氟环唑的合成工艺研究进展

:2008-12-18:(1973-),,,,,刘丽秀1,张鲁新2,张亚敏3(1.,,250014;2.,,250100;3.,,250021):(Epoxiconazole):;;:TQ455.4+7:A:1008-021X(2009)04-0028-03TheResearchonSynthesizingofEpoxiconazoleLIULi-xiu1,ZHANGLu-xin2,ZHANGYa-min3(1.ShandongChemicalIndustryResearchInstitute,Jinan250014,China;2.ShandongResearchInstituteofPesticide,Jinan250100,China;3.JinanNo.6VocationalSchoo,lJinan250021,China)Abstract:Epoxiconazoleisanewtriazole-containingfungicidewithbroad-spectrumandlong-effectiveduration.Andthesyntheticmethodwasintroduced.Keywords:epoxiconazole;fungicide;synthesis1(Epoxiconazole)[1],,1983,;,:LD505000mg/kg,LD502000mg/kg;,LD50(4h)5.3mg/L,,,,,CAS:106325-08-0,:22.1,62.1.11[2](1)Z-1-(2-)-2-(4-)-3--1-10,2-,0.5h,4-,3h,,,,N-,,,Z-1-(2-)-2-(4-)-3--1-28SHANDONGCHEMICALINDUSTRY2009384(2)2--2-(4-)-3-(2-)-Z-1-(2-)-2-(4-)-3--1-3-,,,,,2--2-(4-)-3-(2-)-(3)1H-1,2,4-,(80%,)DMF,2--2-(4-)-3-(2-)-DMF,8h,,,,,,1362.1.22[3]58.9g(0.601mol)18.6g(0.0576mo,l97.2%)Z-3-(1H-1,2,4-)-2-(4-)-1-(2-)-1-150mL1,2-,40,20.6g(0.303mo,l50%),1h,7h,6.9mL38%NaHSO3100mL,50%NaOHpH=3,170mL38%NaHSO3,503h,,,87%~90%2.1.33[4](1)1--3-(2-)-2-(4-)-2-30g(1.25mol)100mL,17g(0.1mol)2-4~5min,,153g(0.95mol)2-800mL1h,30min,157g(0.91mol)4-250mL,0~2,,01~2h,1--3-(2-)-2-(4-)-2-(2)1--3--1-(2-)-2-(4-)-2-29,:4.0g(13.4mmol)1--3-(2-)-2-(4-)-2-2.3g(8.0mmo)1,3--5,5-80mL,(235V/500W)35,5.1g1--3--1-(2-)-2-(4-)-2-(3)3.9g(10.4mmol)1--3--1-(2-)-2-(4-)-2-2.4g(26.4mmol)1H-1,2,4-15mLDMF,754h,15~20mL,,V(DMF)!V()=1:1,,1.85g,58%2.1.44[5](1)2-(4-)-3-(2-)-35g2-200mL4.2g30mL,10,36g4-,30~40,4010h,2-(4-)-3-(2-)-(2)78.2g2-(4-)-3-(2-)-300mL0,50%,30,,6h,100mL,,,,52.5g-2--2-(4-)-3-(2-)-,63%1H-1,2,4-1.55[6](下转第41页)30SHANDONGCHEMICALINDUSTRY2009384,参考文献[1],,,.[J].,1999,7(1):88-93.[2],,.[J].,2001,22(6).[3],.[J].,2001,17(3):66-69.[4],,,.[J].,2004,20(2):63-66.[5].[M].:,1992.[6].[M].,.:,1981.[7].[J].,2003,(4).[8],.[J].,2001,27(4):14-15.[9],,.[J].,2003,3(13):123-126.(30)3.6g(0.058mol)10gKOH100mL,0,86g(0.053mol)2-,10g(0.049mol)2-(1H-1,2,4-)-4∀-50mL,2h,,100mL,,,,[V()!V()=9!1],2.6g,16%1.66[6]2g(0.007mol)1--1-(4-)-2-(1H-1,2,4-)0.5g40mL,2h,60,0.5h,,0.4gKOH1g(0.007mol)2-,6h,50mL,,,,,[V()!V()=9!1],0.9g,39%3,3,;4,5,6,;1,24-1-(2-)-2-(4-)-3--1-,,1H-1,2,4-;1-(2-)-2-(4-)-3--1-,1H-1,2,4-,,,,参考文献[1].Epoxiconazole[J].,1998(3):14-16.[2]Karbach,Stefan.Azolylmethyloxiranesandtheiruseasplant-protectingagents:EP,196038[P].1986-10-01.[3]Hickmann,Eckhard.Processforthrpreparationofcis-2-(1H-1,2-4-triazol-1-ylmethyl)-2,3-di(halophenyl)oxirane:EP,0427061[P].1991-05-01.[4]Kober,Reiner.Stereoselectivepreparationoferythro-1-bromo-3-chloro-1,2-diaryl-2-propanolsandtheirconversionintoazolylmethyloxiranes:EP,0431450[P].1991-06-12.[5]Seele,Rainer.Preparationofherbicidalandplantgrowthregulating(azolylmethyl)oxiranes:EP,0388871[P].1990-09-26.[6]Seele,Rainer.Processforthepreparationofcis-2-(1H-1,2,4-triazol-1-yl-methyl)-2,3-bis(halophenyl)oxiranes:EP,0515876[P].1992-12-02.41,: