The computational analysis and modelling of substitution effects on hydrolysis of formanilides in acidic aqueous solutions
| Autor: | Peter Škorňa, Martin Michalík, Erik Klein, Vladimír Lukeš |
|---|---|
| Rok vydání: | 2017 |
| Předmět: |
Aqueous solution
010405 organic chemistry Substituent General Physics and Astronomy Protonation 010402 general chemistry Rate-determining step 01 natural sciences 0104 chemical sciences Dissociation constant chemistry.chemical_compound Hydrolysis Reaction rate constant chemistry Computational chemistry Amide Organic chemistry Physical and Theoretical Chemistry |
| Zdroj: | Chemical Physics Letters. 687:66-72 |
| ISSN: | 0009-2614 |
| DOI: | 10.1016/j.cplett.2017.08.069 |
| Popis: | Various para, meta and ortho substituted formanilides have been theoretically studied. For trans and cis-isomers of non-substituted formanilide, the calculated B3LYP vibration normal modes were analyzed. Substituent effect on the selected normal modes was described and the comparison with the available experimental data is presented. The calculated B3LYP proton affinities were correlated with Hammett constants, Fujita-Nishioka equation and the rate constants of the hydrolysis in 1 M HCl. Found linear dependences allow predictions of dissociation constants (pKBH+) and hydrolysis rate constants. Obtained results indicate that protonation of amide group may represent the rate determining step of acid catalyzed hydrolysis. |
| Databáze: | OpenAIRE |
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