Author： Schuchmann M.N. Scholes M.L. Zegota H. Von Sonntag C.
Publisher： Informa Healthcare
ISSN： 1362-3095
Source： International Journal of Radiation Biology, Vol.68, Iss.2, 1995-08, pp. : 121-131
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Abstract
The rate constants for reactions of hydroxyl radicals with a number of alkyl phosphates have been determined by competition with KSCN. Hydroxyl radicals react with alkyl phosphates preferentially by H-abstraction at the α-position of the phosphate functions. The resulting α-phosphatoalkyl radicals are not very efficient one-electron reducing agents towards nitro compounds. They react with tetranitromethane (TNM) by addition to form adduct intermediates with absorption maxima at about 300 nm. The rate constants for decay of these TNM adducts to produce the nitroform anion (NF−) and the corresponding α-phosphato-alcohols have been determined by optical and/or conductance detection. The stability of these TNM adducts varies considerably with the chain length (methyl > ethyl > isopropyl) and number (trialkyl > dialkyl > monoalkyl) of the alkyl substituents. Additional formation of proton during or after the decay of the TNM adducts has been tentatively attributed to the hydrolysis of the α-phosphato-alcohols. α-Phosphatoalkyl radicals derived from trimethyl, triethyl, triisopropyl, and diethyl phosphates react with
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