CN114605335A - 一种嘧啶硫醚胺酯类杀虫剂 - Google Patents
一种嘧啶硫醚胺酯类杀虫剂 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
- C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
- C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
- C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
- C07D239/47—One nitrogen atom and one oxygen or sulfur atom, e.g. cytosine
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/54—1,3-Diazines; Hydrogenated 1,3-diazines
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
- C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
- C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
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Abstract
本发明提供了一种嘧啶硫醚胺酯类化合物及其用途，结构如通式Ⅰ所示：
其中R1为：CH3CH2CH2CH2‑，CF3CH2‑，CHF2CH2‑；R2为：
Description
技术领域 本发明属于农药中杀虫剂的领域，涉及一种嘧啶硫醚胺酯类杀虫剂及其用于农业或林业害虫的防治。
背景技术 农业上害虫危害农作物的生长，导致减产及品质下降。目前对害虫的防治主要依赖化学农药，由于大量频繁使用杀虫剂，害虫对其均产生了严重的抗药性，导致用药量越来越大，防效越来越低，持效期缩短，农残升高等一系列问题。新的不同作用机制的杀虫剂的开发及应用，是解决有害生物抗性的有效手段。
在目前的嘧啶胺类化合物中，已经商品化的杀虫剂有flulinufen、嘧螨醚以及环虫腈。Flulinufen是日本宇部兴产(现属住友化学)开发的一种嘧啶胺类杀虫剂。嘧螨醚是20世纪90年代开发的，可有效防治农作物上生长的螨类和蔬菜上的害虫，该化合物的优点在于选择性好、高效低毒。环虫腈(dicyclanil)是一种嘧啶类昆虫生长调节剂，在防治害虫方面具有优良的生物性能。
文献[吴宁捷,龙程,等.新型4-芳氨基嘧啶类衍生物的合成及其杀虫活性[J].有机化学,2019(39):852-856.]报道了一类4-芳氨基嘧啶类衍生物，经生物活性测试表明，在质量浓度500mg/L时，该系列化合物对粘虫(Mythimna separata)的致死率为100％；且在质量浓度降至为20mg/L时，化合物2-甲基-4-[N-(2-氯-4-氟苯基)氨基]-5-[2-三氟甲基-4-(苯氧基)苯基]-6-甲基嘧啶对粘虫和小菜蛾的致死率分别为80％和60％。
在现有技术中，如本发明所述的嘧啶硫醚胺酯类化合物(通式Ⅰ)及其用作农林业杀虫剂未见公开。
发明内容 本发明的目的在于提供一种结构新颖，合成方法简便、安全高效的杀虫剂，它可用于农业或林业害虫的防治。
本发明的技术方案如下：
一种嘧啶硫醚胺酯类化合物及其用途，结构如通式Ⅰ所示：
本发明通式Ⅰ化合物可由如下反应制备：
R1和R2同上。嘧啶胺衍生物与卤代烷进行N-烷基化反应制得产物，具体制备方法见本发明合成实施例。
表1列出了通式Ⅰ化合物的结构与外观。
表1通式Ⅰ化合物结构及外观
本发明的优点和积极效果：
本发明化合物作为农林业杀虫剂，具有结构新颖、制备简便且有一定的杀螨作用的优点。本发明化合物对小菜蛾有优异的抑杀效果，可以达到对农林业害虫的优异效果。其中Ⅰc、Ⅰd、Ⅰf的杀灭效果明显优于商品唑虫酰胺，特别是Ⅰc化合物，在5mg/L超低浓度下杀灭率达到了100％，在1mg/L超低浓度下杀灭率也达到了90％。本发明化合物为含氮杂环酯类化合物，具有生物活性高、对有益生物低毒性、易降解、环境相容性好的特点，特别适用于目前普遍存在的抗药性农业害虫的治理，作为杀虫优异兼具一定杀螨作用的农药新品种具有很好的开发及应用前景。
本发明化合物在防治农林业害虫可单独使用，也可与其它活性物质组合使用，以提高产品的综合性能。
本发明还包括以通式Ⅰ化合物为活性组分的杀虫剂组合物，其中活性组分在组合物的重量百分含量为1～99％。该杀虫剂组合物还包括农业或林业上可接受的载体。
应该明确的是，在本发明的权利要求的限定范围内，可进行各种变动或改动。
具体实施方式
下列合成实例、生测试验结果可用来进一步说明本发明，但不意味着限制本发明。
合成实例
实例1、化合物Ⅰa的制备：
(1)中间体2-巯基-4-氨基-5-羧酸乙酯嘧啶的合成：
在干燥的250mL三口烧瓶中，加入16.92g(0.1mol)2-氰基-3-乙氧基丙烯酸乙酯和7.61g(0.12mol)硫脲，再加入100mL乙醇作为反应溶剂，搅拌，将反应温度升高到回流，向反应液中滴加37.43g(0.22mol)20％的乙醇钠，滴加完毕后继续反应1h，TLC监测反应完全，降温，减压蒸馏除去乙醇，得到中间体2-巯基-4-氨基-5-羧酸乙酯嘧啶。
(2)中间体2-正丁硫基-4-氨基-5-羧酸乙酯嘧啶的合成：
在干燥的250mL三口烧瓶中加入19.73g(0.10mol)2-巯基-4-氨基-5-羧酸乙酯嘧啶和50mL DMF，室温下搅拌10min后，向反应液中缓慢滴加15.07g(0.11mol)溴代正丁烷，滴加完毕后继续反应4h，TLC监测反应完全，将反应液倒入150mL水中，析出固体。抽滤，用30mL水洗涤滤饼，收集滤饼并烘干，得到淡红色固体，收率87％。
(3)化合物Ⅰa的合成:
在干燥的100mL三口烧瓶中，加入中间体2-正丁硫基-4-氨基-5-羧酸乙酯嘧啶和2.53g(10.0mmol)碳酸钾1.66g(12.0mmol)，加入20mL DMF，室温下搅拌0.5h，再加入对叔丁基苄氯1.92g(10.5mmol)，升高温度至80℃反应3～5h，TLC监测反应完全后降温，将反应液加入到60mL水中，用乙酸乙酯(3×30mL)萃取，有机层用饱和食盐水(2×20mL)洗涤并用无水硫酸钠干燥，减压蒸馏除去乙酸乙酯，粗品经柱层析(V(乙酸乙酯):V(石油醚)＝1:10)纯化，得到无色油状物，收率78％。
实例2、化合物Ⅰe的制备：
(1)中间体2-(2,2,2-三氟乙基)硫基-4-氨基-5-羧酸乙酯嘧啶的合成
2-巯基-4-氨基-5-羧酸乙酯嘧啶与三氟碘乙烷反应制备，方法与实例1步骤(2)类似。
(2)化合物Ⅰe的合成：
2-(2,2,2-三氟乙基)硫基-4-氨基-5-羧酸乙酯嘧啶与2-氯-5-氯甲基吡啶反应制备，方法与实例1步骤(3)类似。白色固体，收率78％。
实例3、化合物Ⅰf的制备：
(1)中间体2-(2,2-二氟乙基)硫基-4-氨基-5-羧酸乙酯嘧啶的合成
(a)在干燥的250mL三口烧瓶中加入2,2-二氟乙醇8.20g(0.10mol)、三乙胺10.12g(0.10mol)，再加50mL乙酸乙酯，将反应瓶置于冷肼中，控制温度在10℃以下，搅拌10min后，向反应瓶中缓慢滴加甲基磺酰氯11.46g(0.10mol)，加毕，TLC监测反应完全。减压抽滤，将滤液进行减压蒸馏除去乙酸乙酯，得到中间体2,2-二氟乙醇甲基磺酸酯，无色油状物，收率98％。
(b)在干燥的250mL三口烧瓶中加入2-巯基-4-氨基-5-羧酸乙酯嘧啶19.73g(0.10mol)，然后加入50mL乙醇作为反应溶剂，控制反应温度于室温搅拌10min，再加入中间体2,2-二氟乙醇甲基磺酸酯16.0g(0.11mol)，加毕，将反应温度升高到回流继续反应4h，TLC监测反应完全。减压蒸馏除去多余乙醇，然后倒入80mL水中，用乙酸乙酯(3×50mL)萃取，有机层用饱和食盐水(2×30mL)洗涤并用无水硫酸钠干燥，减压蒸馏除去乙酸乙酯，得到淡黄色固体，收率80％。
(2)化合物Ⅰf的合成：
2-(2,2-二氟乙基)硫基-4-氨基-5-羧酸乙酯嘧啶与2-氰基苄氯反应制备，方法与实例1步骤(3)类似。淡黄色固体，收率71％。
本发明通式Ⅰ化合物的核磁数据如下：
化合物Ⅰa：1H NMR(500MHz,Chloroform-d)δ8.65(s,1H),7.37(d,J＝8.0Hz,2H),7.28(s,2H),4.74(d,J＝5.7Hz,2H),4.32(q,J＝7.1Hz,2H),3.09(t,J＝7.4Hz,2H),1.68(s,2H),1.44(p,J＝7.4Hz,2H),1.37(t,J＝7.1Hz,3H),1.33(s,9H),0.92(d,J＝7.4Hz,3H).
化合物Ⅰb：1H NMR(500MHz,Chloroform-d)δ8.67(s,1H),8.37(s,1H),7.62(d,J＝8.2Hz,1H),7.30(s,1H),4.75(d,J＝6.1Hz,2H),4.33(q,J＝7.1Hz,2H),3.02(t,J＝7.3Hz,2H),1.63(q,J＝7.4Hz,2H),1.41(d,J＝7.5Hz,2H),1.38(d,J＝7.1Hz,3H),0.90(t,J＝7.4Hz,3H).
化合物Ⅰc：1H NMR(500MHz,Chloroform-d)δ8.69(s,1H),7.39(d,J＝8.0Hz,2H),7.27(d,J＝7.5Hz,2H),4.71(d,J＝5.7Hz,2H),4.34(t,J＝7.2Hz,2H),3.88(q,J＝9.9Hz,2H),1.39(t,J＝7.1Hz,3H),1.34(s,9H).
化合物Ⅰd：1H NMR(500MHz,DMSO-d6)δ9.07(t,J＝6.0Hz,1H),8.64(t,J＝3.6Hz,1H),7.83(d,J＝7.0Hz,1H),7.64(t,J＝7.5Hz,1H),7.44(q,J＝7.8Hz,2H),4.91(d,J＝6.0Hz,2H),4.33(q,J＝7.1Hz,2H),3.98(q,J＝10.3Hz,2H),1.33(t,J＝7.1Hz,3H).
化合物Ⅰe：1H NMR(500MHz,Chloroform-d)δ8.76(d,J＝6.6Hz,1H),8.70(s,1H),8.37(d,J＝2.5Hz,1H),7.62(dd,J＝8.2,2.5Hz,1H),7.31(d,J＝8.2Hz,1H),4.72(d,J＝5.9Hz,2H),4.34(q,J＝7.1Hz,2H),3.84(q,J＝9.8Hz,2H),1.38(t,J＝7.1Hz,3H).
化合物Ⅰf：1H NMR(500MHz,Chloroform-d)δ8.86(q,J＝5.5Hz,1H),8.68(d,J＝3.9Hz,1H),7.68(dt,J＝7.9,2.4Hz,1H),7.56(ddq,J＝7.7,4.2,2.2,1.3Hz,1H),7.47–7.35(m,2H),5.77(tq,J＝56.8,4.4Hz,1H),4.93(dd,J＝6.1,3.9Hz,2H),4.36(q,J＝7.1Hz,2H),3.41(tt,J＝15.0,4.3Hz,2H),1.39(t,J＝7.1Hz,3H).
生物活性测试
实例4、杀虫活性测定方法
选择小菜蛾为对象进行杀虫活性试验。对小菜蛾的杀虫活性测试所采用的方法是浸叶法(即由国际杀虫剂抗性行动委员会Insecticide Resistance Action Committee，IRAC所提出的)。具体操作方法为：用直头眼科镊子在提前配置好的药液中将甘蓝叶片浸渍3-5s，然后取出药片，除去多余的药液，每次浸渍1片甘蓝叶片，每个样品做三个平行实验，按照标记顺序将叶片放置于处理纸上。待叶片上的药液晾干后，将其分别放入标记好的10cm长的直型试管中，每个试管内各接种3龄小菜蛾幼虫30头，用纱布盖好管口后放置于标准培养室内。该测试以唑虫酰胺为阳性对照药剂，清水为阴性对照药剂。48h后观察实验结果，判断小菜蛾死亡的标准为：虫体干瘪、变黑、并且用毛笔轻轻触试后无明显反应；判断活虫的标准为：虫体湿润、新鲜、用毛笔清扫并保持动态者。根据调查结果计算死亡率(％)。
死亡率(％)＝[(药剂处理死亡率-空白对照死亡率)/(1-空白对照死亡率)]*100
表2通式Ⅰ化合物的杀小菜蛾活性测试结果
测试结果表明，本发明通式Ⅰ化合物对小菜蛾有优良杀虫活性。其中Ⅰc、Ⅰd、Ⅰf的杀灭效果明显优于唑虫酰胺，在10mg/L低浓度下，Ⅰc、Ⅰf杀灭率达到了100％，Ⅰd杀灭率达到了97％；在5mg/L超低浓度下，Ⅰc杀灭率达到了100％，Ⅰf杀灭率达到了95％。Ⅰa、Ⅰe略低于唑虫酰胺。
实例5、杀螨活性测定方法
对化合物进行杀螨活性测试，测试方法为喷雾法，测试所选用的对象为朱砂叶螨，具体操作方法为：首先将化合物稀释成各种不同浓度的DMF药液，将接有相同数量和成长神态的蚕豆叶片进行喷雾处理，接着将上述处理过的蚕豆叶片放置于24-27℃的室内进行观察培养，于48h后记录朱砂叶螨的生长情况，判断该螨虫死亡的标准为：用毛笔轻轻触动螨虫身体，若毫无反应，则为死虫。该测试中每一个浓度分别设置三组对照实验，计算每三个平行实验的死亡率。
死亡率(％)＝[(药剂处理死亡率-空白对照死亡率)/(1-空白对照死亡率)]*100
表3通式Ⅰ化合物的杀螨活性测试结果
测试结果表明，在质量浓度为50mg/L时，本发明通式Ⅰ化合物对螨虫有一定的杀灭活性，其中化合物Ⅰa、Ⅰc、Ⅰd在50mg/L浓度下对朱砂叶螨的致死率分别为68％、78％、62％。
Claims (3)
1.一种嘧啶硫醚胺酯类化合物及其用途，结构如通式Ⅰ所示：
2.根据权利要求1所述的一种嘧啶硫醚胺酯类化合物的用途，其特征在于通式I化合物用作农业或林业杀虫剂，对农业害虫有防治效果。
3.一种杀虫组合物，含有权利要求1所述的通式Ⅰ化合物为活性组分和农业或林业上可接受的载体。
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