Deuterium isotope effects on methyl transfer to alcohols. Possible asynchronous solvent repolarization and internal structural changes

Journal Article · Tue Dec 15 23:00:00 EST 1981 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00415a042· OSTI ID:5548103

Kurz, J L; Lee, J; Rhodes, S

Alkyl substitution on nucleophilic oxygen causes large changes in the H/sub 2/O/D/sub 2/O kinetic isotope effect (KIE) on methyl transfers to water: ROL + CH/sub 3/X..-->.. RLO/sup +/ CH/sub 3/ + X/sup -/ with L=H,D; R=L. For both Meth/sup +/ and MeOClO/sub 3/, KIE for CH/sub 3/OL is greater than KIE for L/sub 2/O. When the methyl transfer is to L/sub 2/O, the small, strongly hydrogen-bonding L/sub 2/O/sup +/ moiety in the product will be very tightly solvated, and such tight solvation implies a strong coupling force between solvent polarization and internal charge distribution. (MWF)

• Research Organization: Washington Univ., St. Louis, MO
• OSTI ID: 5548103
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:25; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400302* -- Organic Chemistry-- Isotope Effects-- (-1987)
ALCOHOLS
BUTANOLS
CHEMICAL REACTIONS
DATA
DEUTERIUM
EXPERIMENTAL DATA
HYDROGEN COMPOUNDS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
METHANOL
MOLECULAR STRUCTURE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
OXYGEN COMPOUNDS
POLARIZATION
SOLVENTS
STABLE ISOTOPES
WATER