Stereochemical studies. Part 112. Geometrical dependence of intramolecular catalysis in the hydrolysis and aminolysis of aryl esters

Michael I. Page, David Render, G. Bernáth

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Abstract

The spontaneous hydrolyses of a series of p-nitrophenyl esters of 2-aminocarboxylic acids show rate enhancements of ca. 103. These can be attributed to intramolecular general base catalysis by the neighbouring amino group, or to hydrogen-bonding/electrostatic stabilisation of the tetrahedral intermediate formed in the kinetically equivalent mechanism of hydroxide ion attack on the ammonium ion ester. The hydrolysis of the esters catalysed by phosphate and carbonate ions shows rate enhancements of 103 and 102, respectively, attributable to electrostatic/hydrogen-bonding catalysis. Conversely, the aminolysis of the esters with trifluoroethylamine shows a rate enhancement of 102 attributable to intramolecular general base catalysis. In all these reactions there is little dependence of the rate enhancement upon the geometrical relationship between the amino and ester functions. These observations support the suggestion that proton transfer/hydrogen bonding requires relatively little loss of entropy.

Original languageEnglish
Pages (from-to)867-871
Number of pages5
JournalJournal of the Chemical Society, Perkin Transactions 2
Issue number6
DOIs
Publication statusPublished - 1986

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Catalysis
Hydrolysis
Esters
Hydrogen bonds
Electrostatics
Ions
Proton transfer
Carbonates
Ammonium Compounds
Entropy
Stabilization
Phosphates
Acids

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "The spontaneous hydrolyses of a series of p-nitrophenyl esters of 2-aminocarboxylic acids show rate enhancements of ca. 103. These can be attributed to intramolecular general base catalysis by the neighbouring amino group, or to hydrogen-bonding/electrostatic stabilisation of the tetrahedral intermediate formed in the kinetically equivalent mechanism of hydroxide ion attack on the ammonium ion ester. The hydrolysis of the esters catalysed by phosphate and carbonate ions shows rate enhancements of 103 and 102, respectively, attributable to electrostatic/hydrogen-bonding catalysis. Conversely, the aminolysis of the esters with trifluoroethylamine shows a rate enhancement of 102 attributable to intramolecular general base catalysis. In all these reactions there is little dependence of the rate enhancement upon the geometrical relationship between the amino and ester functions. These observations support the suggestion that proton transfer/hydrogen bonding requires relatively little loss of entropy.",
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AU - Bernáth, G.

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N2 - The spontaneous hydrolyses of a series of p-nitrophenyl esters of 2-aminocarboxylic acids show rate enhancements of ca. 103. These can be attributed to intramolecular general base catalysis by the neighbouring amino group, or to hydrogen-bonding/electrostatic stabilisation of the tetrahedral intermediate formed in the kinetically equivalent mechanism of hydroxide ion attack on the ammonium ion ester. The hydrolysis of the esters catalysed by phosphate and carbonate ions shows rate enhancements of 103 and 102, respectively, attributable to electrostatic/hydrogen-bonding catalysis. Conversely, the aminolysis of the esters with trifluoroethylamine shows a rate enhancement of 102 attributable to intramolecular general base catalysis. In all these reactions there is little dependence of the rate enhancement upon the geometrical relationship between the amino and ester functions. These observations support the suggestion that proton transfer/hydrogen bonding requires relatively little loss of entropy.

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