Reactivity of cycloxydim toward singlet oxygen in solution and on wax film

The reactivity of the herbicide cycloxydim (CD) toward singlet oxygen was studied in organic solution and on wax films to mimic the leaf surface. Experiments in solution were conducted in acetonitrile using phenalenone as a sensitizer. For the experiments in the solid state, phenalenone was included in paraffinic wax films and CD deposited at the film surface. By laser flash photolysis we observed that the triplet of phenalenone reacts with CD with a bimolecular rate constant of (9.6 ± 1)×106 M−1 s−1. However, scavenging experiments using β-carotene as a singlet oxygen quencher showed that the observed CD degradation in aerated acetonitrile involves singlet oxygen essentially. The bimolecular rate constant of reaction of CD with singlet oxygen was evaluated to (1.0 ± 0.2)×107 M−1 s−1. Phenalenone included in the wax films also significantly increased the rate of CD photodegradation, the involvement of singlet oxygen being very likely. The photoproducts formed via the singlet oxygen pathway resulted from the oxidation of the thiol group and/or the cyclohexene ring. This study should help to better understand the fate of CD after its spraying on crops.

► We show that cycloxydim is oxidized by 1O2. ► The rate constant of reaction of cycloxydim with 1O2 was measured. ► Triplet phenalenone is also quenched by CD. ► CD reacts with 1O2 when sensitizer is inside wax films and CD on the films surface.