CN1073799C - 4－氯－1－(乙氧甲基)－2－(对氯苯基)－5－(三氟甲基)吡咯－3－腈的应用 - Google Patents

4－氯－1－(乙氧甲基)－2－(对氯苯基)－5－(三氟甲基)吡咯－3－腈的应用 Download PDF

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CN1073799C
CN1073799C CN95106173A CN95106173A CN1073799C CN 1073799 C CN1073799 C CN 1073799C CN 95106173 A CN95106173 A CN 95106173A CN 95106173 A CN95106173 A CN 95106173A CN 1073799 C CN1073799 C CN 1073799C
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trifluoromethyl
pyrroles
aryl
rubigan
nitrile
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CN1116487A (zh
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V·卡姆斯瓦兰
R·F·特纳Jr
J·M·巴顿
D·J·科恩
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Abstract

本发明提供了重要的吡咯啉和甘氨酸中间体，所说中间体的制备方法及其在生产芳基吡咯杀虫剂上的应用。

Description

4-氯-1-(乙氧甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈 的应用
本申请是申请号为CN91112749.6专利申请的分案申请。
本发明的目的在于描述了生产各种杀虫、杀螨及杀线虫的芳基吡咯化合物过程中更为有用的中间体及所述中间体的制备方法。
本发明的目的还在于描述了4-卤代-2-芳基-1-(烷氧甲基)-5-(三氟甲基)吡咯化合物的制备方法，该化合物可用于控制昆虫、螨及线虫害并可保护收获及生长中的庄稼免遭所述的虫害。
本发明另一目的是描述了中间体4-卤代-2-芳基-1-(卤代甲基)-5-(三氟甲基)吡咯化合物。
本发明进一步的目的是描述了一种杀虫、杀螨及杀线虫剂4-氯-1-(乙氧甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈及其用于保护收获及生产中庄稼的方法，
本发明涉及式Ⅰ化合物
Figure C9510617300031
其中A是氢或C1-C4烷基；W是CN、NO2或CO2R6；L是氢或卤素且M和R各自独立地是氢、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚磺酰基、C1-C4烷磺酰基、氰基、硝基、卤素，CF3、R1CF2Z、R2CO或MR3R4，并且当M和R处于邻位时，它们可以和与之相连的碳原子一起形成环，其中MR代表结构
-OCH2O-,-OCF2O-或-CH=CH-CH=CH-；
Z是S(O)n或O；
R1是氢、F、CHF2、CHFCl或CF3；
R2是C1-C4烷基、C1-C4烷氧基或NR3R4；
R3是氢或C1-C4烷基；
R4是氢、C1-C4烷基或R5CO；
R5是氢或C1-C4烷基且
R6是C1-C6烷基、C3-C6环烷基或苯基；
n是整数0、1或2。
本发明还涉及式Ⅱ化合物
Figure C9510617300041
其中A、L、M和R如上述通式(Ⅰ)中所描述，只是当A为氢时，L、M和R中必须至少有一个不是氢。
本发明还涉及上述化合物的制备方法及其在生产芳基吡咯杀虫剂方面的应用。
此外，本发明还指明了式Ⅳ的具有杀虫作用的芳基吡咯化合物的生产方法
Figure C9510617300042
其中R1是C1-C6烷基；
W是CN,NO2或CO2R2；
X是Br,Cl或I；
L是氢或卤素；
M和R各自独立地是氢，C1-C4烷基，C1-C4烷氧基，C1-C4烷硫基，C1-C4烷基亚磺酰基，C1-C4烷基磺酰基，CN,NO2,Cl,Br,F,I,CF3,R3OF2Z,R4CO或NR5R6且当M和R处于邻位时，它们可以和与之相连的碳原子一起形成一个环，其中MR代表结构
-OCH2O-,-OCF2O-，或-CH=CH=CH=CH-；
R2是C1-C6烷基、C3-C6烷氧基或苯基；
R3是氢，F,CHF2,CHFCl或CF3；
R4是C1-C4烷基，C1-C4烷氧基或NR5R5；
R5是氢或C1-C4烷基；
R6是氢，C1-C4烷基或R7CO；
R7是氢或C1-C4烷基；
Z是S(O)n或O且
n是整数0、1或2
该发明包括将式Ⅴ化合物
其中W,L,M及R如上描述，与至少1摩尔当量的卤素，X2，其中X2是Br,Cl或I，更为可取的是在高温下在溶剂存在下反应以得到2-芳基-1-甲基吡咯中间体，将所说的1-甲基吡咯中间体再与另外的至少1摩尔当量的所说卤素反应形成2-芳基-4-卤代-1-甲基吡咯中间体，将所说的4-卤代-1-甲基吡咯中间体进-步与至少1摩尔当量的所说卤素在自由基引发剂的存在下反应形成2-芳基-4-卤代-1-(卤代甲基)吡咯中间体，然后将所说的4-卤代-1-(卤代甲基)吡咯中间体与至少1摩尔当量的碱金属C1-C6醇盐反应得到式Ⅳ化合物。
通式Ⅰ化合物可通过将式Ⅱ化合物与约1.0摩尔当量的式Ⅲ的活化链烯在酸酐及溶剂存在下，任意地在有机碱的存在下反应制得。
H2C=CHW(Ⅲ)
其中W是CN,NC2或CO2R6且R6是C1-C6烷基，C3-C6环烷基或苯基。该制备方法可由流程图Ⅰ加以说明。
                       流程图Ⅰ
Figure C9510617300061
用于本发明方法的溶剂包括质子惰性有机溶剂，例如腈如乙腈；酯如乙酸乙酯，丙酸甲酯等；醚如乙醚，四氢呋喃，二烷，乙二醇二甲醚等；卤代烃如二氯甲烷，1,2-二氯乙烷，氯仿，1,1,1-三氯乙烷，四氯化碳等；羧酰胺如N,N-二甲基甲酰胺，N-甲基吡咯烷酮等；亚砜如二甲基亚砜；砜如四氢噻吩砜；芳香烃类如苯，甲苯，二甲苯等；卤代芳香烃如氯苯，邻-二氯苯等。优选的有机溶剂之一是乙腈。用于本发明方法的合适的酸酐是低级烷基酐如乙酸酐。可用于本发明方法的有机碱是吡啶，吗啉，三(C1-C4)烷基胺，六亚甲基四胺，二甲氨基吡啶等。优选的有机碱是三(C1-C4)烷基胺如三乙基胺。
如流程Ⅱ所示，式Ⅱ化合物可通过合适的芳基醛与合适的胺前体经过Strecker合成形成可被三氟乙酰化的式Ⅲ氨基酸中间体来制备，以得到所需的式Ⅱ化合物。
                       流程图Ⅱ
Figure C9510617300062
A为氢的式Ⅱ化合物也可通过合适的芳基甘氨酸前体三氟乙酰化制得。将这样所得的化合物用烷基化试剂如低级烷基卤化物烷基化给出A为C1-C4烷基的式Ⅱ化合物。用碘甲烷作烷化剂，反应程序如流程图Ⅲ所示。
                       流程图Ⅲ
Figure C9510617300071
本发明化合物是生产用作杀虫，杀螨及杀线虫剂的各种芳基吡咯化合物的中间体。由本发明化合物制得的芳基吡咯杀虫剂有4-卤代-2-(对氯苯基)-1-(取代的)-5-(三氟甲基)吡咯-3-腈化合物。本发明方法的一个实例是：将其中A为甲基，W为CN,L和R为氢且M为Cl的式Ⅰ的吡咯啉化合物在质子惰性溶剂存在条件下，在高温与卤素反应得到其中X为氯、溴或碘的通式Ⅷ和Ⅶ的芳基吡咯杀虫剂。在自由基引发剂如过氧化苯甲酰，2,2＇-偶氮二异丁腈，光化学照射等的作用下，令其进一步与另外的卤素反应，可生成式Ⅵ的相应1-(卤代甲基)吡咯中间体，后者可再与碱金属醇盐如乙醇钠，甲醇钾等进行反应，得到式Ⅳ的芳基吡咯杀虫剂。该反应如流程图Ⅳ所示。
                       流程图Ⅳ
通过改变取代基A,W,L,M和R，卤素试剂及反应条件，可以自式Ⅰ化合物制得许多不同的芳基吡咯杀虫剂、杀螨剂及杀线虫剂。
通式Ⅳ化合物，对于控制昆虫，螨及线虫的害虫及保护正在生长的及已收获的农作物免遭这些害虫的侵害是特别有效的。这些化合物的制备方法通常包括用卤化剂如次卤酸盐，卤素或磺酰卤对2-芳基-5-(三氟甲基)吡咯-3-腈进行卤化，以形成相应的4-卤代吡咯中间体，然后用合适的氯甲基(C1-C6烷基)醚对所说的中间体进行烷化。
现已发现，通式Ⅳ化合物特别是其中X为氯的通式Ⅳ化合物，其方便有效的制备方法是：由通式Ⅴ的吡咯啉化合物在溶剂存在条件下，并最好在高温通过合适卤素的渐增加成以形成通式Ⅶ的4-卤代-1-甲基吡咯中间体，然后就地将通式Ⅶ中间体在自由基引发剂存在下与另外的卤素反应以形成通式Ⅵ的4-卤代-1-(卤甲基)吡咯中间体，再将通式Ⅵ中间体与碱金属C1-C6醇盐进行反应来制备。令人惊奇的是，所需的式Ⅳ化合物用上述过程制备具有很高的产率及纯度。本发明的方法如流程图Ⅴ所示。
                       流程图Ⅴ
Figure C9510617300091
特别有利的是，现已发现卤素的渐增加成可提高反应的产率和产品的纯度。由于避免使用了某些有害的反应试剂如氯甲基乙基醚，本发明的方法还提高了通式Ⅰ化合物生产对环境和人体的安全性。此外，本发明的方法包括一种有效的杀虫、杀螨及杀线虫剂2-(对氯苯基)-4-氯-1-乙氧甲基-5-(三氟甲基)吡咯-3-腈的生产。
可用于本发明方法的合适的溶剂包括质子惰性溶剂，例如卤代芳烃如氯苯、邻二氯苯等及卤代烃如二氯甲烷、四氯化碳、氯仿、1,2-二氯乙烷等。优选的溶剂包括卤代芳烃如氯苯和卤代烃如四氯化碳。适用的自由基引发剂有光，过氧化物如过氧化苯甲酰，二叔丁基过氧化物等，偶氮化合物如偶氮二异丁腈等。优选的自由基引发剂是过氧化苯甲酰和光。本发明方法适用的碱金属醇盐是乙醇钠，甲醇钾等。
本发明方法中，反应速率随温度的升高而加快，因此在约55℃到210℃，优选的是在约70℃到120℃范围内的高温可使氧化作用，环的卤化及侧链的卤化作用以高效且有效的速率进行而不引起不适当的不利的付反应。
很明显，本发明方法包括一种杀虫，杀螨及线虫剂2-(对氯苯基)-4-氯-1-(乙氧甲基)-5-(三氟甲基)吡咯-3-腈的生产。吡咯-3-腈可有效地控制蜱螨目；鳞翅目、鞘翅目、半翅目等。可以有效地加以控制的农业害虫有马铃薯瓢虫，粉纹夜蛾，小菜蛾，菸夜蛾，美洲棉铃虫，甜菜夜蛾，烟草棉铃虫等。可被本发明化合物保护的作物有莴苣，花茎甘蓝，谷物，洋白菜，花椰菜，马铃薯，棉花等。
实际上，当应用于农作物或生长农作物的土壤以保护农作物免遭昆虫，螨及线虫的侵害时，通常约10ppm到10,000ppm，优选的是约100到5,000ppm分散于水或其它合适的液体载体中的2-(对氯苯基)-4-氯-1-(乙氧甲基)-5-(三氟甲基)吡咯-3-腈是有效的，化合物也可有效地保护园艺植物如草皮草免遭如蛴螬，麦长蝽等害虫的侵害。
单独使用时，本发明的4-氯-1-(乙氧甲基)吡咯化合物可有效地控制昆虫，螨和线虫，它也可以与包括杀线虫剂及杀螨剂在内的其它杀害虫化合物联合使用。如本发明化合物可有效地与其它芳基吡咯，磷酸盐，氨基甲酸酯，拟除虫菊酯，甲脒，氯代烃，卤代苯甲酰脲等联合使用。
为了便于对本发明做进一步的了解，下面提供的实施例对其做了更详细的说明。除了如权利要求书中的限定，由此并未对本发明加以限定。术语NMR标志核磁共振，术语HPLC标示高压液相色谱。除非另作说明，所有成份是重量成份。
                      实施例1
               2-(对氯苯基)肌氨酸的制备
Figure C9510617300101
将对氯苯甲醛(153g,1.0mol)在四氢呋喃中的混合物。用甲胺盐酸化物(88g,1.3mol)水溶液，随即用氢化钠(53g,1.0mol)水溶液处理，在室温下搅拌16小时并用甲苯萃取。将有机萃取液依次用10cc吡啶及50cc乙酸酐处理(放热)，在室温下搅拌1/2小时并真空浓缩得到油状残余物。将残余物加入水和浓盐酸1∶1的混合物中，在回流温度下加热2小时，冷却，用水稀释并用50％NaOH溶液中和至约pH2。过滤所得固体沉淀物并将其空气干燥，得到白色固体状标题产品180g(产率89.5％),mp208-213℃。
                        实施例2
         2-(对氯苯基)-N-(三氟乙酰基)肌氨酸的制备
Figure C9510617300111
将2-(对氯苯基)肌氨酸(27g,0.135mol)在无水甲苯中的混合物用20cc三氟乙酸酐处理，搅拌1小时并真空浓缩得到固体残余物。将残余物用甲苯重蒸几次得到红色固体状标题产品38.7g(产率97％),mp117-118℃，通过NMR光谱鉴定。
                         实施例3
             2-苯基-N-(三氟乙酰基)甘氨酸的制备
Figure C9510617300112
将DL-苯基甘氨酸(15.1g,0.10mol)在甲醇中的混合物用三乙胺(10.1g,0.10mol)和三氟乙酸乙酯(17.8g,0.125mol)处理，在室温下搅拌72小时，用甲醇稀释并用Dowex50×8酸性树脂处理。将反应混合物搅拌10分钟并过滤。滤液真空浓缩得到浅黄色固体，将其用1,2-二氯乙烷重结晶得到白色针状标题产品10.5g(产率42％),mp155-157℃。
                        实施例4
          2-对氯苯基-N-(三氟乙酰基)甘氨酸的制备
Figure C9510617300113
将2-(对氯苯基)甘氨酸(37.1g,0.2mol)在甲醇中的混合物用三乙胺(20.2g,0.2mol)处理，搅拌10分钟，用滴加的三氟乙酸乙酯(35.5g,0.25mol)处理，搅拌4天，用甲醇稀释并用Dowex50×8-100离子交换树脂处理。将反应混合物搅拌10分钟并过滤。将滤饼用甲醇洗涤。合并滤液并真空浓缩得到黄色固体，将其用1,2-二氯乙烷重结晶得到白色结晶状标题化合物26.4g(产率46.8％)，mp170-172℃。
                           实施例5
             2-苯基-N-(三氟乙酰基)肌氨酸的制备
将2-苯基-N-(三氟乙酰基)甘氨酸(2.5g,0.01mol)和碘甲烷(11.35g,0.08mol)在四氢呋喃中的混合物一部分一部分地用在矿物油中60％分散度的氢化钠(1.2g,0.03molNaH)处理，在室温下搅拌1小时，在回流温度下加热17小时，冷至室温，依次用乙酸乙酯和1ml水稀释，真空浓缩得到湿的，黄色固体残余物。将残余物分散在乙醚和水的混合物中。醚层用碳酸氢钠溶液洗涤。合并水相，用10％HCl酸化并用乙酸乙酯萃取。将乙酸乙酯萃取液连续地用水，硫代硫酸钠和饱和氯化钠溶液洗涤，用MgSO4干燥并真空浓缩得到浅黄色固体，将其用甲基环己烷重结晶得到白色结晶状标题化合物0.5g，(产率19.1％),mp124-126℃。
                      实施例6
2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈的制备
将2-(对氯苯基)-N-(三氟甲基)肌氨酸(7.4g,0.02mol)的乙腈溶液用乙酸酐(5.1g,0.05mol)，丙烯腈(1.6g,0.03mol)和10滴三乙胺处理，在回流温度下加热5小时，冷却并真空浓缩得到红色油状残余物。将残余物依次用9∶1己烷/乙醚乙酯及二氯甲烷和乙酸乙酯的混合物通过硅胶过滤。合并的滤液真空浓缩得到红色固体状标题产品6.1g(产率85％)，由NMR和质谱分析测定。将部分固体自二氯甲烷中重结晶得到淡黄色针状物，mp158-160℃。
                      实施例7
         2-(对氯苯基)-5-(三氟甲基)-2-吡咯啉-3-腈的制备
Figure C9510617300131
用与实施例6所描述的基本相同的方法并用取代的2-(对氯苯基)-N-(三氟乙酰基)甘氨酸作为起始原料可得到淡黄色固体状标题产品，mp158-160℃。
                      实施例8
4-氯-1-氯甲基-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈的制备
Figure C9510617300132
向2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈(2.85g,0.01mol)的邻二氯苯溶液中加入氯(0.8g,0.011mol)；将所得的溶液在室温下搅拌1小时，在多于2小时内将其缓慢加热至90℃，冷却至50℃，用另外的氯(0.8g,0.11mol)处理，在110℃下加热24小时，冷至室温，再用另外的氯处理并伴随加入小部分过氧化苯甲酰并在110℃下加热4小时或直至经色谱分析反应完全为止。将所得溶液冷却，用偏亚硫酸氢钠溶液洗涤并真空浓缩得到残余物，通过加入庚烷使其结晶，得到白色固体状标题产品，mp107-108℃。
                        实施例9
4-氯-2-(对氯苯基)-1-(乙氧甲基)-5-(三氟甲基)吡咯-3-腈的制备
Figure C9510617300141
将4-氯-1-(氯甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈(2.6g,0.0074mol)的四氢呋喃溶液用乙醇钠的21％wt/wt的变性酒精(3.6ml,0.0096mol)溶液处理，在室温下搅拌1小时，再用另外的2-3滴乙醇钠溶液处理，在回流温度下加热1小时，冷却并倾入水中。将所得沉淀过滤，干燥并自异丙醇中重结晶，得到白色固体状标题产品1.6g(产率60％),mp104.0-104.5℃。
                             实施例10
        2-(对氯苯基)-1-甲基-5-(三氟甲基)吡咯-3-腈的制备
将2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈(2.87g,0.01mol)在氯苯中的混合物用溴(1.76g,0.011mol)的氯苯溶液处理并在100℃下加热4-5小时(直至HPLC分析反应完全)。将反应混合物冷却至室温，用水稀释并用乙酸乙酯萃取。合并有机萃取液，连续地用水，偏亚硫酸氢钠和水洗涤，用MgSO4干燥并真空浓缩，得到浅黄色固体残余物。将该固体用庚烷/乙酸乙酯重结晶得到浅黄色晶体状标题产品2.4g(产率84.2％),mp129.5-130℃。
                            实施例11
4-溴-2-(对氯苯基)-1-甲基-5-(三氟甲基)吡咯-3-腈的制备
Figure C9510617300151
将2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈(2.87g,0.01mol)在四氯化碳和溴(3.2g,0.015mol)中的混合物在回流温度下加热2小时，将其冷至室温，再用另外的溴(3.2g,0.015mol)处理，在回流温度下加热6-7小时(直至HPLC分析反应完全为止)，冷至室温，用偏亚硫酸氢钠水溶液处理并真空浓缩得到残余物。将残余物用庚烷重结晶得到白色晶体状标题产品，mp131-131.5℃。
                       实施例12
4-氯-1-(氯甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈的制备
Figure C9510617300152
向2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈(2.85g,0.01mol)的氯苯溶液中加入氯(0.8g,0.011mol)，将其在室温下搅拌1小时，在90℃下加热2小时，冷至室温，再用另外的氯(1.1g,0.015mol)处理，在110℃下加热24小时，冷至室温并进一步用另外的氯(1.4g,0.02mol)和催化量的过氧化苯甲酰处理并将其在110℃下加热直至HPLC分析反应完全为止。将混合物冷至室温，用偏亚硫酸氢钠水溶液洗涤，干燥(MgSO4)并真空浓缩得到残余物。将残余物用庚烷重结晶得到白色结晶固体状标题产品，mp107-108℃。
                         实施例13
4-溴-1-(溴甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈的制备
将搅拌的2-(对氯苯基)-1-甲基-5-(三氟甲基)-2-吡咯啉-3-腈(2.85g,0.01mol)的四氯化碳溶液在室温下用1.1摩尔当量的溴处理，在70℃下加热2小时，冷至室温并用另外的1.5摩尔当量的溴处理，在回流温度下加热6-12小时，冷至室温，进一步用1.5摩尔当量的溴处理，在70℃下，照射2-4天直至HPLC分析反应完全为止，将其冷至室温并用偏亚硫酸氢钠水溶液洗涤。将有机相真空浓缩得到残余物，将其用庚烷重结晶得到白色晶体状标题产品，mp131.0-131.5℃。
                      实施例14
4-氯-2-(对氯苯基)-1-(乙氧甲基)-5-(三氟甲基)吡咯-3-腈的制备
将4-氯-1-(溴甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈(2.6g,0.0074mol)的四氢呋喃溶液用乙醇钠的21％wt/wt的变性酒精(3.6ml,0.0096mol)溶液处理，在室温下搅拌1小时，用另外的2-3滴乙醇钠溶液处理，在回流温度下加热1小时，冷却并倾入水中。将所得沉淀过滤，干燥并用异丙醇重结晶得到白色固体状标题产品1.6g(产率60％),mp104.0-104.5℃。
                      实施例15
4-溴-1-(乙氧甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈的制备
Figure C9510617300163
将4-溴-1-(溴甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈(4.42g,0.01mol)在无水乙醇中的混合物用乙醇钠(0.715g,0.011mol)的21％wt/wt的乙醇溶液处理，热至80℃-15-20分钟，冷至室温并用水和乙醚稀释。将有机相干燥(MgSO4)并真空浓缩得到一固体残余物，将其用庚烷重结晶得到白色固体状标题产品3.45g(产率85％)，mp91-92℃。
                        实施例16
                    杀虫和杀螨的评价
所有试验采用工业品进行，这里所说的所有浓度都是活性组份的浓度，所有试验保持在27℃。
亚热带粘虫(Spodoptera eridania)，3龄幼虫
将生长到7-8cm的Sieva利马豆(Sieva lima bean)叶浸在试验用悬浮液中同时搅拌3秒钟并置于通风橱中干燥。然后将叶子放入底部铺有潮湿滤纸和10只3龄毛虫的100×10mm培养皿中，将培养皿保持5天后，观察死亡率、减少的进料或对正常蜕变的干扰。
亚热带粘虫，7天残余物
将上述试验处理过的植物于高辐射灯下在暖房中保持7天，这些灯模拟新泽西六月天的强烈阳光并每天保持14小时。7天后，对叶子取样检验并按上面描述的进行评价。
棉红蜘蛛(P-抵抗株)，2-斑螨瓢虫
选则初叶生长到7-8cm的Sieva利马豆植物，修剪成每盒一棵植物并用螨侵染，得到每片叶子约100只螨。将螨侵染的植物浸在试验用配剂中3秒钟并同时搅拌，然后放入通风橱中干燥。将植物保持2天后，用第一片叶子评价成虫杀死情况。第二片叶子在植物上继续保持5天，然后观察卵的杀死情况和/或新出现的若虫。
十一星瓜叶甲，3龄南方南瓜十二星叶甲
将1cc精细滑石放入一个30ml广口细颈玻璃瓶中，将1ml合适的丙酮悬浮液滴在滑石上以使每瓶中有1.25和0.25mg的活性成份。将瓶子置于缓和的空气流下直至丙酮蒸发。将干燥的滑石弄松散、加入1cc谷子种子作为昆虫的食物并向每瓶中加入25ml湿土。盖上瓶盖并将内容物在Vortex混合器上充分混合。之后，向每瓶中加入十只3龄叶甲并弄松瓶盖以使幼虫可以交换空气。此种处理持续6天后，计算死亡率。由于它们很快分解且不易被发现，因此消失的幼虫可算作死亡。本试验所用的浓度分别相当于约50和10kg/ha。
蚕豆蚜(Aphis fabae)，混合龄
试验前一天将花盆中含有约5cm高的单棵旱金莲属植物(Tropae-olum sp)用约100-200只蚜虫侵染。每个花盆用一个#154Devilbiss喷雾器在通风橱中喷洒试验配剂，4rpm转台2个周期，喷头离植物约15cm并直接喷洒，这种可完全覆盖植物和蚜虫。在白色搪瓷浅盘上摆满喷雾的花盆并保持2天后，估算其死亡率。
西部马铃薯微叶蝉(Empoasca abrupta)，成虫
将约5cm长的Sieva利马豆叶浸在试验配剂中3秒钟并同时搅拌，然后放入通风橱中干燥。将叶子放在底部铺有湿滤纸的100×10mm培养皿中，将约10只微叶蝉成虫放入每个培养皿中并保持3天后，计算死亡率。
美洲菸夜蛾(Heliothis virescens)，3龄
将棉花子叶浸在试验配剂中并在通风橱中使其干燥。干燥后，将每个分成四份和十份并分别放在装有5-7m长牙科用纱布条的30ml塑料药杯中。向每个杯中加入一个3龄毛虫并将纸板盖放在杯上。持续处理3天后，计算死亡率并估算减少的进料损失。
美洲菸夜蛾(Heliothis virescens)，卵
将约6-7cm长的嫩棉花叶浸在试验悬浮液中同时搅拌3秒钟，将卵收集在干酪包布上将其分成含约50-100个卵(6-30小时大)的10-20mm的正方形。将有卵的一块方干酪包布也浸在试验悬浮液中并放在处理过的叶子上，将联合体干燥并放入一个杯中(240ml,6cm高，顶部直径9.5cm，底部直径8cm)，杯中已放置了5cm长的湿牙科用纱布条。将一个透明的塑料盖放在杯上并处理3天后，计算死亡率。
德国小蠊，诱饵试验，德国小蠊雄性成虫
在一个30ml广口瓶中通过将1ml1000ppm试验化合物的丙酮溶液滴在1克玉米粉上来制备0.1％诱饵，通过向瓶中通入温和的气流使诱饵干燥，将诱饵放在1品脱Mason广口瓶中并加入10只小蠊雄性成虫，将一个筛网盖放在瓶上并将一小块吸附了10％蜂蜜的棉花放在筛网盖顶端，3天后计算死亡率。
德国小蠊，残余试验，德国小蠊雄性成虫
将1ml1000ppm试验物质的丙酮溶液慢慢滴在150×15mm培养皿的底上以致于使其尽可能均匀覆盖。待沉积物干燥后，在每个培养皿中加入10只小蠊雄性成虫并盖上盖，3天后计算死亡率。
等级标准：
           0=无效        5=56-65％杀死
       1=10-25％杀死     6=66-75％杀死
       2=26-35％杀死     7=76-85％杀死
       3=36-45％杀死     8=86-99％杀死
       4=46-55％杀死     9=100％杀死
                         R-减少的进料
上述评价所得数值见表Ⅰ
                       表Ⅰ
2-(对氯苯基)-4-氯-1-(乙氧甲基)-5-(三氟甲基)吡咯-3-腈杀虫及杀螨的评价
                             评价
                1000    100   10    1     0.1
   试验         ppm     ppm   ppm   ppm   ppm
亚热带粘虫
(3龄幼虫)       9       9     9     0     -
(7天残余物)     9       9     6     -     -
棉红蜘蛛        -       -     9     0     -
蚕豆蚜          -       9     4     0     -
微叶蝉          -       9     9     9     -
美洲菸夜蛾
   (卵)         7        0     -     -    -
 (3龄虫)        9        9     9     -    -
 德国小蠊
 (诱饵)         0        -     -     -    -
 (残余物)       9        0     -     -    -
            50kg/ha     10kg/ha     1kg/ha
十一星瓜叶甲    9         7           0

Claims (2)

1．一种保护生长植物免遭昆虫、螨及线虫侵害的方法，其特征在于向所说的植物的叶子或植物生长的土壤或水中投入4-氯-1-(乙氧甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈。
2．一种控制昆虫、螨及线虫的方法，其特征在于将所说的昆虫、螨及线虫的繁殖地、食物或栖息地接触4-氯-1-(乙氧甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈。
CN95106173A 1990-12-26 1995-06-02 4－氯－1－(乙氧甲基)－2－(对氯苯基)－5－(三氟甲基)吡咯－3－腈的应用 Expired - Fee Related CN1073799C (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/634,288 US5194630A (en) 1990-12-26 1990-12-26 Process for the manufacture of insecticidal 2-aryl-1-(alkoxymethyl)-4-halo-5-(trifluoromethyl)pyrroles
US07/634,287 US5118816A (en) 1990-12-26 1990-12-26 2-aryl-5-(trifluoromethyl)-2-pyrroline compounds useful in the manufacture of insecticidal, nematocidal and acaricidal arylpyrroles
US07/634,288 1990-12-26
US07/634,287 1990-12-26

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CN1073799C true CN1073799C (zh) 2001-10-31

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CN91112749A Expired - Fee Related CN1030765C (zh) 1990-12-26 1991-12-16 在制备芳基吡咯杀虫剂中有用的吡咯啉中间体的制备方法
CN95106138A Expired - Fee Related CN1046503C (zh) 1990-12-26 1995-06-02 芳基吡咯化合物的制备方法
CN95106174A Expired - Fee Related CN1035669C (zh) 1990-12-26 1995-06-02 在制备芳基吡咯杀虫剂中有用的中间体化合物的制备方法
CN95106173A Expired - Fee Related CN1073799C (zh) 1990-12-26 1995-06-02 4－氯－1－(乙氧甲基)－2－(对氯苯基)－5－(三氟甲基)吡咯－3－腈的应用

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CN95106138A Expired - Fee Related CN1046503C (zh) 1990-12-26 1995-06-02 芳基吡咯化合物的制备方法
CN95106174A Expired - Fee Related CN1035669C (zh) 1990-12-26 1995-06-02 在制备芳基吡咯杀虫剂中有用的中间体化合物的制备方法

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KR (1) KR100217319B1 (zh)
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BR (1) BR9105616A (zh)
CZ (1) CZ285566B6 (zh)
DE (2) DE69132346T2 (zh)
DK (1) DK0492171T3 (zh)
EG (1) EG19865A (zh)
ES (1) ES2148142T3 (zh)
FI (1) FI100879B (zh)
GR (1) GR3034739T3 (zh)
HU (1) HU214883B (zh)
IE (1) IE914540A1 (zh)
IL (4) IL116843A (zh)
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PT (1) PT99894B (zh)
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EP0492093B1 (en) * 1990-12-26 1999-03-17 American Cyanamid Company Process for the preparation of 2-aryl 1-substituted-5-(trifluoromethyl)pyrrole compounds useful as insecticidal, acaricidal and nematocidal agents and as intermediates for the manufacture of said agents
YU8592A (sh) * 1991-08-28 1994-06-10 Flumroc Ag. Postupak i uređaj za izradu ploča od mineralnih vlakana primenjenih kao nosač zidnog premaza
US5130328A (en) * 1991-09-06 1992-07-14 American Cyanamid Company N-alkanoylaminomethyl and N-aroylaminomethyl pyrrole insecticidal and acaricidal agents
DE4217725A1 (de) * 1992-05-29 1993-12-02 Bayer Ag Substituierte 2-Arylpyrrole
DE4217722A1 (de) * 1992-05-29 1993-12-02 Bayer Ag Substituierte 2-Arylpyrrole
FR2713640B1 (fr) * 1993-12-15 1996-01-05 Cird Galderma Nouveaux composés aromatiques polycycliques, compositions pharmaceutiques et cosmétiques les contenant et utilisations.
AU722204B2 (en) * 1995-10-31 2000-07-27 Sumitomo Chemical Company, Limited Pesticidal composition
JP4126621B2 (ja) * 1996-11-25 2008-07-30 日本農薬株式会社 殺虫・殺ダニ剤
GB0813042D0 (en) * 2008-07-16 2008-08-20 Syngenta Participations Ag Insecticidal compounds
CN102731363B (zh) * 2011-12-15 2013-09-25 青岛农业大学 一组吡咯杀虫剂化合物
AU2016259360B1 (en) * 2016-11-16 2017-09-07 Rotam Agrochem International Company Limited A novel crystalline form of chlorfenapyr, a process for its preparation and use of the same
CN108976157A (zh) * 2018-09-13 2018-12-11 天津市天地创智科技发展有限公司 溴虫腈晶型ii及其制备方法

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EP0358047A2 (en) * 1988-09-08 1990-03-14 American Cyanamid Company Method of controlling phytopathogenic fungi
US4929634A (en) * 1987-10-23 1990-05-29 American Cyanamid Company Method of and bait compositions for controlling mollusks

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DE3713757A1 (de) * 1987-04-24 1988-11-10 Hoechst Ag Benzolsulfonamidderivate und verfahren zu ihrer herstellung
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EP0358047A2 (en) * 1988-09-08 1990-03-14 American Cyanamid Company Method of controlling phytopathogenic fungi

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ES2148142T3 (es) 2000-10-16
CN1030765C (zh) 1996-01-24
JP4122163B2 (ja) 2008-07-23
CZ285566B6 (cs) 1999-09-15
CN1116487A (zh) 1996-02-14
AU642796B2 (en) 1993-10-28
JPH04342552A (ja) 1992-11-30
HU914113D0 (en) 1992-03-30
FI100879B (fi) 1998-03-13
EG19865A (en) 1996-03-31
SK281358B6 (sk) 2001-02-12
HUT60245A (en) 1992-08-28
IL100212A (en) 1997-04-15
EP0492171A1 (en) 1992-07-01
CN1035669C (zh) 1997-08-20
UA27712C2 (uk) 2000-10-16
IL116844A0 (en) 1996-07-23
JP2002322147A (ja) 2002-11-08
IL116843A0 (en) 1996-07-23
GR3034739T3 (en) 2001-01-31
DK0492171T3 (da) 2000-09-04
AU653899B2 (en) 1994-10-13
EP0492171B1 (en) 2000-08-02
PT99894A (pt) 1992-12-31
KR100217319B1 (ko) 1999-09-01
TW223626B (zh) 1994-05-11
DE69132346T2 (de) 2000-12-28
FI916118A0 (fi) 1991-12-23
CN1046503C (zh) 1999-11-17
ATE195116T1 (de) 2000-08-15
SG47623A1 (en) 1998-04-17
NZ241095A (en) 1994-07-26
CN1120534A (zh) 1996-04-17
EP0826667A1 (en) 1998-03-04
AU9005791A (en) 1992-07-02
CN1117963A (zh) 1996-03-06
AU4495793A (en) 1993-11-18
FI916118A (fi) 1992-06-27
ZW18591A1 (en) 1992-07-15
DE69133140T2 (de) 2003-03-20
IL100212A0 (en) 1992-09-06
ATE226937T1 (de) 2002-11-15
HU214883B (hu) 1998-10-28
RU2066313C1 (ru) 1996-09-10
DE69133140D1 (de) 2002-12-05
IL116843A (en) 1999-08-17
EP0826667B1 (en) 2002-10-30
DE69132346D1 (de) 2000-09-07
CS395691A3 (en) 1992-07-15
IE914540A1 (en) 1992-07-01
KR920012022A (ko) 1992-07-25
CN1063281A (zh) 1992-08-05
BR9105616A (pt) 1992-09-01
PT99894B (pt) 1999-06-30

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