A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic... The oxidation process of the cyclic acetal sorbitylfurfural (SF) has been thoroughly examined from the kinetic, spectroscopic and theoretical point of view. Oxidation has been initiated by the radiolitically produced OH radical in the presence of variable oxygen amounts. Two competing reaction pathways are evidenced which lead to quite different products, although they do not affect the acetal ring integrity. The peroxidation of the hydroxylated furanic ring (k 4=(6.1±0.9)×108 M−1 s−1) maintains the ring structurevia HO 2 • elimination (k 6=(1.9±0.4)×105 s−1). Unlike that, the peroxidation of the pseudo-allylic radical (k 5=(1.9±0.9)×109 M−1 s−1), formedvia β-cleavage, fixes the destructured intermediate, leading to a tetroxide, which slowly decomposes through a Russell mechanism (k 8=(2.3±0.6)×102 s−1). It is confirmed that the steady state concentration of the tetroxide is very low, which suggests a molar absorption coefficient for it around 1.2×104 M−1 cm−1 at 265 nm. The end products of the latter pathway have been characterized as carboxylic and butenald-sorbitol derivatives. The kinetic and spectral data of every step of the process have been fitted by the above outlined mechanism. The energetics of the mechanism has been detailed byab initio computations as well, carrying further substantiation to it. Semi-empirical calculations were also employed to describe the spectral properties of each intermediate. http://www.deepdyve.com/assets/images/DeepDyve-Logo-lg.png Research on Chemical Intermediates Springer Journals

A kinetic, spectral and theoretical investigation on the role of oxygen in the radiolytic oxidation of a sorbityl cyclic acetal

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Publisher
Springer Netherlands
Copyright
Copyright © 2008 by Springer
Subject
Chemistry; Catalysis; Physical Chemistry; Inorganic Chemistry
ISSN
0922-6168
eISSN
1568-5675
D.O.I.
10.1007/BF03039131
Publisher site
See Article on Publisher Site

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