Solvoysis in dipolar aprotic solvents, behavior of 4-(p-substituted phenyl)-4-oxo-2-bromobutanoic acids in dimethyl sulfoxide. Substituent effect

Journal Article · Thu Nov 24 23:00:00 EST 1977 · J. Org. Chem.; (United States)

DOI:https://doi.org/10.1021/jo00444a015· OSTI ID:5345242

Bolognese, A; Scherillo, G

A kinetic study of the substituent effect on the reactivity of 4-(p-substituted phenyl)-4-oxo-2-bromobutanoic acids in the solvolytic elimination in Me/sub 2/SO was carried out. It was found that electron-withdrawing groups increased the rate of reaction and electron-donating groups decreased the rate. Hammett correlation of this substituent effect was obtained with sigma values in Me/sub 2/SO-d/sub 6/ at 36 and 60/sup 0/C. The rho observed value, the isotopic effect, and the leaving group influence support a mechanism in which the proton is lost in the rate-determining step of reaction.

• Research Organization: Univ., Naples
• OSTI ID: 5345242
• Journal Information: J. Org. Chem.; (United States), Journal Name: J. Org. Chem.; (United States) Vol. 42:24; ISSN JOCEA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
CARBOXYLIC ACIDS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DECOMPOSITION
DEUTERIUM
DMSO
HYDROGEN ISOTOPES
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
MONOCARBOXYLIC ACIDS
NUCLEI
ODD-ODD NUCLEI
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
REACTION KINETICS
SOLVOLYSIS
STABLE ISOTOPES
SULFOXIDES