Design,Synthesis And Herbicidal Activity Of New Aurone And Coumarin Derivatives

Natural products lay a foundation of developing high efficiency,high selectivity and environment friendly agrochemicalsdue to the advantages ofhighselectivity,easily biodegradable and good environmental compatibility.Aurone and coumarin aretwo kinds of natural products in plants,which attractmuch attention in the field of medical research,but less in the field of pesticide application research.Base on literaturesand research of our group,this paper describes the design,synthesis and herbicidal activity of 6-aryloxyacetoxy aurone derivatives and 7-aryloxyacetoxy coumarin derivatives.The details are as follows:(1)Synthesis and herbicidal activity of 6-aryloxyacetoxy aurone derivativesUsing resorcinol and chloroacetonitrile as raw materials tosynthesis2,4-dihydroxya-chlorinated acetophenone andthenwieh substituted benzene formaldehyde in the condition of alkaline condensate to 18 key intermediates — — 6-hydroxy aurone derivatives(I-1~I-18),6-hydroxy aurone derivatives(I-1~I-18)and different aromatic oxygen acetyl chloride(D1~D3)make a nucleophilic substitution reaction to get 27 new 6-aryloxyacetoxy aurone derivatives(TM-1~TM-27).The structure of the synthetic compounds areconfirmed by 1H NMR,13 CNMR,IR and elemental analysis.The preliminary herbicidal activity tests' results of rape AGAR method and weed show that part of the target compounds' effectin 10 g/mu inhibiting dicotyledonous rapeseed roots long is the commercialization of 2,4-D,and their selectivity of dicotyledonous rapeseed is better than that of 2,4-D;Pot experiments(dose respectively for 100,50 and 10 g/mu)further verify thatthe effect of stem leaf treatment is much higher than soil treatment's,and performvery high selectivity of dicotyledonous plants,the action mechanism May bedifferent from 2,4-D,they have higher application potential and the value of in-depth study.For example,with cauline leafin 10 g/mu,theinhibition rates of TM-2 for dicotyledonous canola and amaranth were 100% and 92.5% respectively,better than that of 2,4-D.In addition,this kind of compounds show a structure-activity relationship,the location of substituent on the benzene ring(R1 and R2)and electrical have important influence on herbicidal activity.(2)Synthesis and herbicidal activity of 7-aryloxyacetoxy coumarin derivativesDifferent resorcinol and corresponding acetoacetic ester compounds in sulfuric acid catalyst synthesis 9 intermediates——7-hydroxyl coumarin derivatives(I-19~I-27),which were acylated by different aromatic oxygen acetyl chloride(D1~D4),and then 19 new 7-aryloxyacetoxy coumarin derivatives(TM-28~TM-46)was synthesized.All their structure are confirmed by 1H NMR,13 C NMR,IR and elemental analysis.The preliminary herbicidal activity results showed that most of the 7-aryloxyacetoxy coumarin derivatives' inhibition rate for dicotyledonous rapeseed roots long is superior to the control medicine 2,4-D's,and they also have high inhibitory activity for monocotyledon weed.Potted plant experiment(50 g/mu)also showed that the target compounds' inhibitory effect and selectivityisfair to 2,4-D's;And they show some structure-activity relationship,which to be the foundation for our further design compounds with high herbicidal activity.