Electron spin resonance studies. Part 61. The generation and reactions of the t-butoxyl radical in aqueous solution

Abstract
The t-butoxyl radical has been generated in aqueous solution from the reaction between TiIII and ButOOH in a flow system. Evidence is presented which indicates that, although the fragmentation of ButO· to Me· and acetone is rapid under these conditions (k > 106 dm3 mol–1 s–1), competing addition reactions (e.g. to vinyl ethers, furan) and abstraction reactions (with alcohols) can be characterized. ButO· is shown to be electrophilic, like ·OH, in its reactions, but with prop-2-en-1-ol, unlike ·OH, it undergoes abstraction rather than addition. Changes in the behaviour of t-butoxyl at very low pH are attributed to the formation and reaction of the protonated counterpart ButOH+˙.

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