CN106349223A - 含嘧啶硫醚结构的吡唑肟醚化合物的制备方法和应用 - Google Patents
含嘧啶硫醚结构的吡唑肟醚化合物的制备方法和应用 Download PDFInfo
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Abstract
本发明涉及一种含嘧啶硫醚结构的吡唑肟醚化合物(I)及其制备方法和应用。通过吡唑肟(II)与4‑(4,6‑二甲氧基‑2‑嘧啶硫基)苯甲基氯(III)缩合得到。所述含嘧啶硫醚结构的吡唑肟醚化合物(I)对有害昆虫具有防治效果，该类型化合物可用于制备农业、园艺等领域的杀虫剂。
Description
技术领域
本发明属于农药领域，具体涉及一种含嘧啶硫醚结构的吡唑肟醚化合物及其制备方法和用途。
背景技术
害虫的防治一直以来是农药科学研究的核心领域，杀虫剂的广泛使用使得多数害虫得到了有效治理。但随着杀虫剂应用规模的不断扩大，传统农药品种的抗药性问题日益凸显，加上新的病虫害的不断出现，使得新农药的继续研究和开发成为必然选择。
吡唑肟类衍生物是一类重要的含氮杂环化合物，其代表性化合物如唑螨酯，在农药领域的杀虫方面发挥着重要作用。
近年来有一些研究报道了吡唑肟类衍生物具有良好的杀虫、杀螨效果，如Fu等研究发现含吡啶杂环结构的吡唑肟衍生物A和B对蚜虫和螨虫具有较好的抑制作用，化合物A在测试剂量为10mg/L时，对二斑叶螨的杀死率为95％，化合物B在测试剂量为50mg/L时，对蚜虫的杀死率为89％(Pest Manage.Sci.2014,70,1207-1214)；Dai等报道的化合物C和D对蚜虫、螨虫及小菜蛾等表现出优异的杀虫杀螨活性。在测试浓度为100μg/mL时，化合物C和D对蚜虫的防治效果均为100％；化合物C和D对螨虫的防治效果分别为100％和90％；化合物C和D对小菜蛾的防治效果分别为60％和100％(Bioorg.Med.Chem.Lett.2016,26,3818–3821)。
嘧啶环在农业生产方面应用广泛，嘧啶类化合物因其高效、低毒和环境友好等特点已成为杀虫研究的热点领域之一。嘧啶杂环单元结构被广泛地引入到农药分子中，如Chai等人报道的嘧啶类化合物E和F具有较好的杀螨活性，在测试浓度为5mg/L时，化合物E和F对螨虫的防治效果均为100％(Chin.Chem.Lett.2014,25,137-140)。
因此，为了继续从吡唑肟类衍生物中寻找具有较好生物活性的化合物，采用活性亚结构拼接原理，合理地将取代嘧啶基团与吡唑肟骨架结合起来，本发明公开了一类具有农用杀虫应用价值的含嘧啶硫醚结构的吡唑肟醚化合物。
发明内容
本发明的目的是提供针对各种害虫具有优良防治效果，且高效、安全、环境友好的一类含嘧啶硫醚结构的吡唑肟醚化合物，以满足作物保护对高效杀虫剂需求。
本发明的另一目的是提供上述化合物的制备方法。
本发明还有一个目的是提供上述化合物在制备杀虫剂方面的用途。
本发明目的可通过以下措施达到：
本发明所述含嘧啶硫醚结构的吡唑肟醚化合物，其特征在于具备如下结构：
该类含嘧啶硫醚结构的吡唑肟醚化合物制备方法，其特征在于化合物Ⅰa～Ⅰg可通过下列反应合成得到：
其中，中间体Ⅱa～Ⅱg可参照文献(J.Agric.Food Chem.2008,56,10805-10810)的方法合成得到；中间体Ⅲ的合成参照文献报道的常规方法(Chin.Chem.Lett.2014,25,1014-1016)。
通式I化合物对昆虫具有优良的防治活性，因而本发明的化合物可用作制备杀虫剂，进而保护农业、园艺等植物。所述的昆虫有粘虫、稻飞虱和蚜虫等。当然，本发明的化合物可防治的有害生物不限于上述举例的范围。
当由通式I表示的本发明的化合物用作农业、园艺等领域的杀虫剂时，可单独使用，或以杀虫组合物的方式使用，如以式I为活性成分，加上本领域常用的农药助剂加工成水乳剂、悬浮剂、水分散颗粒剂、乳油等。
常用的农药助剂包括:液体载体，如水；有机溶剂如甲苯、二甲苯、环己醇、甲醇、丁醇、乙二醇、丙酮、二甲基甲酰胺、乙酸、二甲亚砜、动物和植物油及脂肪酸；常用的表面性剂如乳化剂和分散剂，包括阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂和两性表面活性剂；其它助剂，如湿润剂、增稠剂等。
由通式I表示的本发明的化合物用作杀虫剂中的活性成分时，在所述杀虫剂中的含量可在0.1％至99.5％的范围内进行选择，并可根据制剂形式和施用方法确定适当的活性成分含量。通常，在水乳剂中含有5％至50％(重量百分比，下同)所述的活性成分，优选其含量为10％至40％；在悬浮剂中含有5％至50％的活性成分，优选其含量为5％至40％。
对于本发明的杀虫剂的使用，可选择常用的施药方法，如茎叶喷雾、水面施用、土壤处理和种子处理等。例如，当采用茎叶喷雾时，作为活性成分的由通式I表示的化合物的可使用浓度范围为1至1000μg/mL的水乳剂、悬浮剂、水分散颗粒剂、乳油，优选其浓度为1至500μg/mL。
本发明公开的含嘧啶硫醚结构的吡唑肟醚化合物对有害昆虫显示出优良的防治效果，因此可用来制备用于农业、园艺等领域的杀虫剂。
具体实施方式
为了便于对本发明的进一步了解，下面提供的实施例对其做了更详细的说明。这些实施例仅供叙述而并非用来限定本发明的范围或实施原则。
实施例1：
将5mmol化合物Ⅱa溶于30mL无水DMF，随后加入12mmol无水碳酸钾和中间体Ⅲ6mmol，升温至55℃，反应10小时。将反应液冷却至室温后,倾入100mL水中，用乙酸乙酯萃取，无水硫酸钠干燥，柱层析分离纯化得到目标化合物Ia。1H NMR(400MHz,CDCl3):δ7.79(s,1H,CH＝N),7.57(d,J＝8.4Hz,2H,Ar-H),7.32(d,J＝8.0Hz,2H,Ar-H),6.82(s,4H,Ar-H),5.71(s,1H,Pyrimidine-H),5.03(s,2H,CH2),3.77(s,3H,OCH3),3.72(s,6H,2×OCH3),3.60(s,3H,N-CH3),2.35(s,3H,CH3).
实施例2：
将4mmol化合物Ⅱb溶于30mL乙腈，随后加入12mmol无水碳酸钾和中间体Ⅲ6mmol，升温回流反应14小时。将反应液冷却至室温后，抽滤，滤去固体，母液减压旋蒸至干，所得残余物经柱层析分离纯化得到目标化合物Ib。1H NMR(400MHz,CDCl3):δ7.80(s,1H,CH＝N),7.56(d,J＝8.4Hz,2H,Ar-H),7.31(d,J＝8.0Hz,2H,Ar-H),7.09(d,J＝8.0Hz,2H,Ar-H),6.77(d,J＝8.8Hz,2H,Ar-H),5.70(s,1H,Pyrimidine-H),5.03(s,2H,CH2),3.71(s,6H,2×OCH3),3.58(s,3H,N-CH3),2.35(s,3H,CH3),2.30(s,3H,CH3).
实施例3：
将4mmol化合物Ⅱc溶于30mL乙腈，随后加入9mmol无水碳酸钾和中间体Ⅲ5mmol，升温回流反应16小时。将反应液冷却至室温后，抽滤，滤去固体，母液减压旋蒸至干，所得残余物经柱层析分离纯化得到目标化合物Ic。1H NMR(400MHz,CDCl3):δ7.81(s,1H,CH＝N),7.56(d,J＝8.0Hz,2H,Ar-H),7.29-7.33(m,4H,Ar-H),7.08-7.12(m,1H,Ar-H),6.88(d,J＝8.0Hz,2H,Ar-H),5.70(s,1H,Pyrimidine-H),5.02(s,2H,CH2),3.72(s,6H,2×OCH3),3.59(s,3H,N-CH3),2.35(s,3H,CH3).
实施例4：
将4mmol化合物Ⅱd溶于30mL乙腈，随后加入8mmol无水碳酸铯和中间体Ⅲ5mmol，升温回流反应15小时。将反应液冷却至室温后，抽滤，滤去固体，母液减压旋蒸至干，所得残余物经柱层析分离纯化得到目标化合物Id。1H NMR(400MHz,CDCl3):δ7.73(s,1H,CH＝N),7.51(d,J＝10.4Hz,2H,Ar-H),7.23(d,J＝10.4Hz,2H,Ar-H),6.75-6.96(m,4H,Ar-H),5.64(s,1H,Pyrimidine-H),4.95(s,2H,CH2),3.65(s,6H,2×OCH3),3.54(s,3H,N-CH3),2.27(s,3H,CH3).
实施例5：
将4mmol化合物Ⅱe溶于25mL干燥的DMF，随后加入8mmol无水碳酸钠和中间体Ⅲ7mmol，升温至80℃，反应19小时。将反应液冷却至室温后倾入80mL水中，用乙酸乙酯萃取，无水硫酸钠干燥，柱层析分离纯化得到目标化合物Ie。1H NMR(400MHz,CDCl3):δ7.80(s,1H,CH＝N),7.58(d,J＝8.0Hz,2H,Ar-H),7.25-7.30(m,4H,Ar-H),6.82(d,J＝8.8Hz,2H,Ar-H),5.70(s,1H,Pyrimidine-H),5.00(s,2H,CH2),3.72(s,6H,2×OCH3),3.59(s,3H,N-CH3),2.34(s,3H,CH3).
实施例6：
将10mmol化合物Ⅱf溶于30mL DMSO，随后加入22mmol无水碳酸钠和中间体Ⅲ13mmol，升温至80℃，反应17小时。将反应液冷却至室温后倾入100mL水中，用乙酸乙酯萃取，无水硫酸钠干燥，柱层析分离纯化得到目标化合物If。1H NMR(400MHz,CDCl3):δ7.80(s,1H,CH＝N),7.58(d,J＝8.4Hz,2H,Ar-H),7.40(d,J＝8.8Hz,2H,Ar-H),7.28(d,J＝8.4Hz,2H,Ar-H),6.77(d,J＝8.8Hz,2H,Ar-H),5.71(s,1H,Pyrimidine-H),5.00(s,2H,CH2),3.72(s,6H,2×OCH3),3.59(s,3H,N-CH3),2.33(s,3H,CH3).
实施例7：
将5mmol化合物Ⅱg溶于30mL DMF，随后加入12mmol无水碳酸铯和中间体Ⅲ6mmol，升温至60℃，反应13小时。将反应液冷却至室温后倾入90mL水中，用乙酸乙酯萃取，无水硫酸钠干燥，柱层析分离纯化得到目标化合物Ig。1H NMR(400MHz,CDCl3):δ7.80(s,1H,CH＝N),7.57-7.60(m,4H,Ar-H),7.28(d,J＝8.4Hz,2H,Ar-H),6.65(d,J＝9.2Hz,2H,Ar-H),5.71(s,1H,Pyrimidine-H),5.00(s,2H,CH2),3.72(s,6H,2×OCH3),3.59(s,3H,N-CH3),2.34(s,3H,CH3).
实施例8：
样品对粘虫的杀虫活性筛选
采用国际抗性行动委员会(IRAC)提出的浸叶法：供试靶标为粘虫，即将适量玉米叶在配好的药液中充分浸润后自然阴干，放入垫有滤纸的培养皿中，接粘虫3龄中期幼虫10头/皿，置于24-27℃观察室内培养，2d后调查结果。以毛笔触动虫体，无反应视为死虫。试验浓度500μg/mL(其它浓度的药液可由500μg/mL的药液稀释而得)。
实施例9：
样品对蚜虫和褐飞虱的杀虫活性筛选
采用国际抗性行动委员会(IRAC)提出的喷雾法：供试靶标为蚜虫和水稻褐飞虱，即分别将接有蚜虫的蚕豆叶片和接有褐飞虱的水稻苗于Potter喷雾塔下喷雾处理，处理后朱砂叶螨和褐飞虱置于24-27℃观察室内培养，蚜虫置于20-22℃观察室内培养，48h后调查结果。以毛笔触动虫体，无反应视为死虫。试验浓度500μg/mL(其它浓度的药液可由500μg/mL的药液稀释而得)。
杀虫活性测试结果表明，所有化合物均表现较好的杀虫活性。在测试剂量为500μg/mL时(表1)，化合物Ⅰa和Ⅰd对粘虫的杀灭效果分别为80％和60％；化合物Ⅰd和Ⅰe对蚜虫的杀灭效果分别为60％和70％；Ⅰa、Ⅰb、Ⅰc、Ⅰd、Ⅰe、Ⅰf和Ⅰg对褐飞虱的杀灭效果分别为80％，100％，100％，100％，100％，90％和80％。
表1.Ia-Ig的杀虫活性数据
以上实验数据表明，将嘧啶硫醚结构单元与吡唑肟活性单元合理地进行组合，得到的新型化合物显示良好的生物活性，其中化合物Ⅰd可选作为杀虫先导，作进一步结构衍生与构效关系研究。这些实验数据为今后继续从事新型吡唑肟类化合物的分子设计、合成与生物活性研究提供了重要的理论依据。
Claims (3)
1.一种含嘧啶硫醚结构的吡唑肟醚化合物，其特征在于具备如下结构：
2.一种含嘧啶硫醚结构的吡唑肟醚化合物的制备方法，其特征在于权利要求书1所示的化合物Ia～Ig通过如下反应合成得到：
3.如权利要求1所示的化合物在制备杀虫剂方面的用途。
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