A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues
Here, we investigated the synthetic processes for the methyl derivatives of sym-triaminobenzene and phloroglucinol, the essential chemical reactants coming into use in the production of dyes and pigments, and medicinal drugs for different purposes. The most eco-benign process for the synthesis of tr...
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MDPI AG
2022-12-01
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| Series: | Molecules |
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| Online Access: | https://www.mdpi.com/1420-3049/27/23/8595 |
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| author | Irina A. Shchurova Natalia A. Alekseyeva Sergey V. Sysolyatin Valeriy V. Malykhin |
| author_facet | Irina A. Shchurova Natalia A. Alekseyeva Sergey V. Sysolyatin Valeriy V. Malykhin |
| author_sort | Irina A. Shchurova |
| collection | DOAJ |
| description | Here, we investigated the synthetic processes for the methyl derivatives of sym-triaminobenzene and phloroglucinol, the essential chemical reactants coming into use in the production of dyes and pigments, and medicinal drugs for different purposes. The most eco-benign process for the synthesis of triamino derivatives involves the catalytic hydrogenation of corresponding nitroarenes. The present study investigated the hydrogenation of 2,4,6-trinitrotoluene, 2,4,6-trinitroxylene, and 2,4,6-trinitromesitylene over a Pd catalyst. A 1% Pd/Sibunit catalyst was found to be preferable to the 5% analogue with a preserved palladium loading because it shortens the reaction time and provides a higher yield of the target product. The hydrogenation in methanol (or mixed methanol/toluene) at 50–55 °C and 0.5 MPa pressure produced 2,4,6-triaminotoluene, 2,4,6-triaminoxylene, and 2,4,6-triaminomesitylene, which were isolated as sulfuric acid salts in 98, 91, and 97% yields, respectively. The hydrolysis process of the resultant salts was examined, and conditions leading to mono-, di-, and trimethyl derivatives of phloroglucinol (90, 77, and 82%, respectively,) were identified. The hydrogenation of the trinitrobenzene homologues in mixed 7:1 (<i>v</i>/<i>v</i>) acetone/water, followed by hydrolysis to the respective polyphenols, was explored. A successful result was achieved only for 2,4,6-trinitrotoluene. The catalyst activity was shown to decline negligibly throughout 10 cycles of reuse. 2-Methylphloroglucinol was synthesized in a high yield ranging from 85 to 91% calculated as 2,4,6-trinitrotoluene. |
| first_indexed | 2024-03-09T17:38:18Z |
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| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-09T17:38:18Z |
| publishDate | 2022-12-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-01696f7806ef41e5843930b93c8ccb232023-11-24T11:44:54ZengMDPI AGMolecules1420-30492022-12-012723859510.3390/molecules27238595A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene HomologuesIrina A. Shchurova0Natalia A. Alekseyeva1Sergey V. Sysolyatin2Valeriy V. Malykhin3Laboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), Biysk 659322, RussiaLaboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), Biysk 659322, RussiaLaboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), Biysk 659322, RussiaLaboratory for Chemistry of Nitrogen Compounds, Institute for Problems of Chemical and Energetic Technologies, Siberian Branch of the Russian Academy of Sciences (IPCET SB RAS), Biysk 659322, RussiaHere, we investigated the synthetic processes for the methyl derivatives of sym-triaminobenzene and phloroglucinol, the essential chemical reactants coming into use in the production of dyes and pigments, and medicinal drugs for different purposes. The most eco-benign process for the synthesis of triamino derivatives involves the catalytic hydrogenation of corresponding nitroarenes. The present study investigated the hydrogenation of 2,4,6-trinitrotoluene, 2,4,6-trinitroxylene, and 2,4,6-trinitromesitylene over a Pd catalyst. A 1% Pd/Sibunit catalyst was found to be preferable to the 5% analogue with a preserved palladium loading because it shortens the reaction time and provides a higher yield of the target product. The hydrogenation in methanol (or mixed methanol/toluene) at 50–55 °C and 0.5 MPa pressure produced 2,4,6-triaminotoluene, 2,4,6-triaminoxylene, and 2,4,6-triaminomesitylene, which were isolated as sulfuric acid salts in 98, 91, and 97% yields, respectively. The hydrolysis process of the resultant salts was examined, and conditions leading to mono-, di-, and trimethyl derivatives of phloroglucinol (90, 77, and 82%, respectively,) were identified. The hydrogenation of the trinitrobenzene homologues in mixed 7:1 (<i>v</i>/<i>v</i>) acetone/water, followed by hydrolysis to the respective polyphenols, was explored. A successful result was achieved only for 2,4,6-trinitrotoluene. The catalyst activity was shown to decline negligibly throughout 10 cycles of reuse. 2-Methylphloroglucinol was synthesized in a high yield ranging from 85 to 91% calculated as 2,4,6-trinitrotoluene.https://www.mdpi.com/1420-3049/27/23/8595trinitrobenzenescatalytic hydrogenationPd/Sibunittriaminobenzeneshydrolysis2-methylphloroglucinol |
| spellingShingle | Irina A. Shchurova Natalia A. Alekseyeva Sergey V. Sysolyatin Valeriy V. Malykhin A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues Molecules trinitrobenzenes catalytic hydrogenation Pd/Sibunit triaminobenzenes hydrolysis 2-methylphloroglucinol |
| title | A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues |
| title_full | A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues |
| title_fullStr | A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues |
| title_full_unstemmed | A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues |
| title_short | A Comparative Study of the Synthesis and Hydrolysis of <i>sym</i>-Triaminobenzene Homologues |
| title_sort | comparative study of the synthesis and hydrolysis of i sym i triaminobenzene homologues |
| topic | trinitrobenzenes catalytic hydrogenation Pd/Sibunit triaminobenzenes hydrolysis 2-methylphloroglucinol |
| url | https://www.mdpi.com/1420-3049/27/23/8595 |
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