Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate
The formation of water structures can provide significant benefits in organic reactions, stabilizing charge and lowering activation energies. Hydrolysis reactions will frequently rely on water networks to accomplish these goals. Here, we used computational chemistry and experimental kinetics to inve...
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MDPI AG
2025-01-01
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| Online Access: | https://www.mdpi.com/1420-3049/30/2/268 |
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| author | Jack B. Suggs Joshua J. Melko |
| author_facet | Jack B. Suggs Joshua J. Melko |
| author_sort | Jack B. Suggs |
| collection | DOAJ |
| description | The formation of water structures can provide significant benefits in organic reactions, stabilizing charge and lowering activation energies. Hydrolysis reactions will frequently rely on water networks to accomplish these goals. Here, we used computational chemistry and experimental kinetics to investigate a model thioester molecule S-ethyl trifluorothioacetate, and extended work on a previously characterized ester p-nitrophenyl trifluoroacetate. We found that the rate-determining steps in these reactions are heavily influenced by the nature of the leaving group. The hydrolysis of S-ethyl trifluorothioacetate was much slower than p-nitrophenyl trifluoroacetate for this reason. We explored differences in the reaction orders with respect to water and examined details of calculated potential energy surfaces of these hydrolysis reactions, highlighting the roles of solvation effects and transition state structures. |
| format | Article |
| id | doaj-art-9c33d53c73524e15b79c678d57a63f83 |
| institution | Kabale University |
| issn | 1420-3049 |
| language | English |
| publishDate | 2025-01-01 |
| publisher | MDPI AG |
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| series | Molecules |
| spelling | doaj-art-9c33d53c73524e15b79c678d57a63f832025-01-24T13:43:20ZengMDPI AGMolecules1420-30492025-01-0130226810.3390/molecules30020268Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl TrifluorothioacetateJack B. Suggs0Joshua J. Melko1Department of Chemistry and Biochemistry, University of North Florida, Jacksonville, FL 32224, USADepartment of Chemistry and Biochemistry, University of North Florida, Jacksonville, FL 32224, USAThe formation of water structures can provide significant benefits in organic reactions, stabilizing charge and lowering activation energies. Hydrolysis reactions will frequently rely on water networks to accomplish these goals. Here, we used computational chemistry and experimental kinetics to investigate a model thioester molecule S-ethyl trifluorothioacetate, and extended work on a previously characterized ester p-nitrophenyl trifluoroacetate. We found that the rate-determining steps in these reactions are heavily influenced by the nature of the leaving group. The hydrolysis of S-ethyl trifluorothioacetate was much slower than p-nitrophenyl trifluoroacetate for this reason. We explored differences in the reaction orders with respect to water and examined details of calculated potential energy surfaces of these hydrolysis reactions, highlighting the roles of solvation effects and transition state structures.https://www.mdpi.com/1420-3049/30/2/268water structureskinetic ratesestersthioesterspotential energy surfacecleavage reactions |
| spellingShingle | Jack B. Suggs Joshua J. Melko Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate Molecules water structures kinetic rates esters thioesters potential energy surface cleavage reactions |
| title | Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate |
| title_full | Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate |
| title_fullStr | Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate |
| title_full_unstemmed | Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate |
| title_short | Hydrolysis Reactions of p-Nitrophenyl Trifluoroacetate and S-Ethyl Trifluorothioacetate |
| title_sort | hydrolysis reactions of p nitrophenyl trifluoroacetate and s ethyl trifluorothioacetate |
| topic | water structures kinetic rates esters thioesters potential energy surface cleavage reactions |
| url | https://www.mdpi.com/1420-3049/30/2/268 |
| work_keys_str_mv | AT jackbsuggs hydrolysisreactionsofpnitrophenyltrifluoroacetateandsethyltrifluorothioacetate AT joshuajmelko hydrolysisreactionsofpnitrophenyltrifluoroacetateandsethyltrifluorothioacetate |