CN109678846B - 含1,2,3-三氮唑结构的吡唑酰胺类化合物及其制备方法和用途 - Google Patents
含1,2,3-三氮唑结构的吡唑酰胺类化合物及其制备方法和用途 Download PDFInfo
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
- A01N43/647—Triazoles; Hydrogenated triazoles
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Abstract
本发明涉及一种含1,2,3‑三氮唑结构的吡唑酰胺类化合物(I)及其制备方法和应用。通过取代基吡唑甲酰基氯(II)与1,2,3‑三氮唑联苯基甲基胺(III)缩合得到。所述含1,2,3‑三氮唑结构的吡唑酰胺类化合物对有害昆虫具有效的防治效果，该化合物可用于制备农业、园艺等领域的杀虫剂。
Description
技术领域
本发明涉及化学农药领域，具体涉及一种含1,2,3-三氮唑结构的吡唑酰胺类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。
吡唑环在农业生产方面应用广泛，吡唑类化合物具有优异的杀虫、杀螨等活性，吡唑杂环被广泛地引入到农药化合物分子中，如吡唑酰胺杀虫杀螨剂吡螨胺和唑虫酰胺，对螨虫、蚜虫等具有优良的杀灭活性(Biochim.Biophys.Acta 1998,1364,236-244)。
1,2,3-三氮唑也为一类重要的含氮杂环，在农药领域的杀虫方面发挥着重要作用。
因此，为了进一步从吡唑酰胺类化合物中寻找具有优良生物活性的化合物，采用活性基团拼接方法，合理地将吡唑酰胺基团与1,2,3-三氮唑骨架衔接在一起，本发明公开了一类具有农用杀虫应用价值的含1,2,3-三氮唑结构的吡唑酰胺类化合物。
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1,2,3-三氮唑结构的吡唑酰胺类化合物，以满足作物保护对高效杀虫剂需求。
本发明的又一个目的是提供上述化合物在制备杀虫剂方面的用途。
本发明的另一目的是提供上述化合物的制备方法。
为解决上述技术问题，本发明的第一方面提供一种含1,2,3-三氮唑结构的吡唑酰胺类化合物，其具有通式I结构，
其中，R＝CH3,C2H5,n-C3H7,2,4-F2C6H3。
优选地，所述含1,2,3-三氮唑结构的吡唑酰胺类化合物具有如下结构：
本发明的第二方面提供上述含1,2,3三氮唑结构的吡唑酰胺类化合物的制备方法，其包括如下步骤：
将化合物Ⅲ溶于有机溶剂中，加入缚酸剂，再在加入中间体Ⅱ，最后反应一段时间，将反应液抽滤，母液减压浓缩，所得残余物分离纯化得目标化合物，
其中，R＝CH3,C2H5,n-C3H7,2,4-F2C6H3
优选地，所述缚酸剂选自吡啶、碳酸氢钠、三乙胺、碳酸钠，所述溶剂选自THF、乙腈、二氯甲烷、三氯甲烷。所述加热反应温度为0℃-82℃，反应时间为8-20小时。
优选地，含1,2,3-三氮唑结构的吡唑酰胺类化合物的制备方法如下：
其中，1,2,3-三氮唑联苯甲基胺中间体III可参照文献(J.Med.Chem.1998,41,2390)的方法合成得到；中间体Ⅱa～Ⅱd参照文献(J.Agric.Food Chem.2013,61,8730-8736)的方法合成得到。
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。所述的昆虫包括鳞翅目害虫如棉铃虫、甜菜夜蛾、小菜蛾、菜青虫、稻纵卷叶螟和二化螟等；同翅目害虫如叶蝉、飞虱、蚓虫、粉虱、木虱科的介壳虫等；双翅目害虫如家蝇、潜叶蝇、蚊类等；直翅目的蝗虫等，鞘翅目的天牛、金龟子、象甲、豆象等害虫等；半翅目的蝽等。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1,2,3-三氮唑结构的吡唑酰胺类化合物对有害昆虫具有优良的防治效果，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
以下结合具体实施例对上述方案做进一步说明。应理解，这些实施例是用于说明本发明而不限于限制本发明的范围。实施例中采用的实施条件可以根据具体厂家的条件做进一步调整，未注明的实施条件通常为常规实验中的条件。
实施例1：
将5mmol化合物Ⅲ溶于30mL四氢呋喃，随后加入20mmol吡啶。室温条件下向其中加入中间体Ⅱa 7mmol，加毕，加热回流反应12小时。停止反应，减压除去溶剂，所得残余物经柱层析分离纯化得到目标化合物Ia。1H NMR(400MHz,CDCl3):δ8.08(d,J＝8.4Hz,2H,Ar-H),7.81(s,2H,Triazole-H),7.47(d,J＝8.8Hz,2H,Ar-H),7.10(s,1H,NH),4.68(d,J＝5.6Hz,2H,CH2),4.15(s,3H,N-CH3),2.23(s,3H,CH3).
实施例2：
将8mmol化合物Ⅲ溶于30mL乙腈，随后加入30mmol碳酸氢钠。室温条件下向其中加入中间体Ⅱb 9mmol，加毕，加热回流20小时。停止反应，减压除去溶剂，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):δ8.08(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,Triazole-H),7.48(d,J＝8.4Hz,2H,Ar-H),7.10(s,1H,NH),4.70(d,J＝5.6Hz,2H,CH2),4.16(s,3H,N-CH3),2.65(q,J＝7.6Hz,2H,CH2),1.24(t,J＝7.6Hz,3H,CH3).
实施例3：
将10mmol化合物Ⅲ溶于35mL二氯甲烷，随后加入25mmol三乙胺。冰浴条件下向其中加入中间体Ⅱc 11mmol，加毕，继续冰浴搅拌15小时。停止反应，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):δ8.08(d,J＝8.4Hz,2H,Ar-H),7.82(s,2H,Triazole-H),7.48(d,J＝8.8Hz,2H,Ar-H),7.10(s,1H,NH),4.70(d,J＝5.6Hz,2H,CH2),4.16(s,3H,N-CH3),2.59(t,J＝7.6Hz,2H,CH2),1.63～1.72(m,2H,CH2),0.96(t,J＝7.6Hz,3H,CH3).
实施例4：
将6mmol化合物Ⅲ溶于35mL三氯甲烷，随后加入20mmol碳酸钠，室温条件下向其中加入中间体Ⅱd 8mmol。加毕，室温搅拌8小时。停止反应，将反应液减压旋蒸至干，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):δ8.09(d,J＝8.8Hz,2H,Ar-H),7.81(s,2H,Triazole-H),7.45～7.50(m,3H,Ar-H),7.17(s,1H,NH),6.91～7.00(m,2H,Ar-H),4.72(d,J＝5.6Hz,2H,CH2),4.26(s,3H,N-CH3).
实施例5：
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，48h后调查结果。以毛笔触动虫体，无反应视为死虫。试验浓度为500μg/mL(其它浓度的药液可由500μg/mL的药液稀释而得)。
实施例6：
样品对蚜虫的杀虫活性筛选
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，即将接有蚜虫的蚕豆叶片于Potter喷雾塔下喷雾处理，处理后蚜虫置于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。试验浓度为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，所有化合物均显示出杀虫活性。在测试剂量为500μg/mL时(表1)，化合物Ⅰa、Ⅰb、Ⅰc和Ⅰd对粘虫的杀虫活性均较高，其杀死率均为100％；化合物Ⅰa、Ⅰb、Ⅰc和Ⅰd对蚜虫的杀虫活性也均较高，其杀死率均达100％。
表1.Ia-Id的初步杀虫活性数据
以上实验数据表明，将1,2,3-三氮唑结构和吡唑酰胺活性单元合理地进行组合，得到的新型化合物表现出良好生物活性，这些实验数据也为今后继续从事新型吡唑酰胺类化合物的分子设计、合成与生物活性研究提供了重要的结构选择模式与理论依据。
以上显示和描述了本发明的基本原理、主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实例的限制，上述实例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等同物界定。
Claims (4)
1.一种含1,2,3-三氮唑结构的吡唑酰胺类化合物I，其特征在于结构为：
2.一种如权利要求1所述的含1,2,3-三氮唑结构的吡唑酰胺类化合物I的制备方法，其特征在于方法如下：
3.如权利要求1所述的含1,2,3-三氮唑结构的吡唑酰胺类化合物I在制备杀虫剂药物方面的用途，所述虫选自粘虫或蚜虫，其特征在于：该化合物单独使用；或以杀虫组合物的方式使用，即以化合物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。
4.如权利要求3所述的含1,2,3-三氮唑结构的吡唑酰胺类化合物I在制备杀虫剂药物方面的用途，其特征在于：化合物I用作杀虫剂中的活性成分时，在所述杀虫剂中的含量在0.1%至99.5%的范围内进行选择。
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