CN109535154B - 含4-芳基噻唑结构的吡唑酰胺类化合物及其制备方法和用途 - Google Patents
含4-芳基噻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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Abstract
本发明涉及一种含4‑芳基噻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4‑芳基噻唑‑2‑甲基胺(III)缩合得到。所述4‑芳基噻唑结构的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4-芳基噻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)。
噻唑类化合物也是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噻唑单元衔接在一起,本发明公开了一类具有农用杀虫应用价值的含4-芳基噻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4-芳基噻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4-芳基噻唑结构的吡唑酰胺类化合物,其具有通式I结构,
优选地,所述含4-芳基噻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4-芳基噻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,
优选地,所述缚酸剂选自吡啶、4-N,N-二甲基吡啶、三乙胺、N,N-二异丙基乙胺、碳酸钠,所述溶剂选自DMF、乙腈、二氯甲烷、三氯甲烷和DMA。所述加热反应温度为0℃-90℃,反应时间为9-28小时。
优选地,含4-芳基噻唑结构的吡唑酰胺类化合物的制备方法如下:
其中,4-芳基噻唑-2-甲基胺中间体IIIa~IIId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4-芳基噻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6mmol化合物Ⅲa溶于30mL乙腈,随后加入30mmol吡啶。室温条件下向其中加入中间体Ⅱa 9mmol,加毕,加热回流反应9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):δ7.55(d,J=8.8Hz,2H,Ar-H),7.49(d,J=8.4Hz,2H,Ar-H),7.46(s,1H,NH),7.31(s,1H,Thiazole-H),4.82(d,J=5.2Hz,2H,CH2),4.14(s,3H,N-CH3),2.25(s,3H,CH3).
实施例2:
将5mmol化合物Ⅲb溶于30mL DMF,随后加入10mmol DMAP(4-N,N-二甲基吡啶)。室温条件下向其中加入中间体Ⅱb 5mmol,加毕,加热至90℃反应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):δ7.83(d,J=8.4Hz,2H,Ar-H),7.69(s,1H,NH),7.45(s,1H,Thiazole-H),7.39(d,J=8.8Hz,2H,Ar-H),4.98(d,J=5.6Hz,2H,CH2),4.16(s,3H,N-CH3),2.67(q,J=7.6Hz,2H,CH2),1.26(t,J=7.6Hz,3H,CH3).
实施例3:
将8mmol化合物Ⅲc溶于35mL二氯甲烷,随后加入30mmol三乙胺。冰浴条件下向其中加入中间体Ⅱb10mmol,加毕,继续冰浴搅拌10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):δ7.93(d,J=8.4Hz,1H,Ar-H),7.84(s,1H,Ar-H),7.67(s,1H,NH),7.50(s,1H,Thiazole-H),7.33~7.36(m,1H,Ar-H),5.00(d,J=5.6Hz,2H,CH2),4.16(s,3H,N-CH3),2.66(q,J=7.6Hz,2H,CH2),1.25(t,J=7.6Hz,3H,CH3).
实施例4:
将4mmol化合物Ⅲd溶于25mL DMA(N,N-二甲基乙酰胺),随后加入20mmol DIEPA(N,N-二异丙基乙胺),室温条件下向其中加入中间体Ⅱc 7mmol。加毕,室温搅拌28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):δ8.16~8.22(m,1H,Ar-H),7.67(s,2H,NH and Triazole-H),6.88~7.00(m,2H,Ar-H),4.98(d,J=5.6Hz,2H,CH2),4.16(s,3H,N-CH3),2.61(t,J=7.6Hz,2H,CH2),1.64~1.74(m,2H,Ar-H),0.98(t,J=7.6Hz,3H,CH3).
实施例5:
将10mmol化合物Ⅲd溶于25mL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 9mmol。加毕,室温搅拌16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Ie。1H NMR(400MHz,CDCl3):δ8.16~8.22(m,1H,Ar-H),7.80~7.84(m,2H,Ar-H),7.78(s,1H,NH),7.68(s,1H,Thiazole-H),7.12~7.17(m,2H,Ar-H),6.89~7.01(m,2H,Ar-H),5.02(d,J=5.2Hz,2H,CH2),4.25(s,3H,N-CH3).
实施例6:
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7:
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、Ⅰd和Ⅰe对粘虫的杀虫活性均较高,其杀死率均为100%;化合物Ⅰa、Ⅰb、Ⅰc、Ⅰd和Ⅰe对蚜虫的杀虫活性也均较高,其杀死率分别为100%,100%,80%,100%和70%。
表1.Ia-Ie的初步杀虫活性数据
以上实验数据表明,将取代噻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)
3.如权利要求1所述的含4-芳基噻唑结构的吡唑酰胺类化合物I在制备杀粘虫药物方面的用途,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,加上农药助剂加工成水乳剂、悬浮剂、水分散颗粒剂、乳油,所述的农药助剂为水、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、阴离子表面活性剂、阳离子表面活性剂、非离子表面活性剂、两性表面活性剂、湿润剂、增稠剂。
4.如权利要求3所述的含4-芳基噻唑结构的吡唑酰胺类化合物I在制备杀粘虫药物方面的用途,其特征在于:化合物I用作杀粘虫药物的活性成分时,在所述杀粘虫药物中的含量在0.1%至99.5%的范围内进行选择。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0462573A1 (en) * | 1990-06-18 | 1991-12-27 | Mitsubishi Chemical Corporation | Pyrazolecarboxamide, insecticidal and miticidal composition, and fungicidal composition for use in agriculture and horticulture |
JP2003160584A (ja) * | 2001-11-22 | 2003-06-03 | Nippon Nohyaku Co Ltd | N−ベンゾチアゾリルメチルピラゾールカルボキサミド誘導体およびこれを有効成分とする殺菌剤 |
JP2005060255A (ja) * | 2003-08-20 | 2005-03-10 | Nippon Nohyaku Co Ltd | カルボキサミド類及びこれを有効成分とする有害生物防除剤 |
CN101495472A (zh) * | 2006-07-31 | 2009-07-29 | 拜尔农科股份有限公司 | 杀真菌剂n-环烷基-羧酸胺衍生物 |
WO2013064079A1 (zh) * | 2011-11-02 | 2013-05-10 | 中国中化股份有限公司 | 吡唑酰胺类化合物作为农用杀菌剂的用途 |
CN103130796A (zh) * | 2013-01-25 | 2013-06-05 | 青岛科技大学 | 一种3-叔丁基吡唑酰胺类化合物及其应用 |
CN104650064A (zh) * | 2014-12-17 | 2015-05-27 | 南开大学 | 一类氨基噻唑羧酸衍生物及其制备方法和用途 |
CN106432216A (zh) * | 2016-08-01 | 2017-02-22 | 南通大学 | 含5‑芳基异噁唑结构的吡唑酰胺类化合物的制备方法和应用 |
CN106608872A (zh) * | 2015-10-26 | 2017-05-03 | 湖南化工研究院有限公司 | 5-吡唑酰胺类化合物及其制备方法与应用 |
CN106608873A (zh) * | 2015-10-26 | 2017-05-03 | 湖南化工研究院有限公司 | 吡唑酰胺类化合物及其制备方法与应用 |
CN106866649A (zh) * | 2017-02-13 | 2017-06-20 | 南通大学 | 含5‑芳基‑1,3,4‑噁二唑结构的吡唑酰胺类化合物的制备方法和应用 |
-
2018
- 2018-12-14 CN CN201811536163.6A patent/CN109535154B/zh not_active Expired - Fee Related
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0462573A1 (en) * | 1990-06-18 | 1991-12-27 | Mitsubishi Chemical Corporation | Pyrazolecarboxamide, insecticidal and miticidal composition, and fungicidal composition for use in agriculture and horticulture |
JP2003160584A (ja) * | 2001-11-22 | 2003-06-03 | Nippon Nohyaku Co Ltd | N−ベンゾチアゾリルメチルピラゾールカルボキサミド誘導体およびこれを有効成分とする殺菌剤 |
JP2005060255A (ja) * | 2003-08-20 | 2005-03-10 | Nippon Nohyaku Co Ltd | カルボキサミド類及びこれを有効成分とする有害生物防除剤 |
CN101495472A (zh) * | 2006-07-31 | 2009-07-29 | 拜尔农科股份有限公司 | 杀真菌剂n-环烷基-羧酸胺衍生物 |
WO2013064079A1 (zh) * | 2011-11-02 | 2013-05-10 | 中国中化股份有限公司 | 吡唑酰胺类化合物作为农用杀菌剂的用途 |
CN103130796A (zh) * | 2013-01-25 | 2013-06-05 | 青岛科技大学 | 一种3-叔丁基吡唑酰胺类化合物及其应用 |
CN104650064A (zh) * | 2014-12-17 | 2015-05-27 | 南开大学 | 一类氨基噻唑羧酸衍生物及其制备方法和用途 |
CN106608872A (zh) * | 2015-10-26 | 2017-05-03 | 湖南化工研究院有限公司 | 5-吡唑酰胺类化合物及其制备方法与应用 |
CN106608873A (zh) * | 2015-10-26 | 2017-05-03 | 湖南化工研究院有限公司 | 吡唑酰胺类化合物及其制备方法与应用 |
CN106432216A (zh) * | 2016-08-01 | 2017-02-22 | 南通大学 | 含5‑芳基异噁唑结构的吡唑酰胺类化合物的制备方法和应用 |
CN106866649A (zh) * | 2017-02-13 | 2017-06-20 | 南通大学 | 含5‑芳基‑1,3,4‑噁二唑结构的吡唑酰胺类化合物的制备方法和应用 |
Non-Patent Citations (2)
Title |
---|
Design, Synthesis, DFT Study and Antifungal Activity of the Derivatives of Pyrazolecarboxamide Containing Thiazole or Oxazole Ring;Zhongzhong,等;《European journal of medicinal chemistry》;20180221;第149卷(第1期);170-181 * |
Optimization of Novel 1-Methyl-1 H-Pyrazole-5-carboxamides Leads to High Potency Larval Development Inhibitors of the Barber"s Pole Worm.;Thuy,等;《Journal of medicinal chemistry》;20181107;第61卷(第23期);10875-10894 * |
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