Kinetics and mechanism of acid-catalyzed hydrolysis of the diazo functional groups of 1-diazo-2-indanone and 2-diazo-1-indanone in aqueous solution
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Bibliographic record
Abstract
Rates of hydrolysis of 1-diazo-2-indanone and 2-diazo-1-indanone were measured in dilute aqueous perchloric acid solutions using both H 2 O and D 2 O as the solvent, and rates of hydrolysis of the latter substrate were measured in dilute aqueous (H 2 O only) formic acid buffer solutions as well. The data for 1-diazo-2-indanone gave the hydronium ion catalytic coefficient k H + = 5.7 × 10 3 (mol/L) 1 s 1 and the isotope effect k H + /k D + = 2.9. The normal direction (k H /k D > 1) of this isotope effect was taken as evidence for a reaction mechanism involving rate-determining hydron transfer from the hydronium ion to the substrate's diazo carbon atom; followed by rapid displacement of diazo nitrogen by a water molecule, giving the observed 1-hydroxy-2-indanone product. The data for 2-diazo-1-indanone, on the other hand, gave a hydronium ion catalytic coefficient two orders of magnitude greater than the value for 1-diazo-2-indanone (k H + = 5.9 × 10 1 (mol/L) 1 s 1 ), and an isotope effect near unity (k H + /k D + = 1.2). It is argued that this isotope effect represents a situation in which diazo carbon hydronation and displacement of diazo nitrogen are each partly rate determining, a conclusion supported by incipient saturation of buffer catalysis in the formic acid buffer solutions. The 100-fold difference in hydronium ion catalytic coefficients for the two substrates is rationalized in terms of differing electron densities on the diazo carbon atoms.Key words: diazo compound hydrolysis, solution kinetics, acid catalysis, solvent isotope effects, buffer catalysis saturation.
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| Category | Codex | Gemma |
|---|---|---|
| Metaresearch | 0.000 | 0.000 |
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