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General‐base catalysed hydrolysis and nucleophilic substitution of activated amides in aqueous solutions
Author(s) -
Buurma Niklaas J.,
Blandamer Michael J.,
Engberts Jan B. F. N.
Publication year - 2003
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.607
Subject(s) - chemistry , nucleophile , reactivity (psychology) , nucleophilic substitution , base (topology) , aqueous solution , medicinal chemistry , hydrolysis , intramolecular force , substitution reaction , leaving group , catalysis , combinatorial chemistry , organic chemistry , medicine , mathematical analysis , alternative medicine , mathematics , pathology
The reactivity of 1‐benzoyl‐3‐phenyl‐1,2,4‐triazole ( 1a ) was studied in the presence of a range of weak bases in aqueous solution. A change in mechanism is observed from general‐base catalysed hydrolysis to nucleophilic substitution and general‐base catalysed nucleophilic substitution. A slight tendency is also observed for the more hydrophobic general bases to show higher reactivity towards 1a . Aspartame is an effective nucleophile, possibly because nucleophilic substitution is subject to intramolecular general‐base catalysis. A general conclusion derived from the present results is that unexpected rate effects can only be rationalised provided that the detailed reaction mechanisms are well understood. Copyright © 2003 John Wiley & Sons, Ltd.