Synthesis Process And Quality Control Of Chiral Pesticide:Acrinathrin

Acrinathrin is a norpyrethric ester and belongs to the group of synthetic pyrethroid compounds which are used as insecticide and acaricide.Acrinathrin is non-systemic in plants and acts,by contact and stomach action,it is used on a wide range of phytophagous mites and thrips.Acrinathrin has good effects on the Panonchus citri Mc Gregor,Brevipoalpus lewisi McGregor,Tetranychus urticae Koch and Apple spider mite.At the same time,Acrinathrin also has insecticidal activities for pests of spiny mouthparts and lepidoptera pests.It can be used for cotton,fruit trees,soybeans,corn,vegetables,tea,grapes,citrus,tobacco and other crops.It has wide application prospects and important development and research value.The main content of this thesis is to study the Synthetic process and quality of Acrinathrin.1.Synthetic process of AcrinathrinThe Wittig reaction was carried out with 2-methoxy-5,5-dimethyl-1,3,2-d ioxaphosphane(Neo-TPP)and(1R,4R,5S)-6,6-dimethyl-4-hydroxy-3-oxabicyclo[3.1.0]-hexan-2-ketone,followed by the esterification reaction with(S)-(3-phe noxyphenyl)hydroxyacetonitrile to provide(1R,3S,Z)-3-(3-tert-butoxy-3-oxopro pan-l-enyl)-2,2-dimethylcyclopropanecarboxylic acid-(S)-cyano(3-benzene)Oxy phenyl)methyl ester(Z-AMT)and furnish the construction of the carbon ske leton.The intermediate 2-methoxy-5,5-dimethyl-1,3,2-dioxaphosphorane(Neo-TPP)is obtained by two-step reaction of substitution and Arbuzov reaction.The tert-butyl ester groups in(1R,3S,Z)-3-(3-tert-butoxy-3-oxopropan-1-enyl)-2,2-dimethylcyclopropanecarboxylic acid-(S)-cyano(3-benzene)Oxyphenyl)meth y1 ester(Z-AMT)are converted into hexafluoroisopropyl group by eliminatio n and esterification reaction to complete the synthesis of the desired Acrin athrin.The total yield of the synthesis of Acrinathrin is 39.6%?2.Quality Control of AcrinathrinWe studied the quality of the synthssized product Acrinathrin by IR,m ass spectrometry,chromatography and differential scanning calorimetry.By c omparing with the standard sample,we analyzed the composite data of the final product,and its structure and purity have been confirmed.The results of mass spectrometry showed that an excimer ion peak m/z 540 was exisre d in the ESI-MS(negative mode)spectrp?m,which was[M-H]' peak,consist ent with the molecular weight,and the dissociation peak was also consistent with the dissociation mode of Acrinathrin.The infraed spectra show that t he n?mber,position,relative intensity,shape of the characteristic absorption bands of the main functional groups and molecular skeletons are very simil ar to those of the standard products.The DSC spectr?m showed spikes at 83.4? and was consistent with the melting point of Acrinathrin.Furthermor e,we developed a HPLC method for the analysis of Acrinathrin isomers.U sing Phenomenex Hyperclone column,wavelength selected as 235nm,and u sing n-hexane and tetrahydrofuran(volume ratio 98.5:1.5)as mobile phase,t hree kinds of isomers of Acrinathrin could be separated well.The precision of.the method is between 0.45-0.92 and the rate of recovery is 99.3%-100.6%.The method can be applied to the determination of isomers in Acrinath rin to improve the quality control of Acrinathrin.