Ketonization of enols in aqueous solution: is carbon protonation always rate-determining?
Summary of "Ketonization of enols in aqueous solution: is carbon protonation always rate-determining?"
The pH-rate profiles for the ketonization of the (E)- and (Z)-photoenols of o-methylacetophenone (MA) in aqueous solution were determined by nanosecond laser flash photolysis. Carbon protonation of the enol anions of MA by solvent water is exceptionally fast, k(0)'(K)≈ 2.0 × 10(7) s(-1), too fast to permit establishment of the acid-base equilibrium on the enol oxygen prior to ketonization. Analysis of the pH-rate profile of the (E)-enol using the common assumption of rate-determining carbon protonation would lead to an erroneous value for the acidity constant of that enol, pK(a,c)(E) = 11.3, which is too high by about two pK units.
Affiliation
Department of Chemistry, University of Basel, CH-4056, Basel, Switzerland. J.Wirz@unibas.ch.
Journal Details
This article was published in the following journal.
Name: Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society
ISSN: 1474-9092
Pages:
Links
- PubMed Source: http://www.ncbi.nlm.nih.gov/pubmed/22277957
- DOI: http://dx.doi.org/10.1039/c2pp05369a
Medical and Biotech [MESH] Definitions
Saline Solution, Hypertonic
Hypertonic sodium chloride solution. A solution having an osmotic pressure greater than that of physiologic salt solution (0.9 g NaCl in 100 ml purified water).
Enzyme Assays
Methods used to measure the relative activity of a specific enzyme or its concentration in solution. Typically an enzyme substrate is added to a buffer solution containing enzyme and the rate of conversion of substrate to product is measured under controlled conditions. Many classical enzymatic assay methods involve the use of synthetic colorimetric substrates and measuring the reaction rates using a spectrophotometer.
Hydrogen Peroxide
A strong oxidizing agent used in aqueous solution as a ripening agent, bleach, and topical anti-infective. It is relatively unstable and solutions deteriorate over time unless stabilized by the addition of acetanilide or similar organic materials.
Estrenes
Unsaturated derivatives of the ESTRANES with methyl groups at carbon-13, with no carbon at carbon-10, and with no more than one carbon at carbon-17. They must contain one or more double bonds.
Osmotic Pressure
The pressure required to prevent the passage of solvent through a semipermeable membrane that separates a pure solvent from a solution of the solvent and solute or that separates different concentrations of a solution. It is proportional to the osmolality of the solution.
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