Design And Synthesis Of Novel Pyrimidinoxyphenoxypropionate Compounds

Acetyl-coenzyme A carboxylase (ACCase) is a key enzyme in fatty acid biosynthesis in both eukaryotes and prokaryotes. ACCase is a biotinylated enzyme that catalyzes the carboxylation of acetyl-CoA to produce malonyl-CoA. Inhibitors of the ACCase have been widely used as herbicides. Aryloxyphenoxypropionate (APP) derivatives have been found to be strong inhibitor of acetyl-coacarboxylase (ACCase) and used as a very important class of postemergence herbicides for the control of annual and perennial grasses in broadleaf crops.In seeking to develop novel herbicides that inhibit both sensitive and resistant forms of ACCase in grass weeds, we introduced the pyramidines and 1,2,3-triazolo[4,5-d] pyrimidines to the APP based on the bioisosterism theory, and synthesized a series ofaryloxyphenoxypropionates as potential inhibitors against ACCase.(1) 48 novel Aryloxyphenoxypropionates containing pyrimidines were synthesized by using the diethyl malonate and amidine as starting materials, their molecular structures were confirmed by NMR, MS, IR. The skeleton structure of the target molecules is shown as follows:(2) Nitrosation location of amino-containing compounds of the pyrimidines were discussed, we also attempted the method for the synthesis of aryloxyphenoxypropionates containing amino-pyrimidines.(3) 16 novel aryloxyphenoxypropionates containing 1,2,3-triazolo[4,5-d]pyrimidines by using the 4,6-dichloropyrimidin-5-amine as the starting material, and their molecular structures were confirmed by NMR, MS, IR. The skeleton structure of the target molecules is shown as follows:(4) The herbicidal activities of the synthesized compounds have been preliminarily investigated. The results indicated that many of them exhibit good herbicidal activity against rape and barnyard grass.The inhibitory rates to root were higher than that to stem, in general, the inhibitory rates of aryloxyphenoxypropionates containing 1,2,3-triazolo [4,5-d]pyrimidines were higher than aryloxyphenoxypropionates containing pyrimidines, and the formers are wealthy of further investigation.