Synthesis And Phloe M Mobility Of Amino Acid-fipronil Oriented Pesticide

Pesticides withphloem mobility can effectively control plant vascular disease and sucking pests,and can improve the pesticide targeting and utilization,thereby reducing the use of pesticides to improve security.Coupling plant endogenous compounds?amino acids,sugars,etc.?with pesticide molecules can effectively and quickly obtain conjugates with phloem mobility.Based on the specificity,broad spectrum and diversity of amino acid carriers,connectingpesticide and amino acidswould obtain new compoundstransported by amino acid carrierswithout shielding each functional binding sites.Guided by the concept of amino acid oriented pesticides,amino acid-fipronil conjugates and different glycine ester-fipronil conjugates were synthesized,they were linked by urea bond.Using fipronil as raw material,the first reaction with phenyl chloroformate to produce active ester,and then with another molecular amine?amino acid?reaction to produce urea structure of the amino acid pesticide conjugates,one pot to build two types of 20 newlyamino acid-fipronil conjugates.All compounds were confirmed by ¹H NMR and ¹³C NMR.The absorption and phloem mobility of five different amino acid ester-fipronil conjugates?2a-2e?in castor cotyledon were tested using high performance liquid chromatography?HPLC?.With the exception of Glyt BuF,all of the Gly F esters were taken up more efficiently than that was Gly F itself,and the Gly F esters being uptake cande-esterified to Gly F.The total quantity of Gly F esters taken up and de-esterified rose with time.The conductivity test showed that there no related ester compound s in the phloem of castor seedling.However,the Gly Fhydrolyzed from Gly F esterscan be tested in phloem.The absorption of Gly esters is much higher than that of Gly F,and particularlyGlyMe F?2a?has the highest total absorption,which is about 10 times than that of Gly F.The distinctive results between Gly F and Gly F esters showed the two conjugates have different phloem loading strategy.The phloem mobility of the amino acid ester conjugates?2f-2m?and the amino acid conjugates?3f-3m?were conducted.The results showed that the conjugates containing hydroxyl group?2j;29±3.2?mol/L?,?3j;35±4.8?mol/L?,?2m;21±2.8?mol/L?,?3m;29±3.5?mol/L?showed excellent phloem mobility of 3-10 times than that of other amino acid-fipronil conjugates.Amino acid ester-fipronil conjugates?2h,2i,2k,2l?showed no phloem mobility.Which showed that the branching withmore lengths and branches of amino acids on the?-carbon is not conducive to the phloem mobility of amino acid pesticide conjugates.All amino acid-fipronil conjugates?3f-3m?andconjugates hydrolyzed fromamino acid esters?2f,2j,2m?can be detected in the phloem fluid.The results showed that amino acid ester-fipronil hydrolyzed into the formation of amino acids-fipronilfor the phloem loading and transportation.The amino acid-fipronilare superior phloem mobility to the amino acid ester-fipronil.This articlecontributed to the study of structure and effect and phloem mobilityof amino acid-oriented pesticidesby synthesizing different amino acid-fipronil conjugates and amino acid ester-fipronil conjugates with different transport properties.Particularly,glycinergic-fipronil conjugates with different phloem loading strategy were synthesized,which provided new clues for clarifying the transport mechanisms of amino acid oriented pesticides.