CN105541794A - 含有七氟异丙基的吡啶基吡唑酰胺类衍生物及其应用 - Google Patents
含有七氟异丙基的吡啶基吡唑酰胺类衍生物及其应用 Download PDFInfo
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- OHFDWGWBLALDBL-UHFFFAOYSA-N ethyl 2-(3-chloropyridin-2-yl)-5-methylpyrazole-3-carboxylate Chemical compound CCOC(=O)C1=CC(C)=NN1C1=NC=CC=C1Cl OHFDWGWBLALDBL-UHFFFAOYSA-N 0.000 description 2
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- RKOUFQLNMRAACI-UHFFFAOYSA-N 1,1,1-trifluoro-2-iodoethane Chemical compound FC(F)(F)CI RKOUFQLNMRAACI-UHFFFAOYSA-N 0.000 description 1
- LFXSHFHOJMKZDE-UHFFFAOYSA-N 2-formamidobenzamide Chemical class NC(=O)C1=CC=CC=C1NC=O LFXSHFHOJMKZDE-UHFFFAOYSA-N 0.000 description 1
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- PSOVNZZNOMJUBI-UHFFFAOYSA-N chlorantraniliprole Chemical compound CNC(=O)C1=CC(Cl)=CC(C)=C1NC(=O)C1=CC(Br)=NN1C1=NC=CC=C1Cl PSOVNZZNOMJUBI-UHFFFAOYSA-N 0.000 description 1
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- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 1
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- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
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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
- C07D401/04—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 directly linked by a ring-member-to-ring-member bond
-
- 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
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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Abstract
本发明涉及如通式(I)所示的含有七氟异丙基的吡啶基吡唑酰胺类衍生物的制备与应用，该类化合物代表一种广谱高效的杀虫杀菌剂结构类型。含有七氟异丙基的吡啶基吡唑酰胺类衍生物用作新型杀虫杀菌剂能很好地防治东方粘虫、小菜蛾、甜菜夜蛾；也很很好地用于防治黄瓜褐斑病、黄瓜细菌性角斑病、黄瓜枯萎病、黄瓜霜霉病、黄瓜白粉病、番茄细菌性斑点病、水稻纹枯病。式中R1、R2、R3的意义见说明书。
Description
一、技术领域
本发明涉及含有七氟异丙基的吡啶基吡唑酰胺类衍生物及其作为杀虫剂和杀菌剂方面的应用，属农药技术领域。
二、背景技术
近年来，农用化学品领域以鱼尼丁受体为靶标杀虫剂的研发取得了突破性进展。日本农药公司、拜耳公司和杜邦公司分别发现了两类高活性杀虫剂-邻苯二甲酰胺类和邻甲酰氨基苯甲酰胺类，这是首次发现作用于靶标鱼尼丁受体的合成杀虫剂，它通过诱导昆虫鱼尼丁受体的活化使内源钙离子库释放，进而导致昆虫死亡。此类杀虫剂表现出高效、广谱、对非靶标生物安全以及与传统杀虫剂无交互抗性等特点。
氯虫酰胺(chlorantraniliprole)，化学名称3-溴-N-[4-氯-2-甲基-6-[(甲氨基甲酰基)苯]-1-(3-氯吡啶-2-基)-1H-吡唑-5-甲酰胺，商品名康宽(Ryanxypyr)。它是美国杜邦公司开发出来的一种新型邻甲酰胺基苯甲酰胺类杀虫剂，属昆虫鱼尼丁受体抑制剂，具有触杀和胃毒作用，表现出高效、广谱、持效和作用机理新颖等特点，可用于防治各种鳞翅目害虫，其防治效果明显优于当前生产中使用的其它商品化杀虫剂品种，对其它杀虫剂不存在交互抗性，且对天敌昆虫安全，可用于蔬菜、甜菜、棉花等作物防治甜菜夜蛾、甘蓝夜蛾、小菜蛾、菜粉蝶、棉铃虫等各种害虫，对各龄期幼虫都有很好的防治效果。目前是鱼尼丁受体类杀虫剂研究的热点。
目前已经商品化的鱼尼丁受体类杀虫剂有以三个：
各大公司也都致力于此类化合物的研究，如拜耳农科创制的新结构：
杜邦公司的新结构：
先正达公司的新结构：
三、发明内容
本发明的目的是提供一类含有七氟异丙基的吡啶基吡唑酰胺类衍生物及其应用，该类化合物具有优异的杀虫、杀菌活性。
本发明是通式(I)所示的含有七氟异丙基的吡啶基吡唑酰胺类衍生物的制备与应用，
式中，R1代表氢、卤素、1-6碳烷基、一个或一个以上相同或不同的卤素原子取代的烷基；R2代表氢、卤素、1-6碳烷基、一个或一个以上相同或不同的卤素原子取代的烷基；R3代表取代或未取代的烷基、烯基、炔基、环烷基。
本发明说述的含有七氟异丙基的吡啶基吡唑酰胺类衍生物可以按如下方法制备：化合物1经过硫酸钾氧化制得化合物2，化合物2与相应的卤代烃反应制得化合物3，化合物3水解得到酸4，化合物4与相应的七氟异丙基取代的苯胺制得目标通式(I)的含有七氟异丙基的吡啶基吡唑酰胺类衍生物。
化合物1是市售的或按已知方法制备的。
本发明还可用表1列出的化合物来说明，但并不限定本发明。
本发明通式(I)的化合物具有优异的杀虫杀菌活性，作为杀虫剂，能用于防治鳞翅目类、鞘翅目类、同翅目类、双翅目类及直翅目类害虫；作为杀菌剂，能用于防治黄瓜褐斑病、黄瓜细菌性角斑病、黄瓜枯萎病、黄瓜霜霉病、黄瓜白粉病、番茄细菌性斑点病、水稻纹枯病。
本发明通式(I)的化合物可以直接使用，也可以加上农业上接受的载体使用，也可以和其他类型杀虫剂杀菌剂复配使用。
四、具体实施方式
以下结合实施例来进一步说明本发明：
实施例一：中间体2的合成
将化合物1(37mmol)溶于100mL乙腈，加入硫酸(74mmol)室温搅拌10min，加入过硫酸钾(56mmol)，升温回流4h后，冷却至55℃，过滤，滤液真空下脱溶，加水100mL，再用二氯甲烷萃取(3×150mL)，有机层合并，干燥，滤液浓缩，剩余物经硅胶色谱柱减压柱层析，洗脱液为乙酸乙酯和石油醚混合溶剂，得白色固体2(62.4％)，m.p.136-138℃.1HNMR(CDCl3，400M)δ：9.35(s，1H，NH)；8.52(d，J＝4.4Hz，1H，pyridyl-H)；7.90(d，J＝8.0Hz，1H，pyridyl-H)；7.43(dd，J1＝4.4Hz，J2＝8.0Hz，1H，pyridyl-H)；6.36(s，1H，pyrazolyl-H)；4.19(q，2H，J＝7.2Hz，CH2)；1.19(t，3H，J＝7.2Hz，CH3).
实施例二：中间体3-甲基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成
将化合物2(7.5mmol)溶于30mLDMF，加入无水碳酸钾(11mmol)，加热至100℃，缓慢滴加碘甲烷(9mmol)的DMF溶液，滴毕，100℃下反应3h，乙酸乙酯萃取(3×50mL)，水洗，有机层干燥，滤液浓缩，得油状液体3-甲基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯。1HNMR(CDCl3，400M)δ：8.54(d，J＝4.6Hz，1H，pyridyl-H)；8.21(d，J＝8.0Hz，1H，pyridyl-H)；7.65(dd，1H，J1＝4.6Hz，J2＝8.0Hz，1H，pyridyl-H)；6.63(s，1H，pyrazolyl-H)；4.20(q，J＝7.0Hz，2H，CH2)；3.80(s，3H，CH3)；1.07(t，J＝7.0Hz，3H，CH3).
实施例三：中间体3-甲基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成
在100mL圆底烧瓶中，加入酯(2.10g，7.5mmol)，20mL甲醇，5mL水和NaOH(0.36g，9mmol)，反应混合物室温搅拌反应6h，减压脱去大部分溶剂，加50mL水稀释，乙酸乙酯(10mL)萃取未反应的有机物，水层用浓盐酸调至pH1.5，析出固体，室温搅拌30min，乙酸乙酯萃取(3×50mL)，水洗，有机层干燥，滤液浓缩，得1.09g白色固体3-甲基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸，产率57.6％，m.p.245-247℃.1HNMR(DMSO-d6，400M)δ：13.50(s，3H，CH3)；8.51(d，J＝4.6Hz，1H，pyridyl-H)；8.18(dd，J＝8.0Hz，1H，pyridyl-H)；7.61(dd，J1＝4.6Hz，J2＝8.0Hz，1H，pyridyl-H)；6.54(s，1H，pyrazolyl-H)；3.85(s，3H，CH3).
实施例四：中间体3-三氟乙氧基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯的合成
将中间体2(3.7mmol)溶于30mLDMF，加入无水碳酸钾(5.5mmol)，加热至100℃，缓慢滴加2，2，2-三氟碘乙烷(4.4mmol)的DMF溶液，滴毕，100℃下反应3h，乙酸乙酯萃取(3×50mL)，水洗，有机层干燥，滤液浓缩，剩余物经硅胶色谱柱减压柱层析，洗脱液为乙酸乙酯和石油醚混合溶剂，得1.28g白色固体3-三氟乙氧基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸乙酯，产率99％，m.p.63-65℃.1HNMR(CDCl3，400M)δ：8.52(dd，J1＝1.6Hz，J2＝4.8Hz，1H，pyridyl-H)；7.91(dd，J1＝1.6Hz，J2＝8.0Hz，1H，pyridyl-H)；7.43(dd，1H，J1＝4.8Hz，J2＝8.0Hz，1H，pyridyl-H)；6.54(s，1H，pyrazolyl-H)；4.66(q，J＝16.4Hz，2H，CH2CF3)；4.20(q，J＝7.2Hz，2H，CH2)；1.22(t，J＝7.2Hz，3H，CH3).
实施例五：中间体3-三氟乙氧基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸的合成
在100mL圆底烧瓶中，加入酯(3.7mmol)，20mL甲醇，5mL水和NaOH(4.5mmol)，反应混合物室温搅拌反应6h，减压脱去大部分溶剂，加50mL水稀释，乙酸乙酯(10mL)萃取未反应的有机物，水层用浓盐酸调至pH1.5，析出固体，室温搅拌30min，乙酸乙酯萃取(3×50mL)，水洗，有机层干燥，滤液浓缩，得0.84g白色固体3-三氟乙氧基-1-(3-氯-2-吡啶基)-1H-吡唑-5-甲酸，产率71.3％，m.p.165-167℃.1HNMR(CDCl3，300M)δ：8.51(dd，J1＝1.6Hz，J2＝4.8Hz，1H，pyridyl-H)；7.92(dd，J1＝1.6Hz，J2＝8.0Hz，1H，pyridyl-H)；7.44(dd，1H，J＝4.8Hz，8.0Hz，pyridyl-H)；6.59(s，1H，pyrazolyl-H)；4.65(q，J＝16.4Hz，2H，CH2CF3).
实施例六：通式(I)化合物合成
将酸4(1.0mmol)溶于20mL二氯甲烷，加入草酰氯(3mmol)，反应混合物在室温反应3h，减压蒸除溶剂得酰氯粗品。在冰浴下，酰氯溶于10mL二氯甲烷中慢慢滴入中间体5(1.3mmol)的20mL二氯甲烷溶液中，然后滴加三乙胺(1.5mmol)作缚酸剂，室温搅拌4h。待反应结束，脱溶，向反应瓶中加入二氯甲烷(60mL)，然后分别用饱和碳酸氢钠水溶液(20mL)、饱和氯化钠水溶液(20mL)和水(50mL)洗涤有有机层，无水Na2SO4干燥，过滤，滤液浓缩，剩余物经硅胶色谱柱减压柱层析，洗脱液为乙酸乙酯和石油醚混合溶剂，得通式(I)的化合物，具体化合物见表1。
实施例六：对小菜蛾幼虫活性
将一定量的待测化合物溶于适量N，N-二甲基甲酰胺，用含有TW-20的水配成400mgL-1的药液，并根据需要稀释成特定浓度，将新鲜的甘蓝叶切成片，在待测药液中浸渍甘蓝叶片，时间3-5秒，甩掉余液。待药液干后，放入具有标记的10cm长的直型试管内，接入3龄小菜蛾幼虫，用纱布盖好管口。将试验处理置于标准处理室内，72h检查结果以拨针轻触虫体，不动者为死亡，每个浓度下重复三次。计算并校正死亡率。表2为部分化合物的测试结果。
实施例七：防治蔬菜病害活体微量筛选试验
选用2片子叶期黄瓜苗，黄瓜褐斑病、白粉病、霜霉病采用孢子悬浮液喷雾接种，黄瓜细菌性角斑病、番茄细菌性斑点病采用菌悬液喷雾接种，黄瓜枯萎病病采用胚根浸种接种方法，水稻纹枯病采用菌丝喷雾接种法。于晴天上午将供试药剂及对照药剂均匀喷施于黄瓜子叶上，2小时后接种病原菌，保湿培养。待对照充分发病后按照分级标准，调查病情，计算病情指数和防效。表3为部分化合物的测试结果。
表1含有七氟异丙基的吡啶基吡唑酰胺类衍生物(I)列表
aThevalueofHRMS[M+Na]+.
表2部分化合物对小菜蛾活性测试结果试验结果
表3部分化合物防治蔬菜病害活体微量筛选试验结果(500mgkg-1)
Claims (4)
1.一种含有七氟异丙基的吡啶基吡唑酰胺类衍生物，其特征在于它具有如下通式(I)所示结构：
式中，R1代表氢、卤素、1-6碳烷基、一个或一个以上相同或不同的卤素原子取代的烷基；R2代表氢、卤素、1-6碳烷基、一个或一个以上相同或不同的卤素原子取代的烷基；R3代表取代或未取代的烷基、烯基、炔基、环烷基。
2.根据权利要求1所述的含有七氟异丙基的吡啶基吡唑酰胺类衍生物，其特征在于。R1为氢、甲基、乙基、异丙基；R2为氢、甲基、乙基、异丙基；R3为甲基、乙基异丙基、烯丙基、炔丙基、三氟乙基。
3.根据权利要求1所述的含有七氟异丙基的吡啶基吡唑酰胺类衍生物的应用，其特征在于它作为杀虫剂，能用于防治鳞翅目类、鞘翅目类、同翅目类、双翅目类及直翅目类害虫。
4.根据权利要求1所述的含有七氟异丙基的吡啶基吡唑酰胺类衍生物的应用，其特征在于它作为杀菌剂，能用于防治黄瓜褐斑病、黄瓜细菌性角斑病、黄瓜枯萎病、黄瓜霜霉病、黄瓜白粉病、番茄细菌性斑点病、水稻纹枯病。
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