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A Comparative Study of the Synthesis and Hydrolysis of sym-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...
Autores principales: | , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
MDPI
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9737077/ https://www.ncbi.nlm.nih.gov/pubmed/36500688 http://dx.doi.org/10.3390/molecules27238595 |
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author | Shchurova, Irina A. Alekseyeva, Natalia A. Sysolyatin, Sergey V. Malykhin, Valeriy V. |
author_facet | Shchurova, Irina A. Alekseyeva, Natalia A. Sysolyatin, Sergey V. Malykhin, Valeriy V. |
author_sort | Shchurova, Irina A. |
collection | PubMed |
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 (v/v) 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. |
format | Online Article Text |
id | pubmed-9737077 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | MDPI |
record_format | MEDLINE/PubMed |
spelling | pubmed-97370772022-12-11 A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues Shchurova, Irina A. Alekseyeva, Natalia A. Sysolyatin, Sergey V. Malykhin, Valeriy V. Molecules Article 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 (v/v) 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. MDPI 2022-12-06 /pmc/articles/PMC9737077/ /pubmed/36500688 http://dx.doi.org/10.3390/molecules27238595 Text en © 2022 by the authors. https://creativecommons.org/licenses/by/4.0/Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (https://creativecommons.org/licenses/by/4.0/). |
spellingShingle | Article Shchurova, Irina A. Alekseyeva, Natalia A. Sysolyatin, Sergey V. Malykhin, Valeriy V. A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title | A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title_full | A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title_fullStr | A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title_full_unstemmed | A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title_short | A Comparative Study of the Synthesis and Hydrolysis of sym-Triaminobenzene Homologues |
title_sort | comparative study of the synthesis and hydrolysis of sym-triaminobenzene homologues |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC9737077/ https://www.ncbi.nlm.nih.gov/pubmed/36500688 http://dx.doi.org/10.3390/molecules27238595 |
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