanesulfonic acid |
| title | Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters |
| title_full | Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters |
| title_fullStr | Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters |
| title_full_unstemmed | Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters |
| title_short | Effect of 2-hexanol and methanol on the <i>one-pot</i> process of dehydration and alkoxycarbonylation for the synthesis of esters |
| title_sort | effect of 2 hexanol and methanol on the i one pot i process of dehydration and alkoxycarbonylation for the synthesis of esters |
| topic | <i>one-pot</i> synthesis ester synthesis alcohol dehydration isomerizing alkoxycarbonylation 2-hexanol methanol palladium catalyst xantphos diphosphine methanesulfonic acid |
| url | https://www.finechem-mirea.ru/jour/article/view/2084 |
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