Kinetics and mechanism of the hydrolysis of 2,2,2-trifluoro-N-(3-methyl-2-cyclohexenylidene )ethylamine - An α,β-unsaturated Schiff base

Margaret Brault, Ralph M. Pollack, Charles L Bevins

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22 Scopus citations

Abstract

The kinetics of the hydrolysis of 2,2,2-trifluoro-N-(3-methyl-2-cyclohexenylidene)ethylamine (I) has been investigated in the range H0 = -1.5 to pH 13 at 25°. The reaction rate is almost independent of pH from pH 0 to pH 13, varying by a factor of less than 3. We propose a mechanism involving rate-determining attack of water on protonated I (IH+) at pH 0-7; at pH > 7 attack of hydroxide ion on IH+ is the slow step; and at H0 < 0 breakdown of the carbinolamine is rate determining. Observed solvent isotope effects (kH2O/kD2O) of 2.44 (pH ∼2) and 1.68 (pH 11-12) are consistent with this interpretation. Rates of hydrolysis for I are compared with those for a closely related β,γ-unsaturated Schiff base and found to be at least 300-fold slower at pH values near neutrality.

Original languageEnglish (US)
Pages (from-to)346-350
Number of pages5
JournalJournal of Organic Chemistry
Volume41
Issue number2
StatePublished - 1976
Externally publishedYes

ASJC Scopus subject areas

  • Organic Chemistry

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