Synthesis, properties, and use of copper-chelating amphiphilic dithiocarbamates as synergists of oxidant-generating herbicides

The effect of herbicides that act by generating active oxygen species is often mitigated by the enzymes of the Halliwell-Asada oxygen detoxification pathway. Use of compounds interfering with this pathway synergizes herbicides, allowing the killing of weeds at lower herbicide doses. We have used different dithiocarbamate chelators (Dtcs) capable of removing copper from superoxide dismutase, the first enzyme of the pathway, suppressing its action. Dtcs with different hydrophilic-lipophilic properties (sodium salts of ethyl (2-(2-ethoxyethoxy)ethyl)-, butyl (2-(2-ethoxyethoxy)ethyl) -, hexyl (2-(2-ethoxyethoxy)ethyl)-, and dibutyldithiocarbamic acids) were synthesized so that they might penetrate plant cuticles better than sodium diethyldithiocarbamate. Octanol-water distribution ratios and the stabilities of their copper complexes were determined. All Dtcs tested had a high affinity for copper. The Dtcs did not prevent iron-catalyzed Fenton reaction leading to hydroxyl radical production in vitro. Therefore they would not protect plants from the oxidative damage caused by herbicide, as do compounds that complex iron and thereby prevent the phytotoxic iron-catalyzed Fenton reaction. These amphiphilic compounds show some synergistic activity in vivo, with paraquat as well as lactofen, herbicides that generate active oxygen species by different mechanisms. The results demonstrate that dithiocarbamates have potential as synergists for oxidant-generating herbicides. (C) 1998 Academic Press.