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Mechanism of α‐substitution reactions of acrylic derivatives
Author(s) -
Hill Jon S.,
Isaacs Neil S.
Publication year - 1990
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.610030503
Subject(s) - chemistry , kinetics , solvent , kinetic isotope effect , amine gas treating , base (topology) , reaction mechanism , substitution reaction , mechanism (biology) , organic chemistry , polymer chemistry , photochemistry , catalysis , deuterium , mathematical analysis , philosophy , physics , mathematics , epistemology , quantum mechanics
Abstract Reactions between acrylic esters, nitriles and similar compounds on the one hand and aldehydes and ketones on the other, catalysed by tertiary amines, lead to α‐(hydroxyalkyl)acrylic compounds. Evidence on the basis of kinetics, volumes of activation and of reaction, and kinetic isotope effects is presented to deduce a mechanism in which amine first undergoes Michael addition, the resulting enolate ion adds to the carbonyl compound in a rate‐determining step and finally base is eliminated. An analysis of the solvent effect on rates is also presented.