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Otto Warburg, the father of cellular bioenergetics, seems to have been the first investigator to report on inhibition of a plant biochemical reaction by a progenitor of a selective herbicide. The year was 1920 and the compound was phenylurethane (ethyl N-phenylcarbam ate or EPC). Warburg found that it strongly inhibited photosynthesis in Chlorella. EPC did not develop into a commercial herbicide, but the isopropyl derivatives (propham and chlorpropham) which were introduced in the late 1940s became selective herbicides. The phenylureas (monuron and diuron) were introduced in the early 1950s and shortly thereafter, interference with the Hill reaction by both phenylureas and phenylcarbamates was reported. During the latter part of the 1950s, into the 1960s, and even now, additional herbicidal chemistry was and is being announced that interferes with the Hill reaction. Duysens, in 1963, identified the site of action of diuron, i.e., on the acceptor side of PS II. Corwin Hansch, in 1966 introduced the SAR or QSAR concept in which inhibitory action of Hill inhibitors was related to various chemical and physical parameters.

Research on Biochemistry of Herbicides: An Historical Overview