The Synthesis And Biological Activity Of Novel Allyl Substituted Diaryl Ethers

In order to discover novel herbicides and lead compounds with high activity, safety and environmental compatibility, 11 series of a total of 111 novel allyl group substituted diaryl ether compounds were designed and synthesized according to the principle of bioactive substructure combination. Their structures were confirmed by NMR, IR, EA and MS Subsequently, the biological activities of target compounds and some important intermediates were evaluated in the greenhouse.Twenty-nine intermediate Baylis-Hillman adducts were prepared at room temperature, using trimethylamine or DABCO as catalyst. Evaluation of their biological activities showed that 3-(hydroxy(4-nitrophenyl)methyl)but-3-en-2-one (BH-28) exhibited efficient fungicidal activity, with 100% control of Phytophthora infestans at 25 g a.i./hm~2; methyl 2-((2,4-dichlorophenyl)(hydroxy) methyl)acrylate (BH-8) showed broad-spectrum herbicidal activity, with 100% control of broad-leaved weeds Zinnia elegans Jacq and Abutilon theophrasti Medic, 80 % and 75 % control of grass weeds Echinochloa crusgalli (L.) Baeuv and Digitaria sanguinalis (L.) Scop respectively at 2000 g ai/hm~2.Rearrangement products 2,3-disubstituted allyl diarylether carboxylate were found when Baylis-Hillman adducts underwent esterification with acyl chloride of diarylether compounds at room temperature, utilizing triethylamine as catalyst.Commercial diphenylether (DPE) and aryloxyphenoxypropionate (APP) herbicides were modified by introducing an electron-withdrawing group (EWG) containing allyl into their structures. Results showed that some modified DPE compounds had better herbicidal activities than the prototype acifluorfen (a commercial DPE herbicide). Traditional APP herbicides show poor selectivity in monocotyledonous crops, are prone to induce crop injury and can only be used alone and only in dicotyledonous crops. The authors found that introducing EWG containing allyl into APP herbicides made the new compounds safe to both dicotyledonous and monocotyledonous crops. At the same time, the new compounds were highly active against grass weeds.Novel arylallylether (AAE) and 2-aryloxypenoxymethyl acrilate (APA) compounds synthesized via Baylis-Hillman reaction showed efficient fungicidal activities. For example, methyl 2-((3-(3-chloro-5-(trifluoromethyl)pyridin-2-yloxy)phenoxy)(phenyl)methyl)acrylate (APA-7) exhibited broad-spectrum fungicidal activity, with 100 % control of wheat powdery...