Isotopically Labeled Synthesis And Identification Of Two Novel Pesticides

Propyl 4-[2-(4,6-dimethoxy-2-pyrimidinyloxy)benzylamino]benzoate (ZJ273), a novel herbicide derived from the chemical lead of 2-pyrimidinyloxy-N-aryl-benzylamine derivatives, was discovered by Lu Long's research team in 1998. It had achieved 4 patents in China, 1 in USA and 1 in Korea. Celangulins is a novel botanical insecticide from Chinese traditional insecticidal plant, Celastrus angulatus Max., and It had gained 3 patents in China. The major insecticidal components of Celangulins are allβ-dihydroagarofuran sesquiterpene polyol esters (such as celangulin V) and 6β-propoxycelangulin V, a novel insecticidal compound with higher insecticidal activity than celangulin V, derived from celangulin V.Though these two novel pesticides have passed temporary registration and industrialized in China, the metabolism, mode of action, action target, safty evaluation, environmental behavior and fate of them have not been clear by now, as has restricted the farther research of these two pesticides. Isotopically labeled pesticides are essential chemicals in the above researches, supported by isotope trace, radio autograph and others techniques, and that they have been the bottleneck of methods and techniques in the researches. This dissertation focuses particularly on study on the synthesis and identification of radioactive isotopically- and stable isotopically-labeled ZJ273 and 6β-propoxycelangulin V.1. The development and validation of an HPLC method is described for the separation and quantitative determination of ZJ273. The chromatographic conditions are following: Inertsil ODS-3 C18 Column (4.6×250mm, 5μm,10nm), Acetonitrile (0.1%TFA)/water (0.1% TFA) = 70/30(by Vol.), flow rate 1.0mL/min, detection 301.7nm, injection volume 20μL, temperature 25℃. In cold reaction condition, the microsynthetic method of ZJ273 was developed from 4,6-dimethoxy-2-pyrimidine, propyl (4-benzylamino) benzoate and phenol and optimized. The total yield was 52⁵6%.2. Starting with radioactive materials of 4-amino[phenyl-U-¹⁴C₆]benzonic acid, 4,6- dichloro-2-methylthio[4,6-¹⁴C₂]pyrimidine, [U-¹⁴C₆]phenol and [phenyl-2,3,4,5,6- 3H5]phenol, four kinds of specifically radiolabeled herbicides, propyl 4-[2-(4,6-dimethoxy-2- pyrimidinyl- oxy)benzylamino]-[phenyl-U-¹⁴C₆]benzoate (A Ring 14C Labeled ZJ273), propyl 4-[2-(4,6- dimethoxy-2-[4,6-¹⁴C₂]pyrimidinyloxy)benzylamino]benzoate (B Ring 14C Labeled ZJ273), propyl 4-[2-(4,6-dimethoxy-2-pyrimidinyloxy)-[phenyl-U-¹⁴C₆]benzylamino]benzoate(C Ring 14C Labeled ZJ273) and propyl 4-[2-(4,6-dimethoxy-2-pyrimidinyloxy)-[phenyl-3,4,5,6-3H4]...