Synthesis And Biological Activities Of Pyrethroid Containing Nitrogen

Pyrethroid belong to bionic pesticide, and they are commonly characterized byhigh efficiency, low toxicity, low residual and good environmental compatibility. Sopyrethroid are important fields of pesticide researching and developing. Seventy-fournovel compounds which are pyrethroid containing amide structure were synthesizedbased on Cycloprothrin acid and Lambda-cyhalothrin acid as the matrix compounds.Their structures were confirmed by IR, ~1HNMR, MS and elemental analysis. The boi-logical activites were studied and the crystal structures of representative compoundswere determined by X-ray diffracttion analysis. It is summarized as follows:1. A new process of preparing 2-(4-ethoxyphenyl)acetic acid was designed with2-(4-hydroxyphenyl)acetic acid as raw material. The process conditions wereoptimized and the yield is above 90％.A new process of preparing Ethyl-2-(4-ethoxyphenyl)propenoate was designedwith phenetole as raw material by Friedel-Crafts reaction and Witting G reaction, andthe yield is about 63％.Cycloprothrin was synthesized from 2-(4-hydroxyphenyl)acetic acid as rawmaterial, by etherification reaction, esterification reaction, ester condensation, aldolcondensation, carbin reaction, ester hydrolyzation and condensation reaction. Theprocess conditions were optimized and the total yield is above 35％. The remarkableadvantages of the route are mild reaction conditions, simple operation, easy obtain ofthe raw materials, etc.2. 3-(2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarbonyl)heterocyclidin-2-(thi)ones, 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanyl-N-sunsttuted piperidin ket-ones and 2,2-dichloro-1-(4-ethoxyphenyl)-N-heterocyclic cyclopropanecarboxamideswere synthesized from 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylic acid,3-(3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarbonyl) hetero-cyclidin-2-(thi)ones, 3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcycloprop-anyl-N-sunsttuted piperidin ketones and 3-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2- dimethyl-N-heterocyclic cyclopropanecarboxamides were synthesized from 3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylic acid. Compo-unds SⅠ-I-1、SⅡ-2-1、SⅠ-2-1 and SⅠ-2-5 were determined by X-ray diffracttionanalysis.3. 2,2-Dichloro-1-(4-ethoxyphenyl)-N-sunsttuted phenyl cyclopropanecarbox-amides and 3-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethyl-N-sunsttuted phenylcyclopropanecarboxamides were synthesized respectively from 2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylic acid and 3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylic acid.4. 1-(2,2-Dichloro-1-(4-ethoxyphenyl) cyclopropanecarbonyl)-3-sunsttutedphenyl thioureas and 1-(3-(2-Chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclo-propanecarbonyl)-3-sunsttuted phenyl thioureas were synthesized respectively from2,2-dichloro-1-(4-ethoxyphenyl)cyclopropanecarboxylic acid and 3-(2-chloro-3,3,3-trifluoroprop-1-enyl)-2,2-dimethylcyclopropanecarboxylic acid.5. The biological activities(insecticidal activities, fungicidal activities andherbicidal activities) of seventy-four novel compounds were preliminary studied. Theresults showed some compounds exhibited certain insecticidal activities andfungicidal activities, e.g., compound SⅡ-1-3 exhibited 90％inhibition ofMythimnaseparate and compounds SⅡ-4-11, SⅡ-5-9, SⅡ-5-11 exhibited above 65％inhibition of Botrytis cinerea. However, all of them did not exhibite herbicidalactivities.