CN106172439B - 磺胺类化合物在防治农业害虫方面的应用 - Google Patents

磺胺类化合物在防治农业害虫方面的应用 Download PDF

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CN106172439B
CN106172439B CN201610535020.8A CN201610535020A CN106172439B CN 106172439 B CN106172439 B CN 106172439B CN 201610535020 A CN201610535020 A CN 201610535020A CN 106172439 B CN106172439 B CN 106172439B
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CN106172439A (zh
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段红霞
张晋陆
袁德凯
杜少卿
顾凌郡
宋敦伦
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China Agricultural University
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    • A—HUMAN NECESSITIES
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/80—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,2

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  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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Abstract

本发明公开了磺胺类化合物在农业害虫防治中的应用，该磺胺类化合物结构式如式I或式II所示：其中，R1代表氢、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基、C1～C4烷硫基、卤素、硝基、氰基、叠氮基、羟基或三氟甲基；R2代表异戊烯基、C1‑C10烷基、苯环、吡啶、噻唑、噻吩、吡咯、呋喃、吡唑、咪唑、吡喃、吡嗪、嘧啶、哒嗪、苯并呋喃、苯并噻吩、吲哚、喹啉、三氟甲基或卤素。采用式I和式II的化合物作为活性成分制成农药，具有良好的杀蚜活性，并且表现出对非靶标蜜蜂低毒。

Description

磺胺类化合物在防治农业害虫方面的应用
技术领域
本发明涉及磺胺类化合物在防治农业害虫方面的应用。
背景技术
以吡虫啉为代表新烟碱杀虫剂是继有机磷、有机氨、氨基甲酸酯及拟除虫菊酯后具有里程碑意义的新一代杀虫剂。因其具有高效、杀虫谱广、对刺吸式口器害虫防治尤为突出，具有根部内吸性、触杀和胃毒作用，低残留、环境友好、对哺乳动物及水生生物安全等特点被广泛应用，占据全球杀虫剂市场的主要份额，全球年销售额不断增长，达到或超过上亿美元(Kagabu S.J.Agric.Food Chem.2011，59，2887-2896)。
由于农药的不正当使用和不合理施用，造成新烟碱类杀虫剂的抗药性和交互抗性日益明显，其中吡虫啉的抗药性高达几十至上百倍，甚至产生了抗性小种(NauenR.Bull.Entomol.Res.1996，86，165-171；Prabhaker N.Bull.Entomol.Res.2005，95，535-543；Frank J Byrne，Pest Management Science,2003，59，347-352；Ninsin KD，PestManagement Science，2005，61，723-727)。蜜蜂作为自然界主要传粉者，具有重要的经济和生态价值，其种群数量大规模的骤减引起各界极大关注。国内外学者推测导致蜜蜂崩溃综合症的原因可能是农药、病原体、寄生虫或生存环境变差等因素，但也有研究指出新烟碱杀虫剂对蜂群的威胁远远大于其它因素。新烟碱杀虫剂的施用会造成蜜蜂运动性功能减退，记忆功能紊乱，影响嗅觉、觅食、导航能力，表现为丧失返回蜂巢的能力等一系列致死和亚致死现象。英国科学学会指出感染寄生真菌的蜜蜂自身免疫力降低，会造成蜜蜂死亡，而新烟碱杀虫剂对非靶标生物有免疫抑制作用，加速病原菌对生物体的侵入(RatnieksF.L.Science,2010，327(5962)，152-153；Lucas A.Garibaldi，Science，2013，339，1608；Gill R.J.Nature,2012，491(7422)，105-108)。可见，新烟碱类杀虫剂对蜜蜂种群的影响已被广泛认可，这极大限制了新烟碱在农业上的广泛使用。
随着结构生物学、分子生物学、生物信息学的迅猛发展，诞生并发展了一门多学科交叉药物研发新方法——计算机辅助药物设计(Computer-aided Drug Design，CADD)。CADD是基于分子模拟技术和数理统计方法，进行虚拟筛选与计算，为化学和生物学搭建平台，在数据库中寻找可能作用于靶标的活性化合物，缩小合成和生物测定范围，缩短新药研发时间，减少人力和财力投入，从而提高新药开发效率(Veselovsky,A.V.Curr.DrugTargets Infect Disord.2003，3，33-40；Bailey,D.Drug Discov.Today2001，6，57-59)。
发明内容
本发明的目的是提供磺胺类化合物在防治农业害虫方面的新应用。
本发明以烟碱乙酰胆碱受体结构为导向，采用药效团和受体结构模型开展结构新颖的新烟碱功能类化合物的虚拟筛选，筛选出如式I或式II所示的磺胺类化合物。
其中，R1代表氢、C1～C4烷基、C1～C4卤代烷基、C1～C4烷氧基、C1～C4烷硫基、卤素、硝基、氰基、叠氮基、羟基或三氟甲基；R2代表异戊烯基、C1-C10烷基、苯环、吡啶、噻唑、噻吩、吡咯、呋喃、吡唑、咪唑、吡喃、吡嗪、嘧啶、哒嗪、苯并呋喃、苯并噻吩、吲哚、喹啉、三氟甲基或卤素。
上述磺胺类化合物可以通过商业渠道采购或通过已有合成手段进行合成。
采用式I和式II的化合物作为活性成分，制成农药，可用于蚜虫等病虫害的防治。
本发明中的磺胺类化合物与新烟碱类化合物对靶标的作用方式类似，但表现出与新烟碱不同的对非靶标生物安全性。并且结构简单、修饰空间大，可作为结构新颖的新烟碱功能类蚜虫防控剂。
具体实施方式
下面通过具体实施例来进一步描述本发明，本领域技术人员应该理解，下面的实施例仅为了更好地理解本发明，并不用来对本发明进行任何限制。
从北京伊诺凯科技有限公司采购了根据式I和式II的两种磺胺类化合物，代号分别记为VS03和VS04，它们的结构式如下：
以它们分别作为农药活性成分，配置成不同浓度的药液，进行下面的测试实验。
杀蚜活性测试实验
实验试虫：大豆蚜(Aphis glycines)采自室内饲养的正常群体，用虫龄、体重及生理状况一致的无翅成虫进行药剂活性筛选试验。
实验方法：采用浸叶法，用大豆叶浸渍于二甲基亚砜配制的药液中，待药液干后接入无翅成虫，主要为胃毒、触杀作用，分别检查24h和48h蚜虫的死亡情况。浓度梯度设置为500、125、31、8和2mg/L。
死亡判断标准：轻触虫体，六足不能动的害虫个体视为死亡个体。
蜜蜂毒性测试实验
实验试虫：意大利成年工蜂(Apismellifera L.)，由北京嘉禾祥瑞蜜蜂养殖基地提供。挑选大小一致，健康活泼的成年工蜂进行试验。
实验方法：试验在温度25.0℃～25.2℃，相对湿度为56.8％～58.6％，微光条件下进行。试验设置3个药液浓度，分别为1.10×104、2.75×103、6.875×102mg/L，丙酮为助剂。试验前先麻醉蜜蜂，后用连续分配器将不同浓度的药液点滴于蜜蜂的中胸背板处，待蜜蜂完全恢复后转移至恢复室中正常饲喂。分别记录24h和48h试验结果。
死亡判断标准：为触碰蜜蜂身体，无任何反应。
上述实验的测试结果如表1-表2所示，表3为农药对蜜蜂毒性等级划分表。
表1高活性化合物对大豆蚜(Aphis glycines)的杀蚜活性
表2高活性化合物对蜜蜂的急性接触毒性
表3农药对蜜蜂毒性等级划分
从以上测试结果可以看出，化合物VS03和VS04的LC50值分别为29.55mg/L和44.08mg/L，具有良好的杀蚜活性，并且表现出对非靶标蜜蜂低毒。
以上实施例仅作为本发明的示例，根据式I和式II的其它磺胺类化合物由于与VS03和VS04具有相同的磺胺基团，因此也具有与VS03和VS04类似的特性。
本发明中的磺胺类化合物与新烟碱类化合物对靶标的作用方式类似，但表现出与新烟碱不同的对非靶标生物安全性。并且结构不同于新烟碱，结构简单修饰空间大，可作为结构新颖的新烟碱功能类蚜虫防控剂。

Claims (1)

1.一种磺胺类化合物在蚜虫防治中的应用，该磺胺类化合物结构式如下：
CN201610535020.8A 2016-07-08 2016-07-08 磺胺类化合物在防治农业害虫方面的应用 Active CN106172439B (zh)

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