CN107987024B - 具生物活性的嘧啶胺类化合物及其制备方法 - Google Patents
具生物活性的嘧啶胺类化合物及其制备方法 Download PDFInfo
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Abstract
Description
技术领域:本发明涉及具生物活性的嘧啶胺类化合物及其制备方法。
背景技术:
由于农药单剂、长期和高剂量的不合理使用,害虫抗药性越来越严重,特别是抗性蚜和抗性螨,如:蚜虫对吡虫啉等药物的抗性,国外报道的二斑叶螨抗性:哒螨灵抗药性1100倍(日)、唑螨酯抗药性870倍(日)、吡螨胺抗药性33倍(日)哒螨灵抗药性480倍(英)、唑螨酯抗药性45倍(英)、吡螨胺抗药性44倍(英)等等。因此创制合成具高效,低抗性的新农药成为了农药研究工作者研究的重要方向。嘧啶类化合物是一类具有广泛生物活性,包括杀虫、除草等活性的含氮杂环类化合物。如:上世纪60年代由ICI Agrochemicals公司开发的抗蚜威(Pirimicarb),用于防治大豆、小麦、玉米等作物及水果、蔬菜上的蚜虫,特别对产生抗性的桃蚜有特效;由ICI Plant Protection Division公司开发的甲基嘧啶磷(Pirimiphos-methyl)是一种广谱性杀虫、杀螨剂,对甲虫和蛾类有较好的防效,尤其是对防治储粮害螨高效;由日本宇部兴产公司先后开发的嘧螨醚(Pyrimidifen)和嘧虫胺(Flufenerim)是一类新型的嘧啶类杀虫剂,前者主要用于防治果、蔬、茶等作物上的叶螨,后者作为嘧啶胺类活性化合物的杰出代表,嘧虫胺具有杀虫、杀螨活性,推测作用机理与唑虫酰胺(tolfenpyrad)类似,为线粒体电子传递抑制剂。基于文献【农药:Vol 52,No.9,639-641,2013】报道,嘧虫胺对蚜虫和叶螨均具有较高的活性,但嘧虫胺对蚜虫(桃蚜)的活性低于吡虫啉(imidacloprid,D2),如在1.25mg/L浓度下,吡虫啉(D2)对桃蚜的活性为73%,远优于同等剂量下嘧虫胺(D1)对桃蚜的活性37%;在10mg/L浓度下,嘧虫胺(D1)对朱砂叶螨的活性为73%,降低浓度至5mg/L时,嘧虫胺(D1)对朱砂叶螨的活性为0%。嘧螨酯(Fluacrypyrim)是1994年由巴斯夫公司研发,日本曹达公司开发的第一个甲氧基丙烯酸酯类杀螨剂,在10-200g/hm2剂量下对苹果、柑橘红蜘蛛等多种螨高效;还有丁基嘧啶磷(Tebupirimfos)等多种杀虫剂。嘧啶结构作为活性结构,在杀虫剂方面特别是对蚜、螨具有好的防杀活性,且少见有抗性的报道,这为广大的农药工作者提供了较大的研究空间。为了设计、合成出具更好杀虫活性的化合物,我们设计、合成了末见文献报道的如结构(I)所示的嘧啶类化合物。
发明内容:本发明的目的在于提供一种具生物活性的嘧啶胺类化合物及其制备方法。
本发明嘧啶胺类化合物用结构通式(Ⅰ)表示:
式中
R为:(C1-C4)直链或支链烷基,烷氧基,烷硫基,烷胺基或苯基;
R1为:(C1-C4)直链或支链烷基或卤代烷基;
R2为:氢,(C1-C4)直链或支链烷基或卤素;
R3为:氢,卤素或(C1-C4)直链或支链烷基;
R4为:(C1-C4)直链或支链烷基或卤素;
W为:氧。
本发明式(I)化合物中的优选化合物为:
本发明式(I)中的化合物可以通过下面的反应合成,具体如下:
将中间体(A)和脒盐在合适的溶剂中,滴加30%的甲醇钠溶液,室温反应1小时,回流1-5小时,反应制得中间体(B)。较佳的溶剂是无水乙醇,较佳的回流温度是3小时。
将中间体(B)和三氯氧磷加入反应瓶中,冰浴冷却下,在-5-15℃条件下慢慢滴加缚酸剂,滴加完毕,室温反应3-20小时,反应制得中间体(C)。较佳的滴加温度是0-5℃,较佳的缚酸剂是三乙胺,较佳的室温反应时间是16小时。
将中间体(C)和苄胺、缚酸剂在合适的溶剂中,加热至60-100℃反应3-6小时,反应制得嘧啶胺类化合物(I)。较佳的缚酸剂是无水碳酸钾,较佳的溶剂是N,N-二甲基甲酰胺,较佳的反应温度是80℃,较佳的反应时间是4小时。
本发明式(I)中的化合物的制备和应用通过下述实施例例示,但这些实施例的技术内容不限制本发明的范围。
合成的部分本发明通式(Ⅰ)所示的化合物见表1。
表1:部分本发明通式(I)所示的化合物
表1中通式(I)所示的化合物的状态、熔点、1H NMR及MS参数。
I1:淡黄色粘固
1H NMR(CDCl3)2.330(s,3H,CH3),2.425(s,3H,CH3),2.495(s,3H,CH3),4.646(d,J=5.4Hz,2H,CH2),5.547(bs,1H,NH),6.890-6.971(m,4H,Ph H),7.109-7.150(m,2H,PhH),7.258-7.307(m,2H,Ph H).
GS-MS M+=353基峰197
I2:棕色粘固
1H NMR(CDCl3)2.363(s,3H,CH3),2.403(s,3H,CH3),2.840(s,3H,CH3),2.843(s,3H,CH3),4.652(d,J=5.4Hz,2H,CH2),4.900(bs,1H,NH),6.888-6.966(m,4H,Ph H),7.125-7.152(m,2H,Ph H),7.268-7.306(m,2H,Ph H);HPLC-MS Pos[M+1]+=334
I3:棕色固体,mp:℃
1H NMR(CDCl3)0.894(t,J=3.9Hz,3H,CH3),1.334-1.466(m,4H,2CH2),2.334(s,3H,CH3),2.416(t,J=4.5Hz,2H,CH2),2.464(s,3H,CH3),2.487(s,3H,CH3),4.658(d,J=5.4Hz,2H,CH2),4.785(bs,1H,NH),6.885-6.971(m,4H,Ph H),7.114-7.155(m,2H,Ph H),7.270-7.292(m,2H,Ph H);GS-MS M+=375基峰375
I4:淡黄色粘固
1H NMR(CDCl3)2.429(s,3H,CH3),2.495(s,3H,CH3),4.668(d,J=5.7Hz,2H,CH2),5.600(bs,1H,NH),6.919-6.981(m,4H,Ph H),7.272-7.333(m,4H,Ph H);GS-MS M+=373基峰217
I5:淡黄色粘固
1H NMR(CDCl3)1.253(t,J=7.5Hz,3H,CH3),2.337(s,3H,CH3),2.535(s,3H,CH3),2.770-2.801(q,J=7.5Hz,2H,CH2),4.658(d,J=5.4Hz,2H,CH2),5.610(bs,1H,NH),6.895-6.979(m,4H,PhH),7.118-7.158(m,2H,Ph H),7.253-7.318(m,2H,Ph H);GS-MS M+=367基峰197
I6:黄色粘固
1H NMR(CDCl3)1.256(t,J=7.5Hz,3H,CH3),2.510(s,3H,CH3),2.724-2.800(q,J=7.5Hz,2H,CH2),4.670(d,J=6.0Hz,2H,CH2),5.600(bs,1H,NH),6.925-6.986(m,4H,PhH),7.272-7.343(m,4H,Ph H);GS-MS M+=387基峰217
I7:淡黄色粘固
1H NMR(CDCl3)1.254(t,J=7.5Hz,3H,CH3),2.176(s,3H,CH3),2.317(s,3H,CH3),2.512(s,3H,CH3),2.748-2.798(q,J=7.5Hz,2H,CH2),4.629(d,J=6.0Hz,2H,CH2),5.580(bs,1H,NH),6.809-6.872(m,3H,Ph H),6.956-6.991(m,1H,Ph H),7.059(s,1H,Ph H),7.232-7.285(m,2H,PhH);GS-MS M+=381基峰211
I8:淡黄色粘固
1H NMR(CDCl3)0.985(t,J=2.1Hz,3H,CH3),1.679-1.756(m,2H,CH2),2.377(s,3H,CH3),2.508(s,3H,CH3),2.742(t,J=7.8Hz,2H,CH2),4.657(d,J=5.4Hz,2H,CH2),5.6102(bs,1H,NH),6.897-6.980(m,4H,Ph H),7.122-7.160(m,2H,Ph H),7.262-7.310(m,2H,Ph H);GS-MSM+=381基峰197
I9:淡黄色粘固
1H NMR(CDCl3)1.226(d,J=5.4Hz,6H,2CH3),2.337(s,3H,CH3),2.517(s,3H,CH3),3.386-2.398(q,J=7.5Hz,1H,CH),4.650(d,J=5.4Hz,2H,CH2),5.525(bs,1H,NH),6.895-6.977(m,4H,Ph H),7.117-7.165(m,2H,Ph H),7.253-7.323(m,2H,Ph H);GS-MS M+=381基峰197
I10:淡黄色固体,mp:55-57.6℃
1H NMR(CDCl3)0.949-0.996(m,2H,CH2),1.113-1.137(m,2H,CH2),2.281-2.324(m,1H,CH),2.333(s,3H,CH3),2.417(s,3H,CH3),4.642(d,J=6.6Hz,2H,CH2),5.445(bs,1H,NH),6.901-6.969(m,4H,Ph H),7.125-7.153(m,2H,Ph H),7.256-7.301(m,2H,Ph H);HPLC-MSPos[M+1]+=380
I11:淡黄色粘固
1H NMR(CDCl3)0.916(d,J=7.5Hz,3H,CH3),1.375-1.474(m,2H,CH2),1.596-1.699(m,2H,CH2),2.337(s,3H,CH3),2.512(s,3H,CH3),2.708-2.761(m,2H,CH2),4.648(d,J=5.7Hz,2H,CH2),5.556(bs,1H,NH),6.896-6.977(m,4H,Ph H),7.121-7.157(m,2H,PhH),7.272-7.320(m,2H,Ph H);HPLC-MS Pos[M+1]+=396
I12:淡黄色粘固
1H NMR(CDCl3)0.956(d,J=5.4Hz,6H,2CH3),2.147-2.193(m,1H,CH),2.337(s,3H,CH3),2.515(s,3H,CH3),2.623(d,J=7.5Hz,2H,CH2),4.650(d,J=5.4Hz,2H,CH2),5.595(bs,1H,NH),6.907-6.980(m,4H,Ph H),7.122-7.157(m,2H,Ph H),7.276-7.314(m,2H,Ph H);HPLC-MSPos[M+1]+=396
I13:白色固体,mp:109.7-110.3℃
1H NMR(CDCl3)2.339(s,3H,CH3),3.986(s,3H,CH3),4.600(d,J=5.4Hz,2H,CH2),6.352(s,1H,NH),6.894-6.972(m,4H,Ph H),7.130-7.161(m,2H,Ph H),7.252-7.274(m,2H,Ph H);GS-MSM+=389基峰197
I14:黄色粘固
1H NMR(CDCl3)2.344(s,3H,CH3),2.594(s,3H,CH3),4.693(d,J=5.7Hz,2H,CH2),5.942(bs,1H,NH),6.914-6.992(m,4H,Ph H),7.141-7.170(m,2H,Ph H),7.273-7.312(m,2H,Ph H);GS-MS M+=407基峰197
I15:淡黄色粘固
1H NMR(CDCl3)0.900-0.961(m,2H,CH2),1.009-1.059(m,2H,CH2),1.251(t,J=7.5Hz,3H,CH3),2.044-2.055(m,1H,CH),2.333(s,3H,CH3),2.712-2.762(q,J=7.5Hz,2H,CH2),4.588(d,J=5.7Hz,2H,CH2),5.600(bs,1H,NH),6.896-6.966(m,4H,Ph H),7.121-7.152(m,2H,Ph H),7.247-7.276(m,2H,Ph H);HPLC-MS Pos[M+1]+=394
I16:淡黄色粘固
1H NMR(CDCl3)1.364(t,J=7.5Hz,3H,CH3),2.329(s,3H,CH3),2.867-2.916(q,J=7.5Hz,2H,CH2),4.812(d,J=5.4Hz,2H,CH2),5.672(bs,1H,NH),6.888-6.994(m,4H,PhH),7.115-7.197(m,2H,Ph H),7.326-7.373(m,2H,Ph H),7.431-7.460(m,3H,Ph H),8.391-8.430(m,2H,Ph H);HPLC-MS Pos[M+1]+=430
I17:淡黄色粘固
1H NMR(CDCl3)2.399(s,3H,CH3),3.976(s,3H,CH3),4.670(d,J=5.7Hz,2H,CH2),6.000(bs,1H,NH),6.904-6.988(m,4H,Ph H),7.143d,J=3.6Hz,2H,Ph H),7.260-7.296(m,2H,Ph H);GS-MS M+=423基峰197
I18:淡黄色固体,mp:105.1-106.9℃
1H NMR(CDCl3)1.339(t,J=6.9Hz,3H,CH3),2.255(s,3H,CH3),2.332(s,3H,CH3),4.284(q,J=6.9Hz,2H,CH2),4.485(d,J=6.9Hz,2H,CH2),5.196(bs,1H,NH),5.853(s,1H,Pyrimidine H),6.877-6.962(m,4H,Ph H),7.112-7.157(m,2H,Ph H),7.225-7.263(m,2H,PhH);GS-MS M+=349基峰349
I19:黄色粘固
1H NMR(CDCl3)1.371(t,J=7.2Hz,3H,CH3),2.333(s,3H,CH3),2.389(s,3H,CH3),4.336(q,J=7.2Hz,2H,CH2),4.633(d,J=6.6Hz,2H,CH2),5.295(bs,1H,NH),6.896-6.961(m,4H,Ph H),7.123-7.154(m,2H,Ph H),7.256-7.285(m,2H,Ph H);GS-MS M+=383基峰197
I20:黄色粘固
1H NMR(CDCl3)1.319(d,J=6.3Hz,6H,2CH3),2.335(s,3H,CH3),2.386(s,3H,CH3),4.628(d,J=5.4Hz,2H,CH2),5.168(q,J=6.3Hz,1H,CH),5.600(bs,1H,NH),6.893-6.964(m,4H,PhH),7.124-7.253(m,2H,Ph H),7.275-7.282(m,2H,Ph H);GS-MS M+=397基峰197
I21:白色固体,mp:63.8-64.5℃
1H NMR(CDCl3)2.333(s,3H,CH3),2.399(s,3H,CH3),2.481(s,3H,CH3),4.651(d,J=5.1Hz,2H,CH2),5.630(bs,1H,NH),6.888-6.969(m,4H,Ph H),7.125-7.256(m,2H,PhH),7.276-7.283(m,2H,Ph H);GS-MS M+=385基峰197
I22:类白色固体,mp:99.2-100.1℃
1H NMR(CDCl3)2.045(s,3H,CH3),2.319(s,3H,CH3),2.333(s,3H,CH3),2.483(s,3H,CH3),4.653(d,J=5.4Hz,2H,CH2),4.800(bs,1H,NH),6.894-6.945(m,4H,Ph H),7.122-7.152(m,2H,Ph H),7.259-7.289(m,2H,Ph H);GS-MS M+=365基峰365
I23:淡黄色粘固
1H NMR(CDCl3)10891(s,3H,CH3),2.328(s,3H,CH3),2.342(s,3H,CH3),3.110(s,6H,2CH3),4.623(d,J=5.4Hz,2H,CH2),4.625(bs,1H,NH),6.890-6.951(m,4H,Ph H),7.115-7.142(m,2H,Ph H),7.282-7.310(m,2H,Ph H);GS-MS M+=362基峰362
I24:淡黄色粘固
1H NMR(CDCl3)1.112(t,J=6.9Hz,6H,2CH3),2.302(s,3H,CH3),2.374(s,3H,CH3),3.533(q,J=7.2Hz,2H,CH2),4.583(d,J=6.0Hz,2H,CH2),5.412(bs,1H,NH),6.883-6.957(m,4H,PhH),7.113-7.141(m,2H,Ph H),7.267-7.289(m,2H,Ph H);GS-MS M+=410基峰197
具体实施方式
合成实施例
实施例1:表1中化合物I5制备。
1、氯代丙酰基乙酸乙酯(A5)的合成:在配有磁力搅拌器、温度计的250mL三口圆底烧瓶中加入二氯甲烷100mL、丙酰乙酸乙酯36.0g(0.25mol),冰浴冷却,在0~5℃条件下慢慢滴加磺酰氯35.4g(0.263mol),滴加完毕后撤除冰浴,室温反应过夜。反应完全后,倒入400mL饱和盐水中,二氯甲烷(100Mlx2)萃取两次,合并有机相,无水硫酸钠干燥,减压脱除溶剂,得亮黄色液体氯代丙酰基乙酸乙酯(A5)39.2g,含量98.0%,收率87.0%。
2、5-氯-6-乙基-2-甲基嘧啶-4-醇(B5)的合成:在配有磁力搅拌器、温度计和冷凝管的250mL三口圆底烧瓶中加入甲醇150mL和盐酸乙脒20.4g(0.22mol),溶解完全后,滴加30%的甲醇钠溶液39.6g(0.22mol),冰浴冷却,在20℃以下慢慢滴加氯代丙酰基乙酸乙酯(A5)39.2g(0.22mol),滴加完毕后撤除冰浴,室温反应1h,加热升温回流3h。反应完全后,反应液冷却,过滤,滤液减压脱除溶剂,得淡黄色固体5-氯-6-乙基-2-甲基嘧啶-4-醇(B5)29.7g,含量94.0%,收率73.9%。
3、4,5-二氯-6-乙基-2-甲基嘧啶(C5)的合成:在配有磁力搅拌器、温度计和冷凝管的的250mL三口圆底烧瓶中加入5-氯-6-乙基-2-甲基嘧啶-4-醇(B5)10.4g(0.06mol),冰浴冷却下,慢慢加入三氯氧磷37.0g(0.24mol),滴加完毕再继续搅拌反应30min,然后在5~10℃条件下慢慢滴加三乙胺24.5g(0.24mol),2h后撤除冰浴,室温反应过夜,反应完全后,将反应液倒入400mL冰水中,二氯乙烷萃取两次,合并有机相,无水硫酸钠干燥,最后减压脱除溶剂得棕色粘固4,5-二氯-6-乙基-2-甲基嘧啶(C5)6.2g,含量92.0%,收率49.6%。
4、5-氯-6-乙基-2-甲基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I5)的合成:在配有磁力搅拌器、温度计和冷凝管的250mL三口圆底烧瓶中加入N,N-二甲基甲酰胺30mL、4,5-二氯-6-乙基-2-甲基嘧啶(C5)2.5g(0.013mol)、4-甲基苯氧基苄胺2.8g(0.013mol)和无水碳酸钾3.6g(0.026mol),加热至80℃,反应4h。反应完全后,倒入400mL饱和盐水中,乙酸乙酯(150Mlx2)萃取两次,合并有机相,无水硫酸钠干燥,脱除溶剂。粗品经硅胶柱层析[v(石油醚):v(乙酸乙酯)=15:1]得到淡黄色粘固5-氯-6-乙基-2-甲基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I5)2.8g,纯度97%。
实施例2:表1中化合物I20制备。
1、4,5-二氯-6-甲基-2-异丙氧基嘧啶(C20)的合成:在配有磁力搅拌器、温度计和冷凝管的的250mL三口圆底烧瓶中加入5-氯-6-甲基-2-异丙氧基嘧啶-4-醇(B20)2.0g(0.01mol),冰浴冷却下,慢慢加入三氯氧磷8.5g(0.056mol),滴加完毕再继续搅拌反应30min,然后在5~10℃条件下慢慢滴加三乙胺1.5g(0.015mol),2h后撤除冰浴,室温反应过夜,反应完全后,将反应液倒入400mL冰水中,二氯乙烷萃取两次,合并有机相,无水硫酸钠干燥,最后减压脱除溶剂得深色粘固4,5-二氯-6-甲基-2-异丙氧基嘧啶(C20)1.8g,含量93.0%,收率76.1%。
2、5-氯-6-甲基-2-异丙氧基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I20)的合成:在配有磁力搅拌器、温度计和冷凝管的250mL三口圆底烧瓶中加入N,N-二甲基甲酰胺30mL、4,5-二氯-6-甲基-2-异丙氧基嘧啶(C20)1.1g(0.005mol)、4-甲基苯氧基苄胺1.7g(0.008mol)和无水碳酸钾2.0g(0.015mol),加热至80℃,反应4h。反应完全后,倒入400mL饱和盐水中,乙酸乙酯(150Mlx2)萃取两次,合并有机相,无水硫酸钠干燥,脱除溶剂。粗品经硅胶柱层析[v(石油醚):v(乙酸乙酯)=10:1]得到黄色粘固5-氯-6-甲基-2-异丙氧基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I20)1.1g,纯度97%。
实施例3:表1中化合物I24制备。
1、4,5-二氯-6-甲基-2-二乙胺基嘧啶(C24)的合成:在配有磁力搅拌器、温度计和冷凝管的的250mL三口圆底烧瓶中加入5-氯-6-甲基-2-二乙胺基嘧啶-4-醇(B24)2.8g(0.013mol),冰浴冷却下,慢慢加入三氯氧磷5.0g(0.033mol),滴加完毕再继续搅拌反应30min,然后在5~10℃条件下慢慢滴加三乙胺3.0g(0.03mol),1h后撤除冰浴,室温反应2h,反应完全后。加入300mL乙酸乙酯,将反应液倒入400mL冰水中,萃取,有机相无水硫酸钠干燥,最后减压脱除溶剂得淡黄色粘固4,5-二氯-6-甲基-2-二乙胺基嘧啶(C24)1.5g,含量95.0%,收率47.5%。
2、5-氯-6-甲基-2-二乙胺基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I24)的合成:在配有磁力搅拌器、温度计和冷凝管的250mL三口圆底烧瓶中加入N,N-二甲基甲酰胺30mL、4,5-二氯-6-甲基-2-二乙胺基嘧啶(C24)1.5g(0.0064mol)、4-甲基苯氧基苄胺1.7g(0.008mol)和无水碳酸钾2.0g(0.015mol),加热至80℃,反应4h。反应完全后,倒入400mL饱和盐水中,乙酸乙酯(150Mlx2)萃取两次,合并有机相,无水硫酸钠干燥,脱除溶剂。粗品经硅胶柱层析[v(石油醚):v(乙酸乙酯)=30:1]得到淡黄色粘固5-氯-6-甲基-2-二乙胺基-N-(4-甲苯氧基)苄基)嘧啶-4-胺(I24)0.7g,纯度95%。
生物活性测试实施例
1、试验靶标:
蚕豆蚜(Aphis fabae);棉红蜘蛛(Tetranychus urticae);粘虫(Mythimnaseparata);
2、试验方法:
对螨综合毒力试验方法:采用叶虫同浸法,将带有试虫(红蜘蛛)的蚕豆苗从茎部剪下,带有试虫的叶部浸入供试药液中10秒,取出后用滤纸将多余的药液吸干,然后插到吸满水的海绵中(直接放在盛有清水的小烧杯中)培养,72h后,统计死亡和存活的头数。实验重复三次,结果取平均值。活性相对于空别对照以百分比计。
对蚜虫综合毒力试验方法:将蚜虫接于刚出土的豆苗上,每株接20头以上,然后将豆苗连同试虫一起浸入配好药剂中,5秒钟后取出,吸去多余药液,插入吸水的海棉中,用玻管罩住,24小时后检查存活和死亡的虫数。实验重复三次,结果取平均值。活性相对于空别对照以百分比计。
对粘虫综合毒力试验方法:采用Potter喷雾法,取鲜嫩的玉米叶剪成大小基本一致的片段,放入事先垫有滤纸的培养皿(Ф90mm)中。然后在皿中接入粘虫3龄幼虫10头,放到Potter喷雾塔下进行定量喷雾,喷药液量1mL,每浓度3次重复。处理完毕,盖上皿盖,置于观察室内培养,定期观察,于72h后统计死亡和存活的头数。实验重复三次,结果取平均值。活性相对于空别对照以百分比计。
死亡率在90%以上为A级,70~90%之间为B级,50~70%之间为C级,0~50%之间为D级。
3、药剂配制:
称取适量的供试药剂,用N,N二甲基甲酰胺(DMF)溶解后,再加入0.2%的Tween80乳化剂,以玻璃棒搅拌均匀,再加入定量的清水配成所需浓度的母液,再用含0.2%Tween80乳化剂的水稀释成试验浓度进行试验,设含溶剂乳化剂的清水为对照。
采用从500mg/L到0.625mg/L多个梯度试验浓度对化合物(I)进行了粘虫、蚜虫、红蜘蛛的防治活性测试,测试结果见下表2-表6。
表2 500mg/L试验浓度下化合物(I)杀虫活性普筛结果
活性测试结果表明:在500mg/L试验浓度下I1,I2,I3,I4,I5,I6,I8,I9,I11,I12,I13,I14,I21,I22对蚜虫或红蜘蛛具80-90%的防杀活性,I6对粘虫、蚜虫和红蜘蛛同时具90%以上的防杀活性。
表3化合物(I)对蚜虫的活性初筛结果
化合物 | 200(mg/L) | 50(mg/L) | 12.5(mg/L) |
I<sub>1</sub> | 96.55 | 92.86 | 89.27 |
I<sub>3</sub> | 90.48 | 61.16 | 69.73 |
I<sub>4</sub> | 54.63 | 46.75 | 21.97 |
I<sub>5</sub> | 100.00 | 96.88 | 88.05 |
I<sub>6</sub> | 100.00 | 97.87 | 62.37 |
I<sub>8</sub> | 17.44 | 12.84 | 1.43 |
I<sub>9</sub> | 73.7 | 62.14 | 34.22 |
I<sub>11</sub> | 39.57 | 29.15 | 22.95 |
I<sub>12</sub> | 45.05 | 22.26 | 5.52 |
I<sub>14</sub> | 100.00 | 56.23 | 13.17 |
I<sub>22</sub> | 56.68 | 18.29 | 6.53 |
表4化合物(I)对红蜘蛛的活性初筛结果
活性测试结果表明:在200mg/L、50mg/L、12.5mg/L试验浓度下I1,I3,I5,I6,I14,对蚜虫具80-90%的防杀活性;I1,I4,I5,I6,I9,对红蜘蛛具80-90%的防杀活性。
表5化合物(I)对红蜘蛛的活性复筛结果
表6化合物(I)对蚜虫的活性复筛结果
活性测试结果表明:I5在20mg/L、10mg/L、5mg/L、2.5mg/L试验浓度下对红蜘蛛具80-90%的防杀活性,优于对照药剂螺虫乙酯;在20mg/L、10mg/L、5mg/L、2.5mg/L、1.25mg/L试验浓度下对蚜虫具80-90%的防杀活性,优于对照药剂吡虫啉。I4对红蜘蛛的防治效果与照药剂螺虫乙酯相当。
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