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CN1038412C - 制备2－芳基－5－三氟甲基 吡咯化合物的方法 - Google Patents

制备2－芳基－5－三氟甲基 吡咯化合物的方法 Download PDF

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CN1038412C
CN1038412C CN93114836A CN93114836A CN1038412C CN 1038412 C CN1038412 C CN 1038412C CN 93114836 A CN93114836 A CN 93114836A CN 93114836 A CN93114836 A CN 93114836A CN 1038412 C CN1038412 C CN 1038412C
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CN1092764A (zh
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V·卡姆斯沃伦
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Wyeth Holdings LLC
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American Cyanamid Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—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
    • 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
    • C07D207/36—Oxygen or sulfur atoms
    • C07D207/40—2,5-Pyrrolidine-diones
    • C07D207/416—2,5-Pyrrolidine-diones 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 other ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—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
    • 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
    • C07D207/36—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—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
    • 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
    • C07D207/42—Nitro radicals

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Abstract

本发明提供制备2-芳基-5-三氟甲基吡咯化合物的方法，这些化合物作为杀虫剂、杀螨剂和杀线虫剂及作为制备所述药剂的中间体是有用的。

Description

制备2-芳基-5-三氟甲基 吡咯化合物的方法
2-芳基-5-三氟甲基吡咯化合物有效地并高效地控制广泛的农学上有害的昆虫、螨虫和线虫。
本发明的一个目的是提供制备适用于昆虫、螨虫和线虫控制的芳基吡咯化合物的方便、直接的方法。本发明的另一个目的是提供在制备下述的2-芳基-5-三氟甲基吡咯化合物中重要中间体的容易利用的来源。
本发明涉及式I的2-芳基-5-三氟甲基吡咯化合物的制备方法其中A为氢或可任意被苯基取代的C1-C6烷基；W为CN、NO2、CO2R1或SO2R1；X为氢或CO2R2；L为氢、F、Cl、Br或I；M和R各自独立地为氢、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、CN、F、Cl、Br、I、NO2、CF3、R3CF2Z、R4CO或NR5R6，当M和R在邻近位置时，可与它们所连着的碳原子一起形成环，其中MR代表-OCHO-、-OCF2O-或-CH＝CH-CH＝CH-；R1为C1-C6烷基、C3-C6环烷基或苯基；R2为C1-C4烷基；R3为氢、F、CHF2、CHFCl或CF3；R4为C1-C4烷基、C1-C4烷氧基或NR5R6；R5为氢或C1-C4烷基；R6为氢、C1-C4烷基或R7CO；R7为氢或C1-C4烷基；Z为S(O)n或0；n为整数0、1或2；该方法包括在酸存在下，可选择地在溶剂存在下，将式II的卤代烯胺
Figure C9311483600051
式中Y为Cl、Br或I，A、W、L、M和R如上所述，与约1摩尔当量三氟丙酮或三氟乙酰乙酸C1-C4烷酯进行反应。
式I的2-芳基-5-三氟甲基吡咯化合物作为杀虫、杀螨和杀线虫剂及作为制造所述药剂的重要中间体是有用的。式I化合物的实用性在美国专利No.5,010,098中有描述。
虽然有已知的方法合成芳基吡咯化合物，但经济的、具有环境合理性的商业规模制备方法仍在寻找之中。本发明提供以简单的一步反应获得有用的芳基吡咯化合物的方法。
现已发现，在酸存在下，可选择地在溶剂存在下，较好地在升温下，将合适的式II所示卤代烯胺与约1摩尔当量三氟丙酮或三氟乙酰乙酸C1-C4烷酯进行反应，可制得式I的2-芳基-5-三氟甲基吡咯化合物。上述反应表示为如下流程I。
                     流程I
Figure C9311483600061
适用于本发明方法的酸为现有技术中一般已知的有机酸，特别是羧酸如乙酸、丙酸等，较佳的为乙酸。适当的溶剂或溶剂混合物可任选地与有机酸一起使用。这样的溶剂可选自有机溶剂，如烃类、芳烃类、卤代烃类、卤代芳烃类及其混合物，这些溶剂的沸点范围为约60℃至250℃。
在升温下如约60℃至约250℃范围内的温度下，本发明的方法是最有效的。较低的反应温度可明显地增加反应时间，过高的温度可导致不适宜的副产物形成和分解。较佳的温度为约70℃至约180℃。
如流程II所示，将合适的式III的烯胺与卤化剂如卤素、N-卤代琥珀酰亚胺、次卤酸盐或类似物反应可制得式II的化合物。                           流程II
Figure C9311483600071
式III的化合物及其制备在美国专利5,128,485中有描述。
式I的2-芳基-5-三氟甲基吡咯化合物是制备重要的芳基吡咯杀虫剂中有用的中间体的来源。例如，在X为COOR1的式I化合物的情况下，通过流程III所示溴化脱羧反应可直接得到式IV的杀虫产物。
                     流程III
同样，通过流程IV所示直接卤化反应，可容易地将X为氢的式I化合物转化为所需的式IV产物或其4-卤代类似物。
                     流程IV
Figure C9311483600073
在醇R8OH的存在下，A为氢的式IV化合物经与氢化钠和二卤甲烷反应可转为式V所示1-(烷氧甲基)吡咯化合物。反应见流程V。
                     流程V
Figure C9311483600081
在上面的流程中，Y’和Y″各自独立地为氯、溴或碘，R8为C1-C6烷基，W、L、M和R如前文关于式I芳基吡咯化合物所描述的。
式V化合物也可用美国专利5,151,536所述方法加以制备。或者，可按如下方法得到式V化合物：在对质子惰性的溶剂如四氢呋喃中，将合适的式IVa吡咯中间体与至少2摩尔当量NaH反应，形成相应的吡咯阴离子，可选择地在升温下用至少1摩尔当量二卤甲烷试剂处理此阴离子，形成反应混合物，并滴加醇R8OH处理此反应混合物以便在反应混合物中保持低的醇总浓度。
式V化合物，特别是其中W为CN，R8为乙基，更特别是其中W为CN，R8为乙基，L和R为氢，及M为氯，是高效杀虫剂、杀螨剂和杀线虫剂。
正如容易看到的那样，通过改变取代基A、L、M、R和W，可从式I的中间体化合物制备各种各样的杀虫芳基吡咯类。
为了利于进一步理解本发明，给出以下实施例以作更具体的阐述。本发明并不被其限制，除非如权利要求书中所限定的。术语IR和NMR分别指红外和核磁共振。术语HPLC指高效液相色谱。
                 实施例1
2-对氯苯基-1-甲基-5-(三氟甲基)吡咯-3-腈的制备
将a-溴-对氯-b-(甲氨基)肉桂腈((E)或(Z)-(5.43g，0.02mol))和三氟丙酮(3.36g，2.7mL，0.03mol)在乙酸中的溶液于80℃加热1-2小时，100℃加热过夜，用水稀释，用乙酸乙酯萃取。合并有机萃取液，水洗，用无水Na2SO4干燥，真空浓缩，得一胶状物。此胶状物经用硅胶和15％乙酸乙酯的庚烷溶液作闪蒸色谱分离，得黄色固体标题产物(1.7g，mp 129°-131℃)，用1H和19FNMR谱分析鉴定。
                 实施例2
2-对氯苯基-5-(三氟甲基)吡咯-3-腈的制备
在100℃下，经4 1/2小时将三氟丙酮(3.36g，2.7mL，0.03mol)的乙酸溶液滴加到β-氨基-α-溴-对氯肉桂腈((E)-或(Z)-(5.15g，0.02mol))的乙酸溶液中。将反应混合液在100℃下加热过夜，用水稀释，用乙酸乙酯萃取。合并有机萃取液，水洗，用无水Na2SO4干燥，真空浓缩，得一胶状物。此胶状物经用硅胶和15％乙酸乙酯的庚烷溶液作闪蒸色谱分离，得黄色固体标题产物(1.8g，mp 129°-131℃)，用1H和19F NMR谱分析鉴定。
                 实施例3
(E)-或(Z)α-溴-对氯-β(甲氨基)肉桂腈的制备
Figure C9311483600102
在55°-60℃下，经30分钟将溴的四氯化碳溶液(10.9mL，33.6g，0.21mol)加到对氯-β-(甲氨基)肉桂腈((E)-或(Z)-(38.53g，0.2mol))在四氯化碳和四氢呋喃的混合溶液中。将反应混合物冷却至室温，真空浓缩至原体积的一半，过滤得到一固体。用四氯化碳稀释此固体，所得混合物加热回流，冷却并过滤，得黄色固体标题产物(43.6g，mp178°-178.5℃)，用1H和13C NMR谱分析。
用基本相同的方法，但用β-氨基-对氯肉桂腈取代对氯-β-(甲氨基)肉桂腈((E)-或(Z)-)，得白色固体(E)-或(Z)-β-氨基-α-溴-对氨肉桂腈，mp190°-191.5℃。
                 实施例4
2-溴-对氯-β-(甲氨基)肉桂腈E或Z异构体的制备
Figure C9311483600111
将70℃的对氯-β-(甲氨基)肉桂腈(19.3g，0.1mol)四氯化碳溶液经30-40分钟滴加溴(16.8g，0.105mol)的四氯化碳溶液进行处理(在加溴过程中如果需要则加四氢呋喃以帮助反应混合物溶解)。在70℃下，将反应混合物搅拌30分钟，冷至室温，浓缩，得到黄色晶形沉淀。将混合物过滤，滤饼用四氯化碳洗涤，干燥，得黄色固体标题产物，18.8g(产率69％)，mp178.0-178.5℃，用IR、NMR和质谱分析鉴定。
                 实施例5
2-(对氯苯基)1-甲基-5-(三氟甲基)吡咯-3-腈(I)
    和4乙酯基-2-(对氯苯基)-1-甲基-5-(三氟甲基)      吡咯-3-腈(II)的制造
Figure C9311483600121
在116°-118℃下，将2-溴-对氯-β-(甲氨基)肉桂腈(10.0g，0.0368mol)和三氟乙酰乙酸乙酯(10.17g，0.0552mol)的乙酸混合液搅拌加热7小时，冷至室温，用水稀释，及用乙酸乙酯萃取。合并萃取液，水洗，用Na2SO4干燥，真空浓缩，得胶状残留物。残留物用硅胶作闪蒸色谱分离，15∶1，乙酸乙酯∶庚烷作洗脱液，得到白色固体标题产物(I)，2.7g，mp 127-129℃，经1H NMR和19FNMR谱分析进行鉴定，还得到另一橙色结晶标题产物(II)，1.65g，mp129°-131℃，经1H NMR和19F NMR谱分析鉴定。
                 实施例6
4-溴-2-(对氯苯基)-5-(三氟甲基)
       吡咯-3-腈的制备将2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈(1当量)四氯化碳溶液用溴(1.8当量)处理，在室温下搅拌直至反应完成，真空浓缩，得定量得率的标题产物，用IR、NMR和质谱分析鉴定。
                 实施例7
4-溴-2-(对氯苯基)-1-(乙氧甲基)-5-
    (三氟甲基)吡咯-3-腈的制备
在≤60℃下，将处于氮气氛下的氢化钠(26.5g，1.105mol)四氢呋喃混合物边搅拌边用4-溴-2-(对氯苯基)-5-(三氟甲基)吡咯-3-腈(1.00g，0.273mol)的四氢呋喃溶液缓慢处理。当添加完成后，用溴氯甲烷(93.0g，0.718mol)处理，加热至63°-65℃，经5.5小时滴加无水乙醇(39.5g，0.859mol)进行处理，63°-65℃下搅拌3小时，真空浓缩。将浓缩物分散在水和二氯甲烷的混合液中。分离出水相，用二氯甲烷洗涤。合并有相机并浓缩。将浓缩物分散在己烷中，冷却至5°-10℃并过滤。滤饼洗涤成白色固体，111.6g(91.3％得率)，用HPLC分析，纯度为91.2％。

Claims (5)

1.式I所示2-芳基-5-三氟甲基吡咯化合物的制备方法
其中
A为氢或可任意被苯基取代的C1-C6烷基；
W为CN、NO2、CO2R1或SO2R1；
X为氢或CO2R2；
L为氢、F、Cl、Br或I；
M和R各自独立地为氢、C1-C4烷基、C1-C4烷氧基、C1-C4烷硫基、C1-C4烷基亚硫酰基、C1-C4烷基磺酰基、CN、F、Cl、Br、I、NO2、CF3、R3CF2Z、R4CO或NR5R6，当M和R在邻近位置时，可与它们所连着的碳原子一起形成环，其中MR代表-OCHO-、-OCF2O-或-CH＝CH-CH＝CH-；
R1为C1-C6烷基、C3-C6环烷基或苯基；
R2为C1-C4烷基；
R3为氢、F、CHF2、CHFCl或CF3；
R4为C1-C4烷基、C1-C4烷氧基或NR5R6；
R5为氢或C1-C4烷基；
R6为氢、C1-C4烷基或R7CO；
R7为氢或C1-C4烷基；
Z为S(O)n或0；
n为整数0、1或2；
其特征在于：在有机酸存在下，可选择地在溶剂存在下，将式II的卤代烯胺
式中Y为Cl、Br或I，A、W、L、M和R如上所述，与1摩尔当量三氟丙酮或三氟乙酰乙酸C1-C4烷酯进行反应。
2.按权利要求1所述的方法，其特征还在于，有机酸为乙酸。
3.按权利要求1所述的方法，其特征还在于，式II的卤代烯胺与1摩尔当量三氟丙酮反应。
4.按权利要求1所述的方法，其特征还在于，反应在60℃至250℃的升温下进行。
5.按权利要求4所述的方法，其特征还在于，反应在70℃至180℃的升温下进行。
CN93114836A 1992-11-25 1993-11-24 制备2－芳基－5－三氟甲基 吡咯化合物的方法 Expired - Fee Related CN1038412C (zh)

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
US07/981,626 US5225568A (en) 1992-11-25 1992-11-25 Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-3-substituted-5-(trifluoromethyl)pyrrole compounds
US07/981,626 1992-11-25
US07/989,271 1992-12-11
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US5010098A (en) * 1987-07-29 1991-04-23 American Cyanamid Company Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof
US5128485A (en) * 1990-12-17 1992-07-07 American Cyanamid Company Synthesis of 2-aryl-5-(trifluoromethyl)pyrroles useful as pesticidal agents and as intermediates for the preparation of said agents
US5151536A (en) * 1990-12-17 1992-09-29 American Cyanamid Company Process for the manufacture of pesticidal 1-(alkoxymethyl) pyrrole compounds

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US5180734A (en) * 1990-11-30 1993-01-19 American Cyanamid Company Insecticidal and acaricidal diarylpyrrolecarbonitrile and diarylnitropyrrole compounds
US5225568A (en) * 1992-11-25 1993-07-06 American Cyanamid Company Process for the preparation of insecticidal, acaricidal and nematicidal 2-aryl-3-substituted-5-(trifluoromethyl)pyrrole compounds

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Publication number Priority date Publication date Assignee Title
US5010098A (en) * 1987-07-29 1991-04-23 American Cyanamid Company Arylpyrrole insecticidal acaricidal and nematicidal agents and methods for the preparation thereof
US5128485A (en) * 1990-12-17 1992-07-07 American Cyanamid Company Synthesis of 2-aryl-5-(trifluoromethyl)pyrroles useful as pesticidal agents and as intermediates for the preparation of said agents
US5151536A (en) * 1990-12-17 1992-09-29 American Cyanamid Company Process for the manufacture of pesticidal 1-(alkoxymethyl) pyrrole compounds

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DK0599036T3 (da) 1997-01-06
BR9304801A (pt) 1994-05-31
CA2109741A1 (en) 1994-05-26
HU213037B (en) 1997-01-28
KR940011446A (ko) 1994-06-21
IL107711A0 (en) 1994-02-27
AU5190293A (en) 1994-06-09
SK279499B6 (sk) 1998-12-02
EP0599036A1 (en) 1994-06-01
ATE146457T1 (de) 1997-01-15
JP3240232B2 (ja) 2001-12-17
SK129093A3 (en) 1994-11-09
DE69306744D1 (de) 1997-01-30
IL107711A (en) 1997-08-14
CZ284072B6 (cs) 1998-08-12
DE69306744T2 (de) 1997-04-10
HU9303332D0 (en) 1994-03-28
CZ242793A3 (en) 1994-06-15
ES2095544T3 (es) 1997-02-16
EP0599036B1 (en) 1996-12-18
JPH06228090A (ja) 1994-08-16
GR3022196T3 (en) 1997-03-31

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