USE OF HYDROGEN ISOTOPE EFFECTS TO IDENTIFY THE ATTACKING NUCLEOPHILE IN THE ENOLIZATION OF KETONES CATALYZED BY ACETIC ACID

Journal Article · Fri Oct 31 23:00:00 EST 1958 · Journal of the American Chemical Society (U.S.)

DOI:https://doi.org/10.1021/ja01554a077· OSTI ID:4291754

Swain, C G; Stivers, E C; Reuwer, Jr, J R; Schaad, L J

Catalysis of enolizaiion by acetic acid is nnt due to an acetic acid molecule acting on the ketonic oxygen and a water molecule removing the proton from carbon, but instead to hydrogen ion acting on the ketonic oxygen and acetaie ion removing the proton from carbon, in the case of alpha -phenylisocaprophenone (a ketone with one alpha hydrogen) in aqueous solution with 8.4 M dioxane (72% dioxane by volume) at 100 . The magnitude of the protium/tritium isotope effect at the carbcn is diagnostic of the attacking nucleophile, increasing as the basicity and reactivity of the nucleophile increases. For catalysis by acetic acid, it has a value (11.4) which is too high for nucleophilic attack by water, but correct for attack by acetate ion. A relation between tritium ived and compared with experimental data. (auth)

• Research Organization: Massachusetts Inst. of Tech., Cambridge
• Sponsoring Organization: USDOE
• NSA Number: NSA-13-002801
• OSTI ID: 4291754
• Journal Information: Journal of the American Chemical Society (U.S.), Journal Name: Journal of the American Chemical Society (U.S.) Vol. Vol: 80; ISSN JACSA
• Country of Publication: Country unknown/Code not available
• Language: English

Related Subjects

ACETATES
ACETIC ACID
ACIDITY
ATOMIC MODELS
CARBON
CATALYSIS
CHEMICAL REACTIONS
CHEMISTRY
COMPOUNDS
DEUTERIUM
DEUTERIUM COMPOUNDS
DIOXANE
ENOLS
ETHYLENE
HYDROGEN
IONS
ISOMERS
ISOTOPE EFFECTS
KETONES
MEASURED VALUES
MOLECULES
NUCLEI
ORGANIC COMPOUNDS
OXIDES
PHENYL RADICALS
PROTONS
SOLUTIONS
SOLVENTS
TEMPERATURE
TRITIUM
WATER