1,2,4-三唑类杀菌剂的合成与生物活性advancein

*(550025)1,2,4-1,2,4-1,2,4-AdvanceinSynthesisandBiologicalActivityof1,2,4-TriazoleDerivativesHuDeyu,SongBaoan*,YangSong,JinLinhong(ResearchandDevelopmentCenterforFineChemicals,GuizhouUniversity,KeylaboratoryofGreenPesticide&AgriculturalBiologicalEngineering,MinistryofEducation,Guiyang550025)Abstract1,2,4-triazolecompoundsplayedanimportantroleinpesticideapplication.Accordingtodifferentstructuresof1,2,4-triazolecompounds,theirchemicalsynthesisandbiologicalactivityarereviewed.Thedevelopingtrendandbroadapplicationprospectsof1,2,4-triazoleandtheirderivativesarealsodiscussed.Keywords1,2,4-Triazole,Fungicide,Synthesis,Biologicalactivity1,2,4-19761,2,41,2,4-11,2,4-[1]903-6-12(Botrytiscinerea)(Rhizoctonia)(Ascochytamaydis)(Gibberellazeae)(CercosporaarachidicolaHori)(Alternariaalternata)39*E-mail:[e-mail](20362004)(20021993)(20011067)2003-12-222004-02-23(R=2-,R1=C4H9)661.17%NSNNNRR11R=3-pyridyl,4-pyridyl,aryl,2-naphthylmethyleneR1=alkyl,aryl,3-pyridyl,4-pyridyl,aroxymethyleneb-naphoxymethyleneNSNNNRNH2COXR=3-pyridyl,4-pyridyl,aryl,X=CH3O,CH3,H,F,Cl,Br,I,NO2.Johi[2]3NNXNHNH2RNNXNHNHCOR1RNNNNXRR1PPA33()(Streptococcusfaecalis)(IZ)=20.03-F(Aspergillnsflarns)(Candidaalbicans)(Curvnlarialunatn)Tiwari[3]4R=4-Cl1000mg/L(Aspergillusniger)(Pyriculariaoryzae)94%(carbendazim)ONNNOCH2R4NNSNNO5Foroumadi[4]1,3,4-5dotuimuaolCandidaalbicausKundel[5]6Mueller[6]7(7--5--6-(2--6-))-1,2,4[1,5-a]63mg/L(Alternariasolani)90%SNOSNNHSNNNNNPh6NNNNR1R2R7NNNN8OMeNR1R2L2L1Tormo[7]85--6-(4,6--2-)-1-(1,1,1--2-)-1,2,4-[1,5-a]50mg/L(Ceraspora)7%90%2003Tormo[8]6-(2,6-)-[1,5-a](9)NNHH2NFFCHCOOEtCOOEtNaOHNNNNOHOHFFNNNNNHClFFi-Pr+n-Bu3N,180oCi-PrNH2/NH39POCl3250mg/L(Alternariasolani)90%21,2,4-[9]10X1=H,X2=4-CH3,X3=4-CH30.05%(Pucciniarecondiata)70%X1COHCCH2CHSX3X2NNN10NNNNNMeNHArSClCH2COOHNNNMeNNNArSCH2COOHKOH/CH3OH/H2O11[10]5-(1--5--1,2,3--4-)-4--1,2,4--3-(11)11c(Ar=o-CH3C6H4)11e(Ar=p-BrC6H4)11i(Ar=p-CH3C6H4)11k(Ar=p-CF3C6H4)5.010-5mol/L10%63.9%[11]2-[1H-1,2,4--1-]-β--β-12THF12X1COCH2NNNCH2CHOX2X1COCNNNCH2CHX2SHX3CNNCH2CHSX3X1COHNX2X1COCHNNNCH2CHSX3X2NaBH4X1CHOHCHNNNCH2CHSX3X2+12120.05%12a(X1,X2,X3=H)80%[12]2-(1H-1,2,4--1-)-2--1--5-1,4-13(2-(1H,1,2,4--1-)-β-)(CH2O)nH2OR1COCCH2NNNR3SHR1COCHCH2SR2NNN13313R2Ar13f(R1=C6H5,R2=4-CH3C6H4)80%R1=t-Bu1390%60%90%13b(R1=Cl-C6H4,R2=4-FC6H4)13k(R1=4-FC6H4,R2=4-ClC6H4)100%Xu[13]N,N-1,2,4-R12NH+CS2+NH3H2OR1NR1CSSNH4COCH2BrRNHNNCOCH2RNNN14COCHRNNNBr14COCHRNNNR1NR1CSS15Br2(P.zeae)(A.solani)(P.piricola)0.005%15d(R1=CH3,R=Ph)32.4%97.4%[14]1616RCOCH2Br+NHNNRCOCH2NNNRCOCHNNNBrSHR1RCOCHNNNSR1Br2HOAc/NaOAc1616(500µg/mL)16c(R=Me3C,R1=F)16d(R=Me3C,R1=Cl)8100%NNNR1O(CH2O)nH2ONNNR1OR2SHNNNR1OSR2NaBH4NNNR1OHSR217[15]α-3-(2-(1H-1,2,4--1-)-3-)510-4%R1=Me3CR1=Ar17c(R1=4-FC6H4,R2=4-ClC6H4)82.6%56%17d(R1=Me3C,R2=2-benzothiazolyl)85%72.4%[16]1,2,4-1,2,4-20(O,O--5-)PSROROSK+ClCH2COOHPSROROSCH2COOH18R1COCH2NNNR1COCHNNNBr1918/Et3NPSROROSCH2COOR1COCHNNN20Br2500mg/L20e(R=Et,R1=4-FC6H4)49.6%[17]2-21t-BuCOCH2NNNt-BuCOCHNNNCH2OHHCHOt-BuCOCNNNCH2RSHt-BuCOCHNNNCH2SRt-BuCHOHCHNNNCH2SRNaBH4Ac2O2121500mg/L100%PGK3[18](S3308)2-4-2-(1H-1,2,4--1-)K2CO31,2,4-NaBH41,2,4-22R1COCH2NNNR1COCNNNCHR2KBH4HClR1CHOHCNNNCHR2R2CHOK2CO3(CH3CO)2O+22500µg/L(R1=C(CH3)3,R2=2-pyridinyl)22c(R1=p-FC6H4,R2=2-pyridinyl)10050µg/L[19]2-(1H-1,2,4--1-)-β-23NNHNClCH2CNNNCH2CNNNN(H3C)2HNHCCNNHClNH2XCNNCHNNNHX.1)DMF/DMA2)HCl/C2H5OH2323g(X=4-NO2)23l(X=2-OCH3)23o(X=4-CF3)23r(X=2-Cl-4-NO2)50µg/mL65%50µg/mL23m(X=4-F)50%Ammar[20]2-(6--2-)(thiocarbohydrazide)1-(6--2-)-1-(5′--4'--(-3-))24H3COCHCOOHCH3+SH2NHNNHNH2H3COCHCH3NNHNSNH2HEtOCNCNH3COCHCH3NNHNSHNCNCNH241mg/LCandidaalbicans,Penialliumchrysogenum,Aspergillusflavus241036mm4Popkiv[21]2-Claisen-Schmidtdimethylsulfoniummethylide1,2,4-25R1R2OR1R2Ot-BuOK(CH3)2SIR1R2OR1R2HOR3CH2NNNNaOH/DMF1,2,4-triazole25R3R3R3CHOKBH4HClBu-tCHCHCHOHClNNNNR1R2OBu-tCHCCClNNNCHCHCOBu-tClNNNNR1R2PhCH3R1R2NH26[22]α,β-(R1=H,R2=CH3)94.7%26a(R1=H,R2=(CH3)2CH)89.594.7%5N-[23]Wittig1,2,4-1-(2-)-1H-1,2,4-27(50mg/L)7100%2-27d(Ar1=4-ClC6H4,Ar2=4-CH3C6H4)100%81%NCOOEtAr1PPh3Ar2NCOCOOEtAr1NAr2NCNHNNNOAr2NNNAr1NK2CO3(s)276Yoo[24][1-(1H-1,2,4--1-)]-1-(28)SiClClClRClTHFSiClRXNaI(1)ClMg(CH2)4MgCl(2)p-XPhMgXSiIRXNNNNaDMFSiNRXNN28(Alternariamali)(RhizoctoniaSolani)(Botrytiscinerea)(Phytophthoracapsici)(Fusuriummoniliforme)(Magnaporthegrisea)(Botryosphaeriadoihideo)12.550µg/LFClPhOEtH28b(R=H,X=F)28c(R=CH3,X=F)965%100%71,2,4-1,2,4-1,2,4-[1](a).1991,49:513~520.(b).1993,13:397~402.(c).1994,15(2):220~223.(d).1993,14(4):512~516.(e).2000,2(4):1~10.[2]KCJoshi,RJain,ADenesetal.Pestic.Sci.,1990,29(2):143~149.[3]STiwari,MHKhan,HNizamuddin.IndianJ.Chem.B,1997,36B(8):711~714.[4]AForoumadi,MMirzaei,SEmamietal.Daru,J.FacultyPharmacy,TehrenUniversityofMedicalSciences,2002,10(1):34~37.[5]MMKan