Synthesis of plastoquinone analogs and inhibition of photosynthetic and mammalian enzyme systems.

New 5-hydroxy- and 5-chloro-6-alkyl-1,4-benzoquinones with one or two methyl groups on the nucleus were synthesized as potential antimetabolites of plastoquinones for biological research on photosynthetic and mammalian enzyme systems; the primary emphasis was on photosynthesis.2,3-Dimethyl-5-hydroxy-6-phytyl-1,4-benzoquinone completely inhibited in chloroplasts the water-dependent electron transport, but photosystem I was insensitive to this analog. The data are consistent with the interpretation that this analog inhibits electron transport in the chain prior to the site of electron donation from the ascorbate-dichlorophenolindophenol couple. Concentrations of 70 muM and 120 muM of this analog caused about 50 and 100% inhibition, respectively, of cyclic photophosphorylation.2,3-Dimethyl-5-hydroxy-6-phytyl-1,4-benzoquinone is a new type of inhibitor of photosynthetic electron transport that specifically inhibits the rate-limiting step between photosystems I and II. Structurally related analogs caused inhibitions in the range of 50-100% in chloroplasts. These analogs showed marginal inhibition in mitochondrial coenzyme Q(10)-oxidase systems from beef heart.