Elucidation of fipronil photodegradation pathways

The phenylpyrazole insecticide fipronil (I) photolyzes to its desthio product (II) in aqueous solution. However, the necessity of an intervening oxidation to a sulfone intermediate (III) has not been resolved, and the photodegradation products of II have not been identified. Using GC-MS, HPLC-UV/vis, electrospray MS, (19)F NMR, and GC-TSD, our objective was to characterize the photodegradation pathways of I, which would clarify the role of III, identify products of II, and explain unbalanced mass accounts in previous studies. Findings showed that II is formed directly and photochemically from I, confirmed by the greater stability of III (t(1/2) 112 h), and that successive oxidations of I to III and then a sulfonate (IV) comprise a second pathway. Compound II underwent photodechlorination, substitution of chlorine by trifluoromethyl, and pyrazole ring cleavage. This work is significant to understanding the photochemistry of novel phenylpyrazole pesticides in the environment.