The metabolic behavior of chlorotoluron in wheat and soil

The degradation of chlorotoluron, 1-(3-chloro-4-methylphenyl)-3,3-dimethylurea, was investigated in laboratory and field-grown wheat and soil. Thin-layer cochromatography and, partially, derivatization and mass spectroscopy were used to elucidate the structures of the metabolites. Wheat treated with 4-methyl[¹⁴C]-phenyl-labeled chlorotoluron rapidly metabolized the herbicide using two independent mechanisms: (I) oxidation of the 4-methylphenyl group to yield 4-hydroxy-methylphenyl and 4-carboxyphenyl derivatives; and (II) N-demethylation. Mechanism (I) clearly predominated over mechanism (II). Young wheat degraded the herbicide mainly to 4-hydroxy-methylphenyl derivatives with only a small fraction being additionally N-monodemethylated. Most of both metabolites was conjugated, most probably, with glucose. In straw and grains of mature field-grown summer wheat treated postemergence with labeled chlorotoluron at a rate corresponding to 2 kg active ingredient/hectare 2.8 ppm and 0.12 ppm radioactivity equivalent to chlorotoluron were found, respectively. About 50% of this terminal radioactivity was nonextractable by organic solvents. No chlorotoluron or its N-demethylated derivatives were present in either plant part. About 40% of the radioactivity in straw consisted of 4-carboxyphenyl derivatives half of which were N-mono- or didemethylated. The rest of the terminal radioactivity was mainly in form of the 4-hydroxymethylphenyl derivative of chlorotoluron. Less than 20% of the soluble metabolites was present as conjugates. In soil mechanism (II) exceeded mechanism (I). At harvest of the wheat the 0.4 ppm radioactivity of the 0- to 30-cm soil layer was composed of 43% chlorotoluron, 36% N-mono- and 3% N-didemethylated chlorotoluron, as well as 13% 4-carboxyphenyl derivatives partly N-demethylated.