WO2011120312A1 - 3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives as insecticides - Google Patents

3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives as insecticides Download PDF

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WO2011120312A1
WO2011120312A1 PCT/CN2010/079844 CN2010079844W WO2011120312A1 WO 2011120312 A1 WO2011120312 A1 WO 2011120312A1 CN 2010079844 W CN2010079844 W CN 2010079844W WO 2011120312 A1 WO2011120312 A1 WO 2011120312A1
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cyano
dichloro
trifluoromethylphenyl
carbon
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PCT/CN2010/079844
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French (fr)
Chinese (zh)
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汪清民
赵奇奇
李永强
熊丽霞
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南开大学
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three 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
    • C07D231/44—Oxygen and nitrogen or sulfur and nitrogen atoms
    • 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
    • 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
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • 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
    • C07D405/12—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 linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl) Pyrazole derivatives and their use as insecticides.
  • the insecticide based on 1-arylpyrazole is mainly ⁇ - represented by fipronil.
  • Aminobutyric acid receptor inhibitors currently available in six commercial or developing varieties, are Fipronil (common name fipronil, trade name Regent, Regent), Ethiprole (common name ethiprole, trade name Curbix, Cool Bi), Acetoprole (acetonitrile), Vaniliprole, Pyrafluprole and Pyriprole, their structure is as follows:
  • Fipronil was discovered by May and Baker in the UK in 1988 and later by Rhone-Poulenc, France. Company development. Fipronil has a wide spectrum of insecticides, it has contact, stomach poisoning and moderate systemic action. It can not only control underground pests, but also prevent and control insects on the ground. It can be used for stem and leaf treatment, soil treatment, and seed treatment. Control a variety of sucking and chewing mouthparts pests. Ethyl nitrile Discovered by Rhone-Poulenc in 1997, 2008 It was officially launched as a highly effective insecticide for controlling rice planthoppers. The insecticidal spectrum of ethionitrile is different from that of fipronil. The activity of lepidoptera is not as good as that of fipronil, but the systemic activity of sorghum and peach aphid is much higher than that of fipronil.
  • CN 1204123C discloses a class of N-phenylpyrazole derivatives having the following structure:
  • CN 1915977A discloses chloroflufenonitrile of the following structure:
  • the present invention is a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the general formula ( I ), as shown in Fig. 1.
  • R 1 represents a 1 - 6 carboalkyl group or an alkyl group substituted by one or more of the same or different halogen atoms
  • R 2 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1
  • R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1
  • X represents O , S or NH ;
  • n 0 or 1.
  • R 1 is a methyl group, a trifluoromethyl group. Or ethyl; R 2 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl or cycloalkyl group; R 3 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or furan Base; X stands for O; n stands for 0 or 1.
  • the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) can be produced by reacting a compound a with an aldehyde to give an imine ( b ), compound b is added with an alcohol or a thiol or an amine to obtain a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative having n of 0 ( I ), further oxidation can produce a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) with n of 1, as shown in Fig. 2.
  • the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative Its application as an insecticide for the control of Lepidoptera, Coleoptera, Heteroptera, Diptera, Orthoptera and Homoptera.
  • R 1 is Me
  • R 2 is Me
  • R 3 is CCl 3
  • X is O
  • n is 1 .
  • R 1 is Me
  • R 2 is n -Pr
  • R 3 is CCl 3
  • X is O
  • n is 1 .
  • R 1 is Et
  • R 2 is n -Pr
  • R 3 is CCl 3
  • X is O
  • n is 1 for controlling aphids.
  • Compound a is commercially available or can be prepared by known methods.
  • the invention may also be illustrated by the compounds listed in Table 1, but is not intended to limit the invention.
  • the compound of the formula ( I ) of the invention has excellent insecticidal activity and can be used for controlling lepidopteran, coleopteran, genus Heteroptera, Diptera, Orthoptera and Homoptera pests.
  • insecticidal activity of some compounds of the formula ( I ) of the present invention against aphids, Culex pipiens pallens, and diamondback moth exceeds the commercial variety Ethiprole.
  • the compound of the formula ( I ) of the present invention may be used as it is, or may be added to an agriculturally acceptable carrier, or may be used in combination with other insecticides and/or acaricides.
  • Figure 1 is a chemical formula ( I ) of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the present invention
  • Figure 2 is a synthetic route diagram of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention.
  • 15mL contains 1mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methoxy
  • ethylaminopyrazole ( I1 ) in dichloromethane, 1 mL of trifluoroacetic acid and 0.23 mL of 30% hydrogen peroxide were added and reacted for 3 h, and the reaction was monitored by TLC.
  • 15 mL of water was added, and the organic phase was washed with 15 mL of water and 15 mL of brine and dried over anhydrous sodium sulfate. Filtration, desolvation, and crude column chromatography gave white solid I11 .
  • test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed.
  • the shoots with about 60 aphids were immersed in the liquid for 5 s, the excess liquid on the leaves was removed, and the test worms were transferred to normal conditions for growth, and the results were observed after 24 hours. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Tables 2 and 3 show the test results for some compounds.
  • Example 7 Activity against Plutella xylostella larvae
  • test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. Cut the fresh cabbage leaves into pieces (6cm ⁇ 2cm), soak in the liquid to be tested for 3s, use the filter paper to remove the excess liquid, dry it in the air, put it into the glass tube, and put 7 healthy ones in each tube. The 3rd instar larvae of Plutella xylostella were added with fresh leaves at any time after 24 h, and the results were observed after 3 days. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Table 5 shows the test results of some compounds.
  • R 1 represents a 1 - 6 carboalkyl group or an alkyl group substituted by one or more of the same or different halogen atoms
  • R 2 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1
  • R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1
  • X represents O , S or NH ;
  • n 0 or 1.
  • R 1 is a methyl group, a trifluoromethyl group. Or ethyl; R 2 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl or cycloalkyl group; R 3 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or furan Base; X stands for O; n stands for 0 or 1.
  • the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) can be produced by reacting a compound a with an aldehyde to give an imine ( b ), compound b is added with an alcohol or a thiol or an amine to obtain a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative having n of 0 ( I ), further oxidation can produce a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) with n of 1, as shown in Fig. 2.
  • the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative Its application as an insecticide for the control of Lepidoptera, Coleoptera, Heteroptera, Diptera, Orthoptera and Homoptera.
  • R 1 is Me
  • R 2 is Me
  • R 3 is CCl 3
  • X is O
  • n is 1 .
  • R 1 is Me
  • R 2 is n -Pr
  • R 3 is CCl 3
  • X is O
  • n is 1 .
  • R 1 is Et
  • R 2 is n -Pr
  • R 3 is CCl 3
  • X is O
  • n is 1 for controlling aphids.
  • Compound a is commercially available or can be prepared by known methods.
  • the invention may also be illustrated by the compounds listed in Table 1, but is not intended to limit the invention.
  • the compound of the formula ( I ) of the invention has excellent insecticidal activity and can be used for controlling lepidopteran, coleopteran, genus Heteroptera, Diptera, Orthoptera and Homoptera pests.
  • insecticidal activity of some compounds of the formula ( I ) of the present invention against aphids, Culex pipiens pallens, and diamondback moth exceeds the commercial variety Ethiprole.
  • the compound of the formula ( I ) of the present invention may be used as it is, or may be added to an agriculturally acceptable carrier, or may be used in combination with other insecticides and/or acaricides.
  • Figure 1 is a chemical formula ( I ) of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the present invention
  • Figure 2 is a synthetic route diagram of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention.
  • 15mL contains 1mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methoxy
  • ethylaminopyrazole ( I1 ) in dichloromethane, 1 mL of trifluoroacetic acid and 0.23 mL of 30% hydrogen peroxide were added and reacted for 3 h, and the reaction was monitored by TLC.
  • 15 mL of water was added, and the organic phase was washed with 15 mL of water and 15 mL of brine and dried over anhydrous sodium sulfate. Filtration, desolvation, and crude column chromatography gave white solid I11 .
  • test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed.
  • the shoots with about 60 aphids were immersed in the liquid for 5 s, the excess liquid on the leaves was removed, and the test worms were transferred to normal conditions for growth, and the results were observed after 24 hours. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Tables 2 and 3 show the test results for some compounds.
  • Example 7 Activity against Plutella xylostella larvae
  • test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. Cut the fresh cabbage leaves into pieces (6cm ⁇ 2cm), soak in the liquid to be tested for 3s, use the filter paper to remove the excess liquid, dry it in the air, put it into the glass tube, and put 7 healthy ones in each tube. The 3rd instar larvae of Plutella xylostella were added with fresh leaves at any time after 24 h, and the results were observed after 3 days. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Table 5 shows the test results of some compounds.

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Abstract

Disclosed are 3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives of general formula (I), their preparation method and their uses as insecticides. Each group in general formula (I) is as that defined in the description. The compounds of the present invention can be used to control lepidopterous, coleopterous, heteropterous, dipterous, orthopterous, and homopterous pests. The insecticidal activities of some compounds against aphis, culex pipiens, and diamondback moth are better than ethiprole.

Description

3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物杀虫剂 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative insecticide
技术领域Technical field
本发明涉及 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物及其作为杀虫剂应用。 The present invention relates to 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl) Pyrazole derivatives and their use as insecticides.
背景技术 Background technique
以 1- 芳基吡唑为骨架的杀虫剂主要是以氟虫腈为代表的 γ- 氨基丁酸受体抑制剂，现有六个已经商品化或正在开发中的品种，它们分别是 Fipronil （通用名氟虫腈，商品名 Regent ，锐劲特）， Ethiprole （通用名乙虫腈，商品名 Curbix ，酷毕）， Acetoprole （乙酰虫腈）， Vaniliprole ， Pyrafluprole 和 Pyriprole ，它们的结构如下： The insecticide based on 1-arylpyrazole is mainly γ- represented by fipronil. Aminobutyric acid receptor inhibitors, currently available in six commercial or developing varieties, are Fipronil (common name fipronil, trade name Regent, Regent), Ethiprole (common name ethiprole, trade name Curbix, Cool Bi), Acetoprole (acetonitrile), Vaniliprole, Pyrafluprole and Pyriprole, their structure is as follows:
Figure PCTCN2010079844-appb-C000001
Figure PCTCN2010079844-appb-C000001
Figure PCTCN2010079844-appb-C000002
Figure PCTCN2010079844-appb-C000002
氟虫腈于 1988 年由英国 May and Baker 公司发现，后来由法国 Rhone-Poulenc 公司开发。氟虫腈杀虫谱广，具有触杀、胃毒和中度内吸作用，既能防治地下害虫，又能防治地上害虫，既可用于茎叶处理和土壤处理，又可用于种子处理，可有效防治多种刺吸式和咀嚼式口器害虫。乙虫腈于 1997 年由 Rhone-Poulenc 发现， 2008 年作为防治稻飞虱的高效杀虫剂正式上市。乙虫腈的杀虫谱与氟虫腈有所不同，对鳞翅目的活性不如氟虫腈，但对高粱蚜和桃蚜的内吸活性远高于氟虫腈。 Fipronil was discovered by May and Baker in the UK in 1988 and later by Rhone-Poulenc, France. Company development. Fipronil has a wide spectrum of insecticides, it has contact, stomach poisoning and moderate systemic action. It can not only control underground pests, but also prevent and control insects on the ground. It can be used for stem and leaf treatment, soil treatment, and seed treatment. Control a variety of sucking and chewing mouthparts pests. Ethyl nitrile Discovered by Rhone-Poulenc in 1997, 2008 It was officially launched as a highly effective insecticide for controlling rice planthoppers. The insecticidal spectrum of ethionitrile is different from that of fipronil. The activity of lepidoptera is not as good as that of fipronil, but the systemic activity of sorghum and peach aphid is much higher than that of fipronil.
CN 1204123C 公开了如下结构的一类 N- 苯基吡唑衍生物： CN 1204123C discloses a class of N-phenylpyrazole derivatives having the following structure:
Figure PCTCN2010079844-appb-C000003
Figure PCTCN2010079844-appb-C000003
CN 1915977A 公开了如下结构的氯氟虫腈：  CN 1915977A discloses chloroflufenonitrile of the following structure:
Figure PCTCN2010079844-appb-C000004
Figure PCTCN2010079844-appb-C000004
发明内容 Summary of the invention
本发明的目的是提供一类 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 及应用，该类化合物具有优异的杀虫活性。 本发明是化学通式为（ I ）的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物，如图 1， SUMMARY OF THE INVENTION It is an object of the present invention to provide a class of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives and their use which have excellent insecticidal activity. The present invention is a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the general formula ( I ), as shown in Fig. 1.
式中， R1 代表 1 － 6 碳烷基或被一个或一个以上相同或不同的卤素原子取代的烷基；Wherein R 1 represents a 1 - 6 carboalkyl group or an alkyl group substituted by one or more of the same or different halogen atoms;
R2 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 2 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
X 代表 O 、 S 或 NH ； X represents O , S or NH ;
n 代表 0 或 1 。 n stands for 0 or 1.
本发明所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）中，优选： R1 为甲基 、三氟甲基或乙基 ； R2 代表取代或未取代的烷基、烯基、炔基或环烷基； R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基或呋喃基； X 代表 O ； n 代表 0 或 1 。In the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention, preferably: R 1 is a methyl group, a trifluoromethyl group. Or ethyl; R 2 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl or cycloalkyl group; R 3 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or furan Base; X stands for O; n stands for 0 or 1.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）可以按如下方法制备：将化合物 a 和醛反应得到亚胺 (b) ，化合物 b 与 醇或硫醇或胺加成可制得 n 为 0 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ），再进一步氧化可制得 n 为 1 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ），如图 2 。The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) can be produced by reacting a compound a with an aldehyde to give an imine ( b ), compound b is added with an alcohol or a thiol or an amine to obtain a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative having n of 0 ( I ), further oxidation can produce a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) with n of 1, as shown in Fig. 2.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，它作为杀虫剂，用于防治鳞翅目类、鞘翅目类、异翅目类、双翅目类、直翅目类以及同翅目类害虫。 The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative Its application as an insecticide for the control of Lepidoptera, Coleoptera, Heteroptera, Diptera, Orthoptera and Homoptera.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，优选的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物为 The use of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative, preferably 3- Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives are
I11 ： R1 为 Me ， R2 为 Me ， R3 为 CCl3 ， X 为 O ， n 为 1 ， I11: R 1 is Me, R 2 is Me, R 3 is CCl 3 , X is O, and n is 1 .
或 I13 ： R1 为 Me ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， Or I13: R 1 is Me, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 .
或 I20 ： R1 为 Et ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， 用于防治 蚜虫。 Or I20: R 1 is Et, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 for controlling aphids.
化合物 a 是市售的或是用已知方法制备的。Compound a is commercially available or can be prepared by known methods.
本发明还可用表 1 中列出的化合物来说明，但并不限定本发明。 The invention may also be illustrated by the compounds listed in Table 1, but is not intended to limit the invention.
本发明通式（ I ）的化合物具有优异的杀虫活性，能用于防治鳞翅目类、鞘翅目类、异翅目类、双翅目类、直翅目类以及同翅目类害虫。The compound of the formula ( I ) of the invention has excellent insecticidal activity and can be used for controlling lepidopteran, coleopteran, genus Heteroptera, Diptera, Orthoptera and Homoptera pests.
本发明通式（ I ）的部分化合物对蚜虫、尖音库蚊、小菜蛾的杀虫活性超过了商品化品种乙虫腈（ Ethiprole ）。The insecticidal activity of some compounds of the formula ( I ) of the present invention against aphids, Culex pipiens pallens, and diamondback moth exceeds the commercial variety Ethiprole.
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，也可以和其它杀虫剂和（或）杀螨剂复配使用。The compound of the formula ( I ) of the present invention may be used as it is, or may be added to an agriculturally acceptable carrier, or may be used in combination with other insecticides and/or acaricides.
附图说明 DRAWINGS
图 1 是本发明的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物的 化学通式（ I ）；Figure 1 is a chemical formula ( I ) of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the present invention;
图 2 是本发明的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）的合成路线图。Figure 2 is a synthetic route diagram of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention.
具体实施方式 detailed description
以下结合实施例来进一步说明本发明： The invention will be further illustrated below in conjunction with the examples:
实施例 1 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b1 ） 的合成Example 1: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(trichloromethylmethyleneamino)pyrazole (b1 ) synthesis
将 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5- 氨基吡唑（ a1 ）（ 11mmol ）， 35g 三氯乙醛及 1g 4Å 分子筛混合，加热回流 36 h ，蒸去三氯乙醛，残余物柱层析，得亚胺 b1 。 收率 44% ，熔点 113-115 °C ， 1 H NMR (CDCl3), δ 8.82 (s, 1H, CH = N), 7.74 (s, 2H, Ph), 2.58 (s, 3H, CH3). Anal. Calcd for C14H6Cl5F3N4S (%): C, 33.86; H, 1.22; N, 11.28; Found: C, 33.99; H, 1.21; N, 11.12 。1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-aminopyrazole ( a1 ) (11 mmol), 35 g of trichloroacetaldehyde and 1 g of 4Å molecular sieves were mixed, heated to reflux for 36 h, trichloroacetaldehyde was distilled off, and the residue was subjected to column chromatography to obtain imine b1 . Yield 44%, melting point 113-115 ° C, 1 H NMR (CDCl 3 ), δ 8.82 (s, 1H, CH = N), 7.74 (s, 2H, Ph), 2.58 (s, 3H, CH 3 ) Anal. Calcd for C 14 H 6 Cl 5 F 3 N 4 S (%): C, 33.86; H, 1.22; N, 11.28; Found: C, 33.99; H, 1.21; N, 11.12.
实施例 2 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 乙硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b2 ） 的合成Example 2: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylthio-5-(trichloromethylmethyleneamino)pyrazole (b2 ) synthesis
将 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 乙硫基 -5- 氨基吡唑（ a2 ）（ 11mmol ）， 35g 三氯乙醛及 1g 4Å 分子筛混合，加热回流 36 h ，蒸去三氯乙醛，残余物柱层析，得亚胺 b2 。收率 53% ，熔点 112-114 °C, 1H NMR (CDCl3), δ 9.00 (s, 1H, CH = N), 7.75 (s, 2H, Ph), 2.95 (q, 3 J HH = 7.2 Hz, 2H, CH2), 1.28 (t,3 J HH = 7.2 Hz, 3H, CH3). Anal. Calcd for C15H8Cl5F3N4S (%): C, 35.29; H, 1.58; N, 10.97; Found: C, 35.21; H, 1.59; N, 10.97 。1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylthio-5-aminopyrazole ( a2 ) (11 mmol), 35 g of trichloroacetaldehyde and 1 g of 4Å molecular sieve was mixed, heated to reflux for 36 h, trichloroacetaldehyde was distilled off, and the residue was subjected to column chromatography to obtain imine b2 . Yield 53%, melting point 112-114 ° C, 1 H NMR (CDCl 3 ), δ 9.00 (s, 1H, CH = N), 7.75 (s, 2H, Ph), 2.95 (q, 3 J HH = 7.2 Hz, 2H, CH 2 ), 1.28 (t, 3 J HH = 7.2 Hz, 3H, CH 3 ). Anal. Calcd for C 15 H 8 Cl 5 F 3 N 4 S (%): C, 35.29; H, 1.58; N, 10.97; Found: C, 35.21; H, 1.59; N, 10.97.
实施例 3 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I1 ） 的合成Example 3: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methyl Synthesis of oxyethyl)aminopyrazole (I1)
将 2mmol 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b1 ）和 10mL 甲醇混合，加热回流， TLC 监测反应。亚胺 b1 反应完毕后，除去绝大部分溶剂，剩余物柱层析，得白色固体 I1 。2 mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(trichloromethylmethyleneamino)pyrazole ( b1 ) and 10 mL of methanol was mixed, heated to reflux, and the reaction was monitored by TLC. After the reaction of the imine b1 is completed, most of the solvent is removed, and the residue is subjected to column chromatography to give a white solid I1 .
实施例 4 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲 基亚磺酰基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I11 ） 的合成Example 4: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylsulfinyl-5-(2,2,2-trichloro-1 - Synthesis of methoxyethyl)aminopyrazole (I11)
15mL 含 1mmol 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I1 ） 的二氯甲烷溶液中，加入 1mL 三氟乙酸和 0.23mL 30% 的双氧水，反应 3h ， TLC 监测反应。 加入 1g 亚硫酸氢钠分解多余的过氧化氢。加入 15mL 水，分液，有机相依次以 15mL 水和 15mL 食盐水洗涤，无水硫酸钠干燥。过滤，脱溶，粗品柱层析，得白色固体 I11 。15mL contains 1mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methoxy To a solution of ethylaminopyrazole ( I1 ) in dichloromethane, 1 mL of trifluoroacetic acid and 0.23 mL of 30% hydrogen peroxide were added and reacted for 3 h, and the reaction was monitored by TLC. Add 1 g of sodium bisulfite to decompose excess hydrogen peroxide. 15 mL of water was added, and the organic phase was washed with 15 mL of water and 15 mL of brine and dried over anhydrous sodium sulfate. Filtration, desolvation, and crude column chromatography gave white solid I11 .
同样，可以合成本发明的其它化合物，见表 1 。 Likewise, other compounds of the invention can be synthesized, as shown in Table 1.
实施例 5 ：蚕豆蚜的叶面触杀活性 Example 5: Foliar contact activity of broad bean meal
将一定量的待测化合物和乙虫腈溶于适量 N,N- 二甲基甲酰胺中，用含有 TW-20 的水配成 200mg L-1 的药液，并根据需要稀释特定浓度。将带有约 60 头蚜虫的嫩枝在药液中浸 5s ，除去叶面上多余的药液，将试虫转移至正常条件下生长， 24h 后查看结果。每个浓度在相同条件下重复三次，并设不含药剂的空白试验做对照。表 2 和表 3 为部分化合物的测试结果。A certain amount of the test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. The shoots with about 60 aphids were immersed in the liquid for 5 s, the excess liquid on the leaves was removed, and the test worms were transferred to normal conditions for growth, and the results were observed after 24 hours. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Tables 2 and 3 show the test results for some compounds.
实施例 6 ：对尖音库蚊幼虫活性 Example 6: Activity against Culex pipiens larvae
将样品用丙酮配制成一定浓度的母液，在 100mL 的烧杯内加入 90mL 水，分别加入不同量的样品母液，再加 10mL 含有 10 头 4 龄蚊幼虫的饲养水。每处理重复 3 次。处理后每天添加少许饲料 , 直到蚊幼虫全部化蛹或死亡。随时将化的蛹吸走。空白对照加与试验体积相同丙酮的水溶液。表 4 为部分化合物的测试结果。 Prepare a sample of acetone to a certain concentration of mother liquor and add 90 mL to a 100 mL beaker. Water, respectively, add different amounts of sample mother liquor, and add 10 mL of feed water containing 10 4-year-old mosquito larvae. Repeat 3 times per treatment. Add a little feed every day after treatment, Until the mosquito larvae are all sputum or die. At any time, the sputum will be sucked away. The blank control was added to an aqueous solution of the same volume as acetone. Table 4 shows the test results of some compounds.
实施例 7 ：对小菜蛾幼虫活性 Example 7: Activity against Plutella xylostella larvae
将一定量的待测化合物和乙虫腈溶于适量 N,N- 二甲基甲酰胺中，用含有 TW-20 的水配成 200mg L-1 的药液，并根据需要稀释特定浓度。将新鲜甘蓝叶切成片（ 6cm × 2cm ），在待测药液中浸 3s ，用滤纸吸去多余药液，在空气中晾干后放入玻璃管中，每管放入 7 头健康的小菜蛾 3 龄幼虫， 24 h 后随时添加新鲜叶片， 3d 后观察结果。每个浓度在相同条件下重复三次，并设不含药剂的空白试验做对照。表 5 为部分化合物的测试结果。A certain amount of the test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. Cut the fresh cabbage leaves into pieces (6cm × 2cm), soak in the liquid to be tested for 3s, use the filter paper to remove the excess liquid, dry it in the air, put it into the glass tube, and put 7 healthy ones in each tube. The 3rd instar larvae of Plutella xylostella were added with fresh leaves at any time after 24 h, and the results were observed after 3 days. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Table 5 shows the test results of some compounds.
表1 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）列表Table 1 List of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives ( I )
式中， R1 代表 1 － 6 碳烷基或被一个或一个以上相同或不同的卤素原子取代的烷基；Wherein R 1 represents a 1 - 6 carboalkyl group or an alkyl group substituted by one or more of the same or different halogen atoms;
R2 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 2 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
X 代表 O 、 S 或 NH ； X represents O , S or NH ;
n 代表 0 或 1 。 n stands for 0 or 1.
本发明所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）中，优选： R1 为甲基 、三氟甲基或乙基 ； R2 代表取代或未取代的烷基、烯基、炔基或环烷基； R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基或呋喃基； X 代表 O ； n 代表 0 或 1 。In the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention, preferably: R 1 is a methyl group, a trifluoromethyl group. Or ethyl; R 2 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl or cycloalkyl group; R 3 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or furan Base; X stands for O; n stands for 0 or 1.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）可以按如下方法制备：将化合物 a 和醛反应得到亚胺 (b) ，化合物 b 与 醇或硫醇或胺加成可制得 n 为 0 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ），再进一步氧化可制得 n 为 1 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ），如图 2 。The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) can be produced by reacting a compound a with an aldehyde to give an imine ( b ), compound b is added with an alcohol or a thiol or an amine to obtain a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative having n of 0 ( I ), further oxidation can produce a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) with n of 1, as shown in Fig. 2.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，它作为杀虫剂，用于防治鳞翅目类、鞘翅目类、异翅目类、双翅目类、直翅目类以及同翅目类害虫。 The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative Its application as an insecticide for the control of Lepidoptera, Coleoptera, Heteroptera, Diptera, Orthoptera and Homoptera.
所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，优选的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物为 The use of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative, preferably 3- Cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives are
I11 ： R1 为 Me ， R2 为 Me ， R3 为 CCl3 ， X 为 O ， n 为 1 ， I11: R 1 is Me, R 2 is Me, R 3 is CCl 3 , X is O, and n is 1 .
或 I13 ： R1 为 Me ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， Or I13: R 1 is Me, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 .
或 I20 ： R1 为 Et ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， 用于防治 蚜虫。 Or I20: R 1 is Et, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 for controlling aphids.
化合物 a 是市售的或是用已知方法制备的。Compound a is commercially available or can be prepared by known methods.
本发明还可用表 1 中列出的化合物来说明，但并不限定本发明。 The invention may also be illustrated by the compounds listed in Table 1, but is not intended to limit the invention.
本发明通式（ I ）的化合物具有优异的杀虫活性，能用于防治鳞翅目类、鞘翅目类、异翅目类、双翅目类、直翅目类以及同翅目类害虫。The compound of the formula ( I ) of the invention has excellent insecticidal activity and can be used for controlling lepidopteran, coleopteran, genus Heteroptera, Diptera, Orthoptera and Homoptera pests.
本发明通式（ I ）的部分化合物对蚜虫、尖音库蚊、小菜蛾的杀虫活性超过了商品化品种乙虫腈（ Ethiprole ）。The insecticidal activity of some compounds of the formula ( I ) of the present invention against aphids, Culex pipiens pallens, and diamondback moth exceeds the commercial variety Ethiprole.
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，也可以和其它杀虫剂和（或）杀螨剂复配使用。The compound of the formula ( I ) of the present invention may be used as it is, or may be added to an agriculturally acceptable carrier, or may be used in combination with other insecticides and/or acaricides.
附图说明 DRAWINGS
图 1 是本发明的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物的 化学通式（ I ）；Figure 1 is a chemical formula ( I ) of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative of the present invention;
图 2 是本发明的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）的合成路线图。Figure 2 is a synthetic route diagram of the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) of the present invention.
具体实施方式 detailed description
以下结合实施例来进一步说明本发明： The invention will be further illustrated below in conjunction with the examples:
实施例 1 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b1 ） 的合成Example 1: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(trichloromethylmethyleneamino)pyrazole (b1 ) synthesis
将 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5- 氨基吡唑（ a1 ）（ 11mmol ）， 35g 三氯乙醛及 1g 4Å 分子筛混合，加热回流 36 h ，蒸去三氯乙醛，残余物柱层析，得亚胺 b1 。 收率 44% ，熔点 113-115 °C ， 1 H NMR (CDCl3), δ 8.82 (s, 1H, CH = N), 7.74 (s, 2H, Ph), 2.58 (s, 3H, CH3). Anal. Calcd for C14H6Cl5F3N4S (%): C, 33.86; H, 1.22; N, 11.28; Found: C, 33.99; H, 1.21; N, 11.12 。1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-aminopyrazole ( a1 ) (11 mmol), 35 g of trichloroacetaldehyde and 1 g of 4Å molecular sieves were mixed, heated to reflux for 36 h, trichloroacetaldehyde was distilled off, and the residue was subjected to column chromatography to obtain imine b1 . Yield 44%, melting point 113-115 ° C, 1 H NMR (CDCl 3 ), δ 8.82 (s, 1H, CH = N), 7.74 (s, 2H, Ph), 2.58 (s, 3H, CH 3 ) Anal. Calcd for C 14 H 6 Cl 5 F 3 N 4 S (%): C, 33.86; H, 1.22; N, 11.28; Found: C, 33.99; H, 1.21; N, 11.12.
实施例 2 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 乙硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b2 ） 的合成Example 2: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylthio-5-(trichloromethylmethyleneamino)pyrazole (b2 ) synthesis
将 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 乙硫基 -5- 氨基吡唑（ a2 ）（ 11mmol ）， 35g 三氯乙醛及 1g 4Å 分子筛混合，加热回流 36 h ，蒸去三氯乙醛，残余物柱层析，得亚胺 b2 。收率 53% ，熔点 112-114 °C, 1H NMR (CDCl3), δ 9.00 (s, 1H, CH = N), 7.75 (s, 2H, Ph), 2.95 (q, 3 J HH = 7.2 Hz, 2H, CH2), 1.28 (t,3 J HH = 7.2 Hz, 3H, CH3). Anal. Calcd for C15H8Cl5F3N4S (%): C, 35.29; H, 1.58; N, 10.97; Found: C, 35.21; H, 1.59; N, 10.97 。1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-ethylthio-5-aminopyrazole ( a2 ) (11 mmol), 35 g of trichloroacetaldehyde and 1 g of 4Å molecular sieve was mixed, heated to reflux for 36 h, trichloroacetaldehyde was distilled off, and the residue was subjected to column chromatography to obtain imine b2 . Yield 53%, melting point 112-114 ° C, 1 H NMR (CDCl 3 ), δ 9.00 (s, 1H, CH = N), 7.75 (s, 2H, Ph), 2.95 (q, 3 J HH = 7.2 Hz, 2H, CH 2 ), 1.28 (t, 3 J HH = 7.2 Hz, 3H, CH 3 ). Anal. Calcd for C 15 H 8 Cl 5 F 3 N 4 S (%): C, 35.29; H, 1.58; N, 10.97; Found: C, 35.21; H, 1.59; N, 10.97.
实施例 3 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I1 ） 的合成Example 3: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methyl Synthesis of oxyethyl)aminopyrazole (I1)
将 2mmol 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-( 三氯甲基亚甲 氨基 ) 吡唑（ b1 ）和 10mL 甲醇混合，加热回流， TLC 监测反应。亚胺 b1 反应完毕后，除去绝大部分溶剂，剩余物柱层析，得白色固体 I1 。2 mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(trichloromethylmethyleneamino)pyrazole ( b1 ) and 10 mL of methanol was mixed, heated to reflux, and the reaction was monitored by TLC. After the reaction of the imine b1 is completed, most of the solvent is removed, and the residue is subjected to column chromatography to give a white solid I1 .
实施例 4 ： 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲 基亚磺酰基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I11 ） 的合成Example 4: 1-(2,6-Dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylsulfinyl-5-(2,2,2-trichloro-1 - Synthesis of methoxyethyl)aminopyrazole (I11)
15mL 含 1mmol 1-(2,6- 二氯 -4- 三氟甲基 ) 苯基 -3- 氰基 -4- 甲硫基 -5-(2,2,2- 三氯 -1- 甲氧乙基 ) 氨基 吡唑（ I1 ） 的二氯甲烷溶液中，加入 1mL 三氟乙酸和 0.23mL 30% 的双氧水，反应 3h ， TLC 监测反应。 加入 1g 亚硫酸氢钠分解多余的过氧化氢。加入 15mL 水，分液，有机相依次以 15mL 水和 15mL 食盐水洗涤，无水硫酸钠干燥。过滤，脱溶，粗品柱层析，得白色固体 I11 。15mL contains 1mmol of 1-(2,6-dichloro-4-trifluoromethyl)phenyl-3-cyano-4-methylthio-5-(2,2,2-trichloro-1-methoxy To a solution of ethylaminopyrazole ( I1 ) in dichloromethane, 1 mL of trifluoroacetic acid and 0.23 mL of 30% hydrogen peroxide were added and reacted for 3 h, and the reaction was monitored by TLC. Add 1 g of sodium bisulfite to decompose excess hydrogen peroxide. 15 mL of water was added, and the organic phase was washed with 15 mL of water and 15 mL of brine and dried over anhydrous sodium sulfate. Filtration, desolvation, and crude column chromatography gave white solid I11 .
同样，可以合成本发明的其它化合物，见表 1 。 Likewise, other compounds of the invention can be synthesized, as shown in Table 1.
实施例 5 ：蚕豆蚜的叶面触杀活性 Example 5: Foliar contact activity of broad bean meal
将一定量的待测化合物和乙虫腈溶于适量 N,N- 二甲基甲酰胺中，用含有 TW-20 的水配成 200mg L-1 的药液，并根据需要稀释特定浓度。将带有约 60 头蚜虫的嫩枝在药液中浸 5s ，除去叶面上多余的药液，将试虫转移至正常条件下生长， 24h 后查看结果。每个浓度在相同条件下重复三次，并设不含药剂的空白试验做对照。表 2 和表 3 为部分化合物的测试结果。A certain amount of the test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. The shoots with about 60 aphids were immersed in the liquid for 5 s, the excess liquid on the leaves was removed, and the test worms were transferred to normal conditions for growth, and the results were observed after 24 hours. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Tables 2 and 3 show the test results for some compounds.
实施例 6 ：对尖音库蚊幼虫活性 Example 6: Activity against Culex pipiens larvae
将样品用丙酮配制成一定浓度的母液，在 100mL 的烧杯内加入 90mL 水，分别加入不同量的样品母液，再加 10mL 含有 10 头 4 龄蚊幼虫的饲养水。每处理重复 3 次。处理后每天添加少许饲料 , 直到蚊幼虫全部化蛹或死亡。随时将化的蛹吸走。空白对照加与试验体积相同丙酮的水溶液。表 4 为部分化合物的测试结果。 Prepare a sample of acetone to a certain concentration of mother liquor and add 90 mL to a 100 mL beaker. Water, respectively, add different amounts of sample mother liquor, and add 10 mL of feed water containing 10 4-year-old mosquito larvae. Repeat 3 times per treatment. Add a little feed every day after treatment, Until the mosquito larvae are all sputum or die. At any time, the sputum will be sucked away. The blank control was added to an aqueous solution of the same volume as acetone. Table 4 shows the test results of some compounds.
实施例 7 ：对小菜蛾幼虫活性 Example 7: Activity against Plutella xylostella larvae
将一定量的待测化合物和乙虫腈溶于适量 N,N- 二甲基甲酰胺中，用含有 TW-20 的水配成 200mg L-1 的药液，并根据需要稀释特定浓度。将新鲜甘蓝叶切成片（ 6cm × 2cm ），在待测药液中浸 3s ，用滤纸吸去多余药液，在空气中晾干后放入玻璃管中，每管放入 7 头健康的小菜蛾 3 龄幼虫， 24 h 后随时添加新鲜叶片， 3d 后观察结果。每个浓度在相同条件下重复三次，并设不含药剂的空白试验做对照。表 5 为部分化合物的测试结果。A certain amount of the test compound and ethiprole were dissolved in an appropriate amount of N,N-dimethylformamide, and a solution containing 200 mg of L -1 was formulated with water containing TW-20, and a specific concentration was diluted as needed. Cut the fresh cabbage leaves into pieces (6cm × 2cm), soak in the liquid to be tested for 3s, use the filter paper to remove the excess liquid, dry it in the air, put it into the glass tube, and put 7 healthy ones in each tube. The 3rd instar larvae of Plutella xylostella were added with fresh leaves at any time after 24 h, and the results were observed after 3 days. Each concentration was repeated three times under the same conditions, and a blank test containing no drug was set as a control. Table 5 shows the test results of some compounds.
表1 、3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）列表Table 1. List of 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives ( I )
Figure PCTCN2010079844-appb-C000005
Figure PCTCN2010079844-appb-C000005
编号 Numbering R1 R 1 R2 R 2 R3 R 3 X X n n 熔点（ ℃ ） Melting point ( °C )
I1 I1 Me Me Me Me CCl3 CCl 3 O O 0 0 91-92 91-92
I2 I2 Me Me Et Et CCl3 CCl 3 O O 0 0 127-128 127-128
I3 I3 Me Me n -Pr n -Pr CCl3 CCl 3 O O 0 0 147-149 147-149
I4 I4 Me Me FCH2CH2 FCH 2 CH 2 CCl3 CCl 3 O O 0 0 129-131 129-131
I5 I5 Me Me ClCH2CH2 ClCH 2 CH 2 CCl3 CCl 3 O O 0 0 142-144 142-144
I6 I6 Et Et Me Me CCl3 CCl 3 O O 0 0 123-124 123-124
I7 I7 Et Et Et Et CCl3 CCl 3 O O 0 0 137-139 137-139
I8 I8 Et Et n -Pr n -Pr CCl3 CCl 3 O O 0 0 119-121 119-121
I9 I9 Et Et FCH2CH2 FCH 2 CH 2 CCl3 CCl 3 O O 0 0 147-149 147-149
I10 I10 Et Et ClCH2CH2 ClCH 2 CH 2 CCl3 CCl 3 O O 0 0 123-125 123-125
I11 I11 Me Me Me Me CCl3 CCl 3 O O 1 1 110-112 110-112
I12 I12 Me Me Et Et CCl3 CCl 3 O O 1 1 98-100 98-100
I13 I13 Me Me n -Pr n -Pr CCl3 CCl 3 O O 1 1 158-160 158-160
I14 I14 aa Me Me FCH2CH2 FCH 2 CH 2 CCl3 CCl 3 O O 1 1 150-152 150-152
I15 I15 bb Me Me FCH2CH2 FCH 2 CH 2 CCl3 CCl 3 O O 1 1 141-143 141-143
I16 I16 cc Me Me ClCH2CH2 ClCH 2 CH 2 CCl3 CCl 3 O O 1 1 151-153 151-153
I17 I17 dd Me Me ClCH2CH2 ClCH 2 CH 2 CCl3 CCl 3 O O 1 1 133-135 133-135
I18 I18 Et Et Me Me CCl3 CCl 3 O O 1 1 147-149 147-149
I19 I19 Et Et Et Et CCl3 CCl 3 O O 1 1 133-134 133-134
I20 I20 Et Et n -Pr n -Pr CCl3 CCl 3 O O 1 1 49-51 49-51
I21 I21 Et Et FCH2CH2 FCH 2 CH 2 CCl3 CCl 3 O O 1 1 67-69 67-69
I22 I22 Et Et ClCH2CH2 ClCH 2 CH 2 CCl3 CCl 3 O O 1 1 52-54 52-54
I23 I23 CF3 CF 3 Me Me Ph Ph O O 1 1 104-105 104-105
I24 I24 CF3 CF 3 Me Me 4-NO2-Ph4-NO 2 -Ph O O 1 1 143-145 143-145
I25 I25 CF3 CF 3 Me Me 2-furanyl 2-furanyl O O 1 1 152-154 152-154
I26 I26 CF3 CF 3 Me Me styrenyl Styrenyl O O 1 1 104-107 104-107
I27 I27 Me Me Me Me CCl3 CCl 3 S S 0 0 油状物 Oily
I28 I28 Me Me Me Me CCl3 CCl 3 S S 1 1 油状物 Oily
I29 I29 Me Me Me Me CCl3 CCl 3 NH NH 0 0 油状物 Oily
I30 I30 Me Me Me Me CCl3 CCl 3 NH NH 1 1 油状物 Oily
注： a,b: I14 和 I15 为两对对映异构体； c,d: I16 和 I17 为两对对应异构体。Note: a, b: I14 and I15 are two pairs of enantiomers; c, d: I16 and I17 are two pairs of isomers.
表 2 部分化合物和乙虫腈对蚜虫的叶面触杀活性 Table 2 Leaf contact toxicity of some compounds and ethiprofen to aphids
编号 Numbering 测试浓度（ mg kg-1 ）及杀虫活性（ % ）Test concentration (mg kg -1 ) and insecticidal activity (%)
200 200 100 100 50 50 25 25 10 10 5 5 2.5 2.5
I1 I1 100 100 100 100 100 100 94 94 89 89 43 43 0 0
I2 I2 100 100 100 100 56 56 43 43 0 0 0 0
I3 I3 100 100 100 100 90 90 43 43 21 twenty one 0 0 0 0
I4 I4 100 100 100 100 100 100 74 74 62 62 28 28 0 0
I5 I5 100 100 100 100 100 100 98 98 73 73 69 69 62 62
I6 I6 93 93 90 90 80 80 62 62 0 0
I7 I7 90 90 86 86 75 75 35 35 0 0
I8 I8 95 95 90 90 85 85 53 53 0 0
I9 I9 100 100 100 100 100 100 29 29 11 11 0 0
I10 I10 100 100 100 100 100 100 100 100 51 51 0 0
I11 I11 100 100 100 100 100 100 100 100 100 100 88 88 0 0
I12 I12 100 100 100 100 100 100 100 100 85 85 63 63 0 0
I13 I13 100 100 100 100 100 100 100 100 100 100 91 91 0 0
I14 I14 100 100 100 100 100 100 100 100 100 100 72 72 43 43
I15 I15 100 100 100 100 100 100 100 100 100 100 70 70 46 46
I16 I16 100 100 100 100 100 100 100 100 96 96 61 61 0 0
I17 I17 100 100 100 100 100 100 100 100 100 100 68 68 0 0
I18 I18 100 100 100 100 100 100 96 96 87 87 76 76 0 0
I19 I19 100 100 100 100 100 100 100 100 100 100 81 81 0 0
I20 I20 100 100 100 100 100 100 100 100 100 100 100 100 89 89
I21 I21 100 100 100 100 100 100 100 100 100 100 73 73 43 43
I22 I22 100 100 100 100 100 100 100 100 48 48 0 0
乙虫腈 Ethyl nitrile 100 100 100 100 100 100 100 100 31 31 0 0
表 3 部分化合物和乙虫腈对蚜虫叶面触杀活性的 LC50 值Table 3 LC 50 values of leaf compound contact activity of some compounds and ethiprofen on aphids
编号 Numbering 回归方程 Regression equation LC50 (mg kg-1)LC 50 (mg kg -1 ) 毒力指数 Virulence index
I11 I11 y = -2.3051 + 5.0099x y = -2.3051 + 5.0099x 2.8848 2.8848 4.2 4.2
I13 I13 y = -2.1989 + 4.9845x y = -2.1989 + 4.9845x 2.7616 2.7616 4.3 4.3
I20 I20 y = -0.7833 + 4.5433x y = -0.7833 + 4.5433x 1.4873 1.4873 7.9 7.9
乙虫腈 Ethyl nitrile y = -7.9808 + 7.4646x y = -7.9808 + 7.4646x 11.7263 11.7263 1 1
表 4 部分化合物和乙虫腈杀蚊幼虫活性 Table 4 Activity of some compounds and acetonitrile larvae
编号 Numbering 测试浓度（ m g kg-1 ）及杀虫活性（ % ）Test concentration (mg kg -1 ) and insecticidal activity (%)
100 100 50 50 25 25 10 10 5 5 2.5 2.5
I1 I1 100 100 100 100 100 100 100 100 100 100 70 70
I2 I2 100 100 100 100 100 100 100 100 100 100 80 80
I3 I3 100 100 100 100 100 100 100 100 100 100 100 100
I4 I4 100 100 100 100 100 100 40 40
I5 I5 100 100 100 100 100 100 100 100 20 20
I6 I6 100 100 100 100 100 100 100 100 100 100 30 30
I7 I7 100 100 100 100 100 100 100 100 0 0
I8 I8 100 100 100 100 100 100 100 100 50 50
I9 I9 100 100 100 100 100 100 100 100 0 0
I10 I10 100 100 100 100 100 100 100 100 100 100 60 60
I11 I11 100 100 50 50
I12 I12 100 100 100 100 30 30
I13 I13 100 100 100 100 50 50
I14 I14 20 20
I15 I15 50 50
I16 I16 100 100 40 40
I17 I17 50 50
I18 I18 100 100 100 100 0 0
I19 I19 100 100 100 100 40 40
I20 I20 100 100 100 100 0 0
I21 I21 100 100 20 20
I22 I22 100 100 0 0
乙虫腈 Ethyl nitrile 100 100 100 100 50 50
表 5 部分化合物和乙虫腈 对小菜蛾的活性 Table 5 Activity of some compounds and ethiprofen against Plutella xylostella
编号 测试浓度（ mg kg-1 ）及杀虫活性（ % ）
200 100 50 25 10 5 2.5
I1 100 100 100 100 86 76 25
I2 100 100 100 84 68 43 0
I3 100 100 36 17 0
I4 100 100 100 100 89 81 34
I5 100 100 100 100 100 87 62
I6 100 100 94 34 0
I7 100 100 96 44 18
I8 100 100 89 58 17
I9 100 100 100 100 29 0
I10 100 100 88 43 27 0
I11 100 100 100 100 91 88 34
I12 100 100 100 100 85 63 0
I13 100 100 100 100 71 30 0
I14 100 100 100 92 77 56 0
I15 100 100 100 89 76 54 0
I16 100 100 100 100 81 60 0
I17 100 100 100 100 79 56 0
I18 100 100 86 31 0
I19 100 100 100 100 72 29 0
I20 100 100 100 87 44 27 0
I21 100 100 91 46 30 0
I22 100 100 100 46 32 0
乙虫腈 100 100 100 69 23 0 　
。
Numbering Test concentration (mg kg -1 ) and insecticidal activity (%)
200 100 50 25 10 5 2.5
I1 100 100 100 100 86 76 25
I2 100 100 100 84 68 43 0
I3 100 100 36 17 0
I4 100 100 100 100 89 81 34
I5 100 100 100 100 100 87 62
I6 100 100 94 34 0
I7 100 100 96 44 18
I8 100 100 89 58 17
I9 100 100 100 100 29 0
I10 100 100 88 43 27 0
I11 100 100 100 100 91 88 34
I12 100 100 100 100 85 63 0
I13 100 100 100 100 71 30 0
I14 100 100 100 92 77 56 0
I15 100 100 100 89 76 54 0
I16 100 100 100 100 81 60 0
I17 100 100 100 100 79 56 0
I18 100 100 86 31 0
I19 100 100 100 100 72 29 0
I20 100 100 100 87 44 27 0
I21 100 100 91 46 30 0
I22 100 100 100 46 32 0
Ethyl nitrile 100 100 100 69 twenty three 0
.
Description Of DrawingsDescription Of Drawings
Figure PCTCN2010079844-appb-C000006
图1
Figure PCTCN2010079844-appb-C000007
 图2
Figure PCTCN2010079844-appb-C000006
 figure 1
Figure PCTCN2010079844-appb-C000007
 figure 2

Claims (6)

  1. 一种 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 ，其特征在于，它具有如下通式（ I ）所示结构： A 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative characterized by having the following formula (I ) shown structure:
    Figure PCTCN2010079844-appb-C000008
    Figure PCTCN2010079844-appb-C000008
    式中， R1 代表 1 － 6 碳烷基或被一个或一个以上相同或不同的卤素原子取代的烷基；Wherein R 1 represents a 1 - 6 carboalkyl group or an alkyl group substituted by one or more of the same or different halogen atoms;
    R2 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 2 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
    R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基、 1 － 6 碳烃羰基、 1 － 6 碳烃氧羰基、苯氧羰基、苄氧羰基、萘基、色满、 2 ， 3 －二氢－ 1 ， 4 －苯并二噁嗪、 4H-1 ， 3 －苯并二噁嗪、 2 ， 3 －二氢－苯并呋喃、苯并呋喃、苯并噻唑、 1 ， 3 －苯并噁唑、 1 ， 2 －苯并异噁唑或苯并咪唑，各基团是未取代的，或是被一个或一个以上下述基团取代：卤素、 1 － 4 碳烷基、 1 － 4 碳烷氧基、 1 － 4 碳卤代烷基、 1 － 4 碳卤代烷氧基、 1 － 4 碳烷氧烷基、 1 － 4 碳烷硫基、 1 － 4 碳烷基亚磺酰基、 1 － 4 碳烷基磺酰基、硝基、氰基、羟基、羧基、 1 － 4 碳烷基羰基、 1 － 4 碳烷氧基羰基或亚胺基；R 3 represents a substituted or unsubstituted alkyl group, alkenyl group, alkynyl group, cycloalkyl group, phenyl group, 1 - 6 carbon hydrocarbon carbonyl group, 1 - 6 carbon hydrocarbon oxycarbonyl group, phenoxycarbonyl group, benzyloxycarbonyl group, naphthyl group, Chromo, 2,3-dihydro-1,4-benzodioxazine, 4H-1,3-benzodioxazine, 2,3-dihydro-benzofuran, benzofuran, benzothiazole 1, 1 - 3 - benzoxazole, 1 , 2 - benzisoxazole or benzimidazole, each group being unsubstituted or substituted by one or more of the following groups: halogen, 1 - 4 Carboxyalkyl, 1 - 4 carboalkoxy, 1 - 4 carbohaloalkyl, 1 - 4 carbohaloalkoxy, 1 - 4 carboaloxyl, 1 - 4 alkylalkylthio, 1 - 4 alkyl Sulfinoyl group, 1 - 4 carbon alkylsulfonyl group, nitro group, cyano group, hydroxyl group, carboxyl group, 1 -4 carbon alkylcarbonyl group, 1 - 4 carbon alkoxycarbonyl group or imine group;
    X 代表 O 、 S 或 NH ；X represents O , S or NH ;
    n 代表 0 或 1 。n stands for 0 or 1.
  2. 据权利要求 1 所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 ，其特征在于 R1 为甲基 、三氟甲基或乙基 ； R2 代表取代或未取代的烷基、烯基、炔基或环烷基； R3 代表取代或未取代的烷基、烯基、炔基、环烷基、苯基或呋喃基； X 代表 O ； n 代表 0 或 1 。The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative according to claim 1, wherein R 1 is methyl, trifluoromethyl or Ethyl; R 2 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl or cycloalkyl group; R 3 represents a substituted or unsubstituted alkyl, alkenyl, alkynyl, cycloalkyl, phenyl or furanyl group. ; X stands for O ; n stands for 0 or 1.
  3. 一种 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物的制备方法，其特征在于，按照如下步骤制备， 将化合物 a 和醛反应得到亚胺 b ，亚胺 b 与 醇、硫醇或胺加成制得 n 为 0 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）。A process for the preparation of a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative, which is prepared by reacting a compound a with an aldehyde according to the following procedure Addition of imine b , imine b to alcohol, thiol or amine to give 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivatives with n of 0 ( I ).
  4. 根据权利要求 3 所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物的制备方法，其特征在于， n 为 0 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）再进一步氧化制得 n 为 1 的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 （ I ）。The process for producing a 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative according to claim 3, wherein 3-cyanide wherein n is 0 The -1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative ( I ) is further oxidized to give 3-cyano-1-(2,6-di) with n Chloro-4-trifluoromethylphenyl)pyrazole derivatives ( I ).
  5. 权利要求 1 所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，其特征在于它作为杀虫剂，用于防治鳞翅目类、鞘翅目类、异翅目类、双翅目类、直翅目类以及同翅目类害虫。The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative according to claim 1 The application is characterized in that it is used as an insecticide for controlling lepidopteran, coleoptera, Heteroptera, Diptera, Orthoptera and Homoptera pests.
  6. 根据权利要求 5 所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物 的应用，其特征在于，所述的 3- 氰基 -1-(2,6- 二氯 -4- 三氟甲基苯基 ) 吡唑衍生物为The 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative according to claim 5 Application, characterized in that the 3-cyano-1-(2,6-dichloro-4-trifluoromethylphenyl)pyrazole derivative is
    I11 ： R1 为 Me ， R2 为 Me ， R3 为 CCl3 ， X 为 O ， n 为 1 ， I11: R 1 is Me, R 2 is Me, R 3 is CCl 3 , X is O, and n is 1 .
    或 I13 ： R1 为 Me ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， Or I13: R 1 is Me, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 .
    或 I20 ： R1 为 Et ， R2 为 n -Pr ， R3 为 CCl3 ， X 为 O ， n 为 1 ， 用于防治 蚜虫。 Or I20: R 1 is Et, R 2 is n -Pr , R 3 is CCl 3 , X is O, and n is 1 for controlling aphids.
PCT/CN2010/079844 2010-03-29 2010-12-16 3-cyano-1-(2,6-dichloro-4-trifluoromethyl phenyl)pyrazole derivatives as insecticides WO2011120312A1 (en)

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