Chemically induced dynamic electron polarization study of the rates of hydrogen abstraction reactions of carbonyls. Position dependence and deuterium effect

Journal Article · Thu May 02 00:00:00 EDT 1991 · Journal of Physical Chemistry; (United States)

DOI:https://doi.org/10.1021/j100162a043· OSTI ID:5975031

Tominaga, Keisuke; Yamauchi, Seigo; Hirota, Noboru ^[1]

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1. Kyoto Univ. (Japan)

Using time-resolved EPR, the authors have investigated the hydrogen abstraction reaction of carbonyls, especially acetone, with alkanes and 2-propanol to examine the position and type dependence of the reaction and the reaction mechanism. It is concluded that all the secondary hydrogens at different positions of alkanes are abstracted at almost equal rates, which cannot be explained by a simple MO theory. The results for the reactivities of the hydrogens of the different types are consistent with related studies, i.e., k{sub 1}/k{sub 2} {le} 0.1 and k{sub 2}/k{sub 3} {approx equal} 0.1, where k{sub 1}, k{sub 2}, and k{sub 3} are abstraction rate constants for primary, secondary, and tertiary hydrogens, respectively. As for the deuterium isotope effects on the reaction rates of acetone and cyclopentanone with 2-propanol, k{sub H}/k{sub D}, are found to be around 3-4 with no significant temperature dependence. The implication of this result is briefly discussed.

• OSTI ID: 5975031
• Journal Information: Journal of Physical Chemistry; (United States), Vol. 95:9; ISSN 0022-3654
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ACETONE
DEHYDRIDATION
DEUTERIUM
ISOTOPE EFFECTS
KETONES
ALKANES
CHEMICAL REACTION KINETICS
COMPARATIVE EVALUATIONS
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
ISOTOPIC EXCHANGE
ORGANIC OXYGEN COMPOUNDS
POLARIZATION
PROPANOLS
TEMPERATURE DEPENDENCE
TEMPERATURE RANGE 0065-0273 K
TEMPERATURE RANGE 0273-0400 K
TIME RESOLUTION
ALCOHOLS
CHEMICAL REACTIONS
DATA
EVALUATION
HYDROCARBONS
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPES
KINETICS
LIGHT NUCLEI
MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
REACTION KINETICS
RESOLUTION
RESONANCE
STABLE ISOTOPES
TEMPERATURE RANGE
TIMING PROPERTIES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation