Reaction of tert-butoxy radicals with phenols. Comparison with the reactions of carbonyl triplets
Journal Article
·
· J. Am. Chem. Soc.; (United States)
Tert-butoxy radicals generated in the photodecomposition of di-tert-butyl peroxide react efficiently with phenols to yield the corresponding phenoxy radicals. Typical rate constants in benzene at 22/sup 0/C are 3.3 x 10/sup 8/ and 1.6 x 10/sup 9/ M/sup -1/ s/sup -1/ for phenol and p-methoxyphenol, respectively. The process is considerably slower in polar solvents; e.g., when pyridine is used as cosolvent, the rate constant for phenol drops to 4.1 x 10/sup 6/ M/sup -1/ s/sup -1/ as a result of strong hydrogen bonding which decreases the reactivity of the phenolic O-H group. Isotope effects (H/D) are typically in the 3 to 5 range. 5 figures, 4 tables.
- Research Organization:
- Univ. of Notre Dame, IN
- OSTI ID:
- 6268195
- Journal Information:
- J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 103:14; ISSN JACSA
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400303 -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ALKOXY RADICALS
AROMATICS
BUTOXY RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
PHENOLS
RADICALS
REACTION KINETICS
SOLVENTS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE
400301* -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400303 -- Organic Chemistry-- Isotope Exchange & Isotope Separation-- (-1987)
ALKOXY RADICALS
AROMATICS
BUTOXY RADICALS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
DATA
DEUTERIUM
EXPERIMENTAL DATA
HYDROGEN ISOTOPES
HYDROXY COMPOUNDS
INFORMATION
ISOTOPE EFFECTS
ISOTOPES
KINETICS
LIGHT NUCLEI
NUCLEI
NUMERICAL DATA
ODD-ODD NUCLEI
ORGANIC COMPOUNDS
ORGANIC SOLVENTS
PHENOLS
RADICALS
REACTION KINETICS
SOLVENTS
STABLE ISOTOPES
TEMPERATURE DEPENDENCE