RATES OF REACTION OF SINGLET OXYGEN WITH SULFIDES

Autor:	Bruce Malcolm Monroe
Rok vydání:	1979
Předmět:	chemistry.chemical_classification Chloroform Sulfide Singlet oxygen Thioanisole chemistry.chemical_element General Medicine Photochemistry Biochemistry Sulfur Reaction rate chemistry.chemical_compound Reaction rate constant chemistry Physical and Theoretical Chemistry Methyl group
Zdroj:	Photochemistry and Photobiology. 29:761-764
ISSN:	1751-1097 0031-8655
DOI:	10.1111/j.1751-1097.1979.tb07762.x
Popis:	—Reaction rate constants for the reaction of singlet oxygen with a series of 24 sulfides in chloroform have been measured by inhibition of the self-sensitized photooxidation of rubrene. The reaction rate constant is sensitive to steric effects, decreasing as the carbons α- to sulfur become more highly substituted. Addition of a methyl group to each of the carbons α- to sulfur decreases the rate constant by about a factor of 10. From a series of p- and m-substituted thioanisoles, a ρ of -1.67 ± 0.09 was found. A much better correlation was found with σ than with σ+ indicating there is no resonance interaction with the reaction center. Typical rate constants are: di-n-butyl sulfide, 2.3 × 107M-1 s-1; CBZ-L-methionine methyl ester, 1.4 × 107; di-s-butyl sulfide, 1.8 × 106; di-t-butyl sulfide, 1.3 × 105; and thioanisole, 2.3 × 106.
Databáze:	OpenAIRE
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