CN105503712B - 一种吡乙苯醚肟酯化合物及其制备方法与应用 - Google Patents

一种吡乙苯醚肟酯化合物及其制备方法与应用 Download PDF

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CN105503712B
CN105503712B CN201510920900.2A CN201510920900A CN105503712B CN 105503712 B CN105503712 B CN 105503712B CN 201510920900 A CN201510920900 A CN 201510920900A CN 105503712 B CN105503712 B CN 105503712B
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pyrrole
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CN105503712A (zh
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张建军
孙国绍
林乐
金淑惠
王道全
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Abstract

本发明公开了属于农业化学技术领域的一种吡乙苯醚肟酯化合物及其制备方法与应用。以对羟基苯甲醛为原料，在DMF中与碳酸钾反应，得到中间产物II；中间产物II先与氢化钠反应为醇钠后与2‑氟吡啶反应得到中间产物III；中间产物III在甲醇中与吡啶和盐酸羟胺得到中间产物IV；中间产物IV在二氯甲烷中与各类羧酸、DCC和吡啶反应得到最终产物I所示的吡乙苯醚肟酯化合物。本发明化合物及其制剂具有杀虫及杀卵活性，且对虫卵的杀死活性良好，具有很高的农药研究价值。

Description

一种吡乙苯醚肟酯化合物及其制备方法与应用
技术领域
本发明属于农业化学技术领域，特别涉及一种吡乙苯醚肟酯化合物及其制备方法与应用。
背景技术
杂环化合物尤其是含氮杂环化合物由于其具有生物活性高、环境相容性好、作用靶标新颖等特性，已成为农药和医药创制中的研究热点。吡啶是有机合成中一个十分重要的杂环，和苯是生物电子等排体，但两者的疏水性差别较大，苯疏水常数为1.96，吡啶为0.65，因此吡啶代替苯环得到的新化合物往往具有更高的生物活性和内吸性、较低的毒性等优点。
烷氧基吡啶类化合物主要具有杀虫、杀螨、杀线虫及抑制植物病原菌的活性，如吡丙醚是日本住友化学株式会社于1983年创制研发的一类烷氧吡啶保幼激素类几丁质合成抑制剂，可用于防治同翅目、缨翅目、双翅目、鳞翅目等农业害虫，被广泛应用于水果、蔬菜、棉花和观赏植物上的白粉虱和蚧壳虫的防治以及公共卫生蚊蝇控制和动物保健中，具有高效低毒、用量少、持效时间长、对作物安全、对鱼类低毒等特点，是一种具有发展潜力的第三代杀虫剂。
肟酯类化合物具有优良的杀虫、杀菌、除草及抗植物病毒活性，大部分品种还具有低毒、低残留等优点，一直受农药开发者的青睐。肟酯结构广泛存在于各种农药医药分子中，其中肟菌酯是其典型的代表，但是目前还未有将同时含有吡啶、苯基和肟酯等基团的化合物用于农药的开发中。
发明内容
本发明针对现有技术中存在的缺点，其目的在于提供一种吡乙苯醚肟酯化合物及其制备方法与应用。
为了实现上述目的，本发明采取的技术方案如下：
一种吡乙苯醚肟酯化合物(CAU-PD)，所述化合物的结构通式如下：
其中，R为乙基、丁基、2-呋喃基、2-噻吩基、3-吡啶基、3-(2-氯吡啶)基、2,2,3,3-四甲基-环丙基、3-(2,2-二甲基-乙烯基)-2,2-二甲基-环丙基、3-(2-氯-3,3,3-三氟-丙烯基)-2,2-二甲基-环丙基、3-(2,6-二氯吡啶)基、1-(4-氯苯基)-2-甲基-丙基，4-甲基-苄基，β-萘甲基，苯基，4-乙氧基-苯基，4-甲氧基-苄基，3-氟-苯基，4-氯-苯基，4-甲氧基-苯基或2-(1-甲醛基)-苯基。
一种吡乙苯醚肟酯化合物的制备方法，所述制备方法的合成路线为：
包括下述步骤：
1)以对羟基苯甲醛为原料，在DMF中与碳酸钾反应，得到式II所示化合物；
2)将式II所示的化合物先与氢化钠反应为醇钠后与2-氟吡啶反应得到式III所示化合物；
3)将式III所示化合物在甲醇中与吡啶和盐酸羟胺得到式IV所示化合物；
4)将式IV在二氯甲烷中与各类羧酸、DCC和吡啶反应得到式I所示的吡乙苯醚肟酯化合物。
一种吡乙苯醚肟酯化合物在制备杀虫剂方面的应用。
所述杀虫剂能够杀灭小菜蛾、桃蚜、苹果黄蚜或棉铃虫卵。
所述杀虫剂的剂型为乳油、可湿性粉剂、悬浮剂、粉剂、可溶性粉剂、水剂、水分散粒剂、烟剂、颗粒剂或种衣剂。
一种杀虫剂，所述杀虫剂的活性成分为权利要求1所述的吡乙苯醚肟酯化合物。
一种杀虫剂乳油，所述的杀虫剂乳油各组分的质量百分数为：1-10％的吡乙苯醚肟酯化合物，5-15％的乳化剂，0.1-1％的渗透剂和余量的溶剂。
所述的乳化剂为农乳0208、GFC、0203B、OP-10或吐温-60；所述的溶剂为甲苯或二甲苯。
一种杀虫剂可湿性粉剂，所述的杀虫剂可湿性粉剂各组分的质量百分数为：15-50％的吡乙苯醚肟酯化合物，10-20％的表面活性剂和30-75％的白碳黑。
所述的表面活性剂为NNO。
本发明的有益效果为：制备吡乙苯醚肟酯化合物所需原料便宜，反应路线简单，产物具有杀虫及杀卵活性，且对虫卵的杀死活性良好。杀卵测定结果表明，所述化合物对棉铃虫卵的孵化均表现出一定抑制作用，部分化合物对棉铃虫卵的抑制率超过对照药剂吡丙醚，具有很高的农药研究价值。
附图说明
图1为吡乙苯醚肟酯化合物(CAU-PD)中CAU-PD-19的核磁共振氢谱图。
图2为吡乙苯醚肟酯化合物(CAU-PD)中CAU-PD-19的核磁共振碳谱图。
图3为吡乙苯醚肟酯化合物(CAU-PD)中CAU-PD-19的高分辨质谱图。
具体实施方式
下面通过具体的实施例对本发明进一步说明。应当注意到，这里给出的描述和实施例仅仅是为了描述本发明的具体实施方式，使技术人员更容易理解本发明，并不限定本发明的保护范围。
下述实施例中所述实验方法，如无特殊说明，均为常规方法；所述试剂和材料，如无特殊说明，均可从商业途径获得。
实施例1：吡乙苯醚肟酯化合物(CAU-PD)中CAU-PD-19(R＝3-吡啶基)的制备及结构鉴定：
在250mL圆底烧瓶中加入10g(82.0mmol)对羟基苯甲醛，30mL DMF溶解，然后加入22.6g(163.8mmol)碳酸钾和12.3g(98.3mmol)2-溴乙醇，100℃下反应12h；TLC(V(石油醚):V(乙酸乙酯)＝5：1)确定原料反应完全后冷却至室温，将反应液倒入水中，用200mL乙酸乙酯萃取3次，无水硫酸钠干燥，浓缩，柱色谱(V(石油醚):V(乙酸乙酯)＝10：1)分离得到白色产物11.3g，产率83％。
(2)在500mL圆底烧瓶中加入5.0g(30.1mmol)步骤(1)中所得产物，用40mL干燥DMF溶解，冰浴下，加入1.4g(36.1mmol)氢化钠搅拌半小时后，加入3.5g(36.1mmol)2-氟吡啶，60℃下反应7h；TLC检测反应完全后冷却至室温，将反应液倒入水中，用100mL乙酸乙酯萃取3次乙酸乙酯，无水硫酸钠干燥，浓缩，柱色谱(V(石油醚):V(乙酸乙酯)＝15：1)分离得到白色产物6.0g，产率82％。
(3)在250mL圆底烧瓶中加入4.4g(18.0mmol)步骤(2)中所得产物，甲醇溶解，加入5.7g(72.0mmol)吡啶和1.5g(21.6mmol)盐酸羟胺，常温反应3h后，加入1mol/L盐酸水溶液中和反应液至中性，用80mL乙酸乙酯萃取3次，无水硫酸钠干燥，浓缩，重结晶得产物4.3g，产率92％。
(4)在250ml圆底烧瓶中加入1.5g(5.8mmol)步骤(3)所得产物，干燥二氯甲烷溶解后，加入1.6g(7.5mmol)DCC和0.9g(7.5mmol)烟酸，室温反应过夜，TLC检测反应完全后，用二氯甲烷和水萃取，有机相干燥，浓缩后柱层析得CAU-PD-19无色固体1.9g，产率90％。
(5)结构鉴定：对获得的CAU-PD-19固体的结构进行进行鉴定，CAU-PD-19的核磁共振氢谱图如图1所示；CAU-PD-19的核磁共振碳谱图如图2所示；CAU-PD-19的高分辨质谱图如图3所示。从图3可知，CAU-PD-19质荷比(m/z)的质谱鉴定结果为364.1294，其理论计算值为364.1292，差值仅为-0.46，说明获得的CAU-PD-19化合物的结构准确无误。
结构确证数据为：
1H NMR(CDCl3,300MHz)δ:9.31-9.36(m,1H,ArH),8.85(dd,J＝4.9Hz,1.7Hz,1H,ArH),8.53(s,1H,CH＝N),8.39-8.43(m,1H,ArH),8.17-8.19(dd,J＝1.3Hz,5.1Hz,,1H,ArH),7.75-7.80(m,2H,ArH),7.58-7.64(m,1H,ArH),7.47(dd,J＝4.9Hz,8.0Hz,1H,ArH),6.97-7.15(m,2H,ArH),6.92(ddd,J＝0.8Hz,5.1Hz,7.0Hz,1H,ArH),6.82(d,J＝8.4Hz,1H,ArH),4.73(m,2H,PhOCH2),4.41(m,2H,OCH2)；
13CNMR(75MHz,CDCl3)δ:163.10,162.60,161.70,156.66,153.53,150.55,146.54,138.54,136.97,130.14,124.79,123.26,122.25,116.91,114.96,111,14,66.52,63.63；
HRMS(ESI)calcd for C20H18N3O4(M+H)+364.1292,found 3364.1294.
其他通式为CAU-PD的系列化合物均按照上述方法制备得到。它们的化合物编号，R对应的取代基团、理化数据见表1，结构鉴定的核磁共振氢谱、质谱数据见表2。
表1:通式为CAU-PD的系列化合物的编号、取代基团、理化数据
注：Me:甲基；Naphthyl:萘基；Py:吡啶基；Furan:呋喃；Thiophene：噻吩；
Cyclopropane：环丙烷；Dichloroethenyl：二氯乙烯基；Propyl:丙烷基；Ph:苯基
表2:通式为CAU-PD系列化合物核磁共振氢谱、质谱数据
注：Pos：质谱测定的正离子模式；Neg：质谱测定的负离子模式
实施例2：吡乙苯醚肟酯化合物(CAU-PD)中CAU-PD-19(R＝苯基)制剂的配制方法。
(1)乳油：在100mL容量瓶中加入1-10g化合物CAU-PD-19,5-15g乳化剂，0.1-1g渗透剂，然后用溶剂(如甲苯，二甲苯等)定容得CAU-PD-19质量分数为1-10％的乳油。
其他通式为CAU-PD系列化合物的乳油均可按照上述方法制备得到。
(2)可湿性粉剂：取15-50g化合物CAU-PD-19，10-20g表面活性剂，30-75g白碳黑，经混合粉碎后得CAU-PD-19质量分数为15-50％的可湿性粉剂。
其他通式为CAU-PD的系列化合物的可湿性粉剂均可按照上述方法制备得到。
实施例3：通式为CAU-PD的系列化合物杀虫、杀卵活性的测定。
(1)杀桃蚜试验：将带桃蚜叶片在药液中浸渍5s，晾干后记录桃蚜数并将其放入加有保湿滤纸的培养皿中，培养皿加盖后放入25±1℃的光照培养箱中。每个药剂处理30头以上，24-48小时后检查结果，计算其校正死亡率(％)，与对照药剂(吡丙醚)比对，判断药剂毒力大小。通式为CAU-PD的系列化合物对桃蚜的杀虫活性数据见表3。
表3：通式为CAU-PD系列化合物对桃蚜的杀虫活性
注：对照药剂吡丙醚和样品均为600mg/L
从表3的结果看，通式为CAU-PD系列化合物在600mg/L的测定浓度下能够杀死桃蚜，但是对桃蚜的杀虫活性表现不理想。
(2)杀小菜蛾试验：将油菜叶在药液中浸渍5s，晾干后放入加有保湿滤纸的培养皿中，接入小菜蛾的2龄幼虫，培养皿加盖后放入25±1℃光照培养箱中。每个药剂处理10头以上，分别在第2天和第3天检查结果。轻触虫体，不能正常爬行个体视为死亡，计算其校正死亡率(％)，与对照药剂比对，判断药剂毒力大小。通式为CAU-PD的系列化合物对小菜蛾的杀虫活性数据见表4。
表4：通式为CAU-PD系列化合物对小菜蛾的杀虫活性
注：对照药剂吡丙醚和样品均为600mg/L
从表4的结果看，通式为CAU-PD系列化合物在600mg/L的测定浓度下能够杀死小菜蛾，但是对小菜蛾的杀虫活性表现不理想。
(3)杀卵试验：将带卵纱布在药液中浸渍10s，晾干后放于加有保湿滤纸的培养皿中，用保鲜膜封口，培养皿加盖后放入25±1℃的光照培养箱中。记录卵孵化率，直到空白对照处理的卵不再孵化为止。计算其校正卵孵化抑制率(％)。与对照药剂(吡丙醚)比对，判断药剂毒力大小。通式为CAU-PD的系列化合物对棉铃虫卵的孵化抑制率见表5。
表5：通式为CAU-PD系列化合物对棉铃虫卵的孵化抑制率
注：对照药剂吡丙醚和样品均为600mg/L
从表5结果可以看出，通式为CAU-PD系列化合物在600mg/L的测定浓度下，部分化合物对棉铃虫卵的抑制率超过对照药剂吡丙醚，表明所述化合物对虫卵具有很好杀死活性。
供试靶标的来源：小菜蛾(Plutella xylostella Linnaeus)：2006年采自北京市蔬菜田，在室内用十字花科蔬菜叶片饲养，饲养条件为室温27±1℃，湿度为80％，光照强度为2000lx,光照时间为每天12h。在室内饲养条件下，用虫龄、体重及生理状况一致的2龄初幼虫进行药剂活性筛选试验；
桃蚜(Myzus persicae Sulzer)采自北京市海淀区。
棉铃虫(Helicoverpa armigera Hubner)卵：2005年采自邯郸棉田的成虫，长期在室内不跟药剂接触进行人工饲料饲养，产卵后1-2天的卵进行药剂杀卵试验。
中国农业大学可在符合国家有关规定且经相关部门批准后向公众提供。

Claims (10)

1.一种吡乙苯醚肟酯化合物，其特征在于，所述化合物的结构通式如下：
其中，R为4-甲基-苄基、β-萘甲基、2-呋喃基、3-(2-氯-3,3,3-三氟-1-丙烯基)-2,2-二甲基-环丙基、2-(3,6-二氯吡啶)基、丙基、甲基、2-噻吩基、2,2,3,3-四甲基-环丙基。
2.权利要求1所述的一种吡乙苯醚肟酯化合物的制备方法，其特征在于，所述制备方法的合成路线为：
包括下述步骤：
1)以对羟基苯甲醛为原料，在DMF中与碳酸钾反应，得到式II所示化合物；
2)将式II所示的化合物先与氢化钠反应为醇钠后与2-氟吡啶反应得到式III所示化合物；
3)将式III所示化合物在甲醇中与吡啶和盐酸羟胺得到式IV所示化合物；
4)将式IV在二氯甲烷中与各类羧酸、DCC和吡啶反应得到式I所示的吡乙苯醚肟酯化合物。
3.权利要求1所述的一种吡乙苯醚肟酯化合物在制备杀虫剂方面的应用。
4.根据权利要求3所述的应用，其特征在于，所述杀虫剂能够杀灭小菜蛾、桃蚜、苹果黄蚜或棉铃虫卵。
5.根据权利要求3所述的应用，其特征在于，所述杀虫剂的剂型为乳油、悬浮剂、粉剂、水剂、烟剂、颗粒剂或种衣剂。
6.一种杀虫剂，其特征在于，所述杀虫剂的活性成分为权利要求1所述的吡乙苯醚肟酯化合物。
7.一种杀虫剂乳油，其特征在于，所述杀虫剂乳油各组分的质量百分数为：1-10％权利要求1所述的吡乙苯醚肟酯化合物，5-15％的乳化剂，0.1-1％的渗透剂和余量的溶剂。
8.根据权利要求7所述的一种杀虫剂乳油，其特征在于，所述的乳化剂为农乳0208、GFC、0203B、OP-10或吐温-60；所述的溶剂为甲苯或二甲苯。
9.一种杀虫剂可湿性粉剂，其特征在于，所述的杀虫剂可湿性粉剂各组分的质量百分数为：15-50％权利要求1所述的吡乙苯醚肟酯化合物，10-20％的表面活性剂和30-75％的白碳黑。
10.根据权利9所述的一种杀虫剂可湿性粉剂，其特征在于，所述的表面活性剂为NNO。
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