Photolytic demethylation of monuron and demethylmonuron in aqueous solution

Photochemical demethylation of monuron [3-(4-chlorophenyl)-1, 1-dimethylurea] and of demethylmonuron [ 1-(4-chlorophenyl)-3-methylurea] in aqueous solution was investigated. The photoproducts identified in this study were formaldehyde, formic acid and carbon dioxide. These products indicate that demethylation occurs either by oxidation of a methyl group to hydroxymethyl which is readily cleaved to yield formaldehyde, or by further oxidation to an N-formyl group, which is slowly hydrolysed under weakly acidic conditions to yield formic acid. Samples equilibrated either with air or oxygen (> 99 % purity) gave essentially the same yield of oxidation products. Experimental evidence indicated that extensive photodegradation of formaldehyde was occurring during photolysis, causing low recoveries of formaldehyde. Consequently, with [²H₃-methyl]demethylmonuron and deuterated water, only steady state concentrations of formaldehyde could be measured in an isotopic study.