Entropy-controlled reactivity of singlet oxygen (/sup 1/. delta. g) toward furans and indoles in toluene. A variable-temperature study by pulse radiolysis

Journal Article · Wed May 23 04:00:00 EDT 1979 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00505a036· OSTI ID:6104802

Gorman, A A ^[1]; Lovering, G; Rodgers, M A.J.

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1. Univ. of Manchester, England

The pulse radiolysis technique has been used to produce singlet oxygen O/sub 2/*(/sup 1/..delta..g), the subsequent reactivity of which has been followed by the time-resolved bleaching of diphenylisobenzofuran (DPBF). The rate constants for reaction of O/sub 2/*(/sup 1/..delta..g) with a series of furans, cyclopentadiene, and some indoles have been determined. These constants are temperature independent, and it is concluded that the reactions involve either (a) a concerted step leading directly to endoperoxide or dioxetane which is purely entropy controlled, or (b) production in a rate-determining entropy-controlled step of an intermediate which rapidly rearranges to products.

• OSTI ID: 6104802
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 101:11; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALKENES
AROMATICS
AZOLES
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CRYOGENIC FLUIDS
CYCLOALKENES
CYCLOPENTADIENE
DATA
DATA FORMS
DECOMPOSITION
DIENES
ELEMENTS
ENERGY LEVELS
ENTROPY
EXPERIMENTAL DATA
FLUIDS
FURANS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INDOLES
INFORMATION
IRRADIATION
ISOLATED VALUES
KINETICS
LOW TEMPERATURE
MEDIUM TEMPERATURE
NONMETALS
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
ORGANIC OXYGEN COMPOUNDS
OXYGEN
PHYSICAL PROPERTIES
POLYENES
PULSED IRRADIATION
PYRROLES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
REACTION INTERMEDIATES
REACTION KINETICS
REACTIVITY
TEMPERATURE DEPENDENCE
THERMODYNAMIC PROPERTIES
TOLUENE