CN1030765C - 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 - Google Patents
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 Download PDFInfo
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- C07D207/22—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
- C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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,其中所制备的吡咯啉具有下述结构:
其中M、R、L、W、A的定义同说明书。
Description
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,
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NR3R4,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。
(I)
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
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、R3CF2Z、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环烷基或苯基;
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)m或O且
n是整数0,1或2
该方法包括将式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或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-甲基吡咯中间体进一步与至少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,NO2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。
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,二噁烷,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;砚如四氢噻吩砜;芳香烃类如苯,甲苯,二甲苯等;卤代芳香烃如氰苯,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Strccker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
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
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VII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。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、甲氯化碳、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副反应。
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标示核磁共振,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
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
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晶38.7g(产率97%),mp117-118℃,通过NMR光谱鉴定。
实施例3
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
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Dower50×8-100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)肌氮酸的制备
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%分散度的氢化钾(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
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51/2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
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
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氯化苯甲酰并在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
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
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
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
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
将4-氯-1-(溴甲基)-2-(对氯苯基)-5-(三氟甲基)吡咯-5-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
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
Claims (1)
A是氢或C1-C4烷基;
W是CN,NO2或CO2R6;
L是氢或卤素且
M和R各自独立地为氢,C1-C3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,卤素,CF3,R1CF2Z,R2CO或NR3R4,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)m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
其中A,L,M和R如上定义,与约0.1摩尔当量的具有结构式
H2C=CHW
其中W如上定义的链烯和任意催化量的有机碱在酸酐和溶剂存在下进行反应。
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
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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 |
US634,287 | 1990-12-26 | ||
US634,288 | 1990-12-26 |
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CN95106174A Division 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 Division 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 |
CN95106138A Division CN1046503C (zh) | 1990-12-26 | 1995-06-02 | 芳基吡咯化合物的制备方法 |
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CN1063281A CN1063281A (zh) | 1992-08-05 |
CN1030765C true CN1030765C (zh) | 1996-01-24 |
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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 |
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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EP (2) | EP0826667B1 (zh) |
JP (2) | JPH04342552A (zh) |
KR (1) | KR100217319B1 (zh) |
CN (4) | CN1030765C (zh) |
AT (2) | ATE195116T1 (zh) |
AU (2) | AU642796B2 (zh) |
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) |
NZ (1) | NZ241095A (zh) |
PT (1) | PT99894B (zh) |
RU (1) | RU2066313C1 (zh) |
SG (1) | SG47623A1 (zh) |
SK (1) | SK281358B6 (zh) |
TW (1) | TW223626B (zh) |
UA (1) | UA27712C2 (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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FR2609985B1 (fr) * | 1987-01-26 | 1989-04-14 | Rhone Poulenc Chimie | Procede de n-o trifluoroacetylation des a, o diaminoacides monocarboxyliques aliphatiques satures |
US4891442A (en) * | 1987-03-09 | 1990-01-02 | Texaco Inc. | Process for synthesis of β-phenylalanine |
DE3713757A1 (de) * | 1987-04-24 | 1988-11-10 | Hoechst Ag | Benzolsulfonamidderivate und verfahren zu ihrer herstellung |
US5010098A (en) * | 1987-07-29 | 1991-04-23 | American Cyanamid Company | Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof |
US4929634A (en) * | 1987-10-23 | 1990-05-29 | American Cyanamid Company | Method of and bait compositions for controlling mollusks |
DE3820528A1 (de) * | 1988-06-16 | 1989-12-21 | Bayer Ag | Mittel zur insekten- und milbenabwehr |
EP0358047A3 (en) * | 1988-09-08 | 1991-05-29 | American Cyanamid Company | Method of controlling phytopathogenic fungi |
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