Secondary deuterium isotope effects for certain acyl transfer reactions of phenyl formates

Journal Article · Tue Jan 02 23:00:00 EST 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00495a028· OSTI ID:6299353

do Amaral, L ^[1]; Bastos, M P; Bull, H G; Ortiz, J J; Cordes, E H

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1. Universidade de Sao Paulo, Brazil

Kinetic ..cap alpha.. secondary deuterium isotope effects, k/sub D//k/sub H/, for formyl group transfer from either the 4-methoxyphenyl or 4-nitrophenyl esters, or both, of formic and deuterioformic acids to a variety of oxygen acceptors have been measured at 25/sup 0/C in aqueous solution: hydroperoxide ion, 1.12; 2-propynol anion, 1.13; hexafluoropropan-2-ol anion, 1.14; and water, 1.22. In addition, corresponding isotope effects have been obtained for general-base-catalyzed formyl group transfer from the same substrates to acetate, 1.21, formate, 1.23, and trimethylamine N-oxide, 1.20. The ..cap alpha.. secondary deuterium isotope effect for acid-catalyzed hydrolysis of both esters has been determined to be 1.24. These data are interpreted to reflect considerable, and perhaps complete, carbon--oxygen bond formation in the transition state for addition of oxygen nucleophiles to phenyl formates. Finally, corresponding isotope effects were determined for reaction of fluoride, 1.19, and azide, 1.14, which also suggest substantial covalent bond formation between ester and nucleophile in the transition state. 4 tables.

• OSTI ID: 6299353
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:1; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400302 -- Organic Chemistry-- Isotope Effects-- (-1987)
ACETATES
ALCOHOLS
AMINES
AQUEOUS SOLUTIONS
AZIDES
BARYONS
CARBOXYLIC ACID SALTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
DEUTERIUM COMPOUNDS
DISPERSIONS
ELEMENTARY PARTICLES
ESTERS
FERMIONS
FLUORIDES
FLUORINE COMPOUNDS
FORMATES
HADRONS
HALIDES
HALOGEN COMPOUNDS
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROLYSIS
HYDROXY COMPOUNDS
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
LYSIS
MEDIUM TEMPERATURE
MIXTURES
NITROGEN COMPOUNDS
NUCLEI
NUCLEONS
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
PH VALUE
PROTONS
REACTION KINETICS
SOLUTIONS
SOLVOLYSIS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
WATER