Publication Type Journal Article
Title Basic hydrolysis of quinolinyl N,N-dimethylcarbamates: a two-step mechanism
Authors Daniel Silva Fatima Norberto Susana Santos Jim Iley
Groups HC
Journal JOURNAL OF PHYSICAL ORGANIC CHEMISTRY
Year 2011
Month November
Volume 24
Number 11
Pages 1081-1087
Abstract The reactivity of 6-quinolinyl and 8-quinolinyl N,N-dimethylcarbamates was examined in several aqueous basic media. A quadratic dependence was observed for the constant rates upon hydroxide concentration for both compounds, which is a typical behaviour of a mechanism involving a base-catalysed deprotonation of the tetrahedral intermediate with the formation of a dianion at high concentrations of hydroxide ion, while at lower concentrations a specific-base catalysed addition-elimination mechanism seems to be predominant. The reactivity of 8-quinolinyl N,N-dimethylcarbamate was also studied in several amine buffers, showing specific base catalysis. The reactivity of 6-quinolinyl N,N-dimethylcarbamate was studied in H2O and in D2O and the solvent isotope effect supports the proposal of a mechanism involving a specific-base hydrolysis. All results confirm the existence of a mechanism with a rate determining step involving the substrate anion and a second mole of hydroxide ion. This mechanism was so far unknown for carbamate reactivity, being only known to occur with amides. Copyright (C) 2011 John Wiley \& Sons, Ltd.
DOI http://dx.doi.org/10.1002/poc.1835
ISBN
Publisher
Book Title
ISSN 0894-3230
EISSN
Conference Name
Bibtex ID ISI:000296908000010
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