WO2008134970A1 - Anthranilamide compounds and the use thereof - Google Patents

Anthranilamide compounds and the use thereof Download PDF

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Publication number
WO2008134970A1
WO2008134970A1 PCT/CN2008/070832 CN2008070832W WO2008134970A1 WO 2008134970 A1 WO2008134970 A1 WO 2008134970A1 CN 2008070832 W CN2008070832 W CN 2008070832W WO 2008134970 A1 WO2008134970 A1 WO 2008134970A1
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Prior art keywords
alkyl
hydrogen
group
halogenated
alkoxy
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PCT/CN2008/070832
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French (fr)
Chinese (zh)
Inventor
Changling Liu
Baoshan Chai
Aiying Guan
Hong Zhang
Yongwu Peng
Junfeng Wang
Huichao Li
Zhinian Li
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Sinochem Corporation
Shenyang Research Institute Of Chemical Industry
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Priority claimed from CN2007100111786A external-priority patent/CN101298435B/en
Priority claimed from CN 200710011176 external-priority patent/CN101298451B/en
Priority claimed from CN2008100571021A external-priority patent/CN101497602B/en
Application filed by Sinochem Corporation, Shenyang Research Institute Of Chemical Industry filed Critical Sinochem Corporation
Publication of WO2008134970A1 publication Critical patent/WO2008134970A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • 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
    • C07D231/16—Halogen atoms or nitro radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the invention belongs to the field of agricultural insecticides and fungicides.
  • it relates to an orthoformylbenzamide compound and composition, and the use thereof as an insecticidal or bactericidal agent in agriculture or other fields. Background technique
  • invertebrate pests The control of invertebrate pests is extremely important in achieving high planting efficiency. Damage to growing and stored crops by invertebrate pests can cause a significant reduction in productivity and, consequently, an increase in consumer spending. Many of the products used for these purposes are commercially available, but new compounds that are more efficient, low cost, low toxic, environmentally safe or have different modes of action are still needed. O-formylaminobenzamides (Finedine Receptor Inhibitors) are effective insecticides for the prevention and treatment of invertebrate pests in recent years.
  • the object of the present invention is to provide an anthranilic benzene which can control various pests and diseases at a small dose.
  • Formic acid compounds which can be applied to agriculture to control crop diseases and insect pests.
  • the present invention provides an o-formylaminobenzamide compound, as shown in Formula I:
  • A is selected from N or CH;
  • B is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated dC 6 alkyl, dC 6 alkoxy, dC 6 alkane Thio group, dC 6 alkylsulfonyl group, dC 6 alkylcarbonyl group, dC 6 alkoxy dC 6 alkyl group, dC 6 alkoxycarbonyl group, dC 6 alkoxycarbonyl dC 6 alkyl group or ⁇ dC 6 alkoxy group dC 6 alkyl;
  • C is selected from hydrogen or halogen
  • R 2 is selected from the group consisting of hydrogen, halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, ⁇ ⁇ unsubstituted or substituted by the following groups: methyl, dimethyl Base, acetyl, methylsulfonyl;
  • R 3 is selected from the group consisting of halogen, CS H 2 , OCH 2 CN, dC 6 alkyl, halogenated dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 alkoxy, dC 6 alkylthio, halogenated dC 6 Alkylthio, dC 6 alkylsulfonyl, halogenated dC 6 alkylsulfonyl, dC 6 alkylcarbonyl, dC 6 alkoxyfluorenyl, dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkoxy, dC 6 alkylthio dC 6 alkyl, halogenated dC 6 alkylthio dC 6 alkyl, C 2 -C 6 alkenyloxy, halogenated C
  • R 5 is selected from the group consisting of CN dC 4 alkyl, halogenated dC 6 alkyl, -NHCOCH 2 CN - HCOCF3 H 2 CF 3 - 0 -CH 2 C0 2 CH 3 -CH(C0 2 Et) 2 C3 ⁇ 4C ie CH 3)2 - CHR 6 (CH 2 ) nX
  • R 5 may also be selected from a cyano-substituted dC 6 alkyl group;
  • 3 ⁇ 4R 5 can form a five or six ring
  • n is selected from an integer of 0 1-10;
  • X is selected from OR 7 SR 7 or R 7 R 8 ;
  • R 7 is selected from the group consisting of hydrogen, dC 6 alkyl, dC 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, dC 6 alkylcarbonyl, dC 3 haloalkylcarbonyl, C 2 -C 6 alkane Oxycarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, dC 3 haloalkylsulfonyl, phenylsulfonyl, dC 6 alkylamido, dC 6 alkylthioamido, phenylamido or benzene a thioamido group; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen,
  • Ql l Q12 Q13 Q14 is selected from hydrogen or CC 3 alkyl.
  • Preferred compounds in the present invention are:
  • A is selected from N or CH;
  • B is selected from the group consisting of hydrogen, halogen, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
  • C is selected from hydrogen or halogen
  • R 2 is selected from halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, ⁇ ⁇ unsubstituted or substituted by the following groups: methyl, dimethyl, Acetyl or mesyl;
  • R 3 is selected from halogen, dC 3 alkyl, halogenated dC 3 alkyl or halogenated dC 3 alkoxy;
  • R 5 is selected from CN, dC 4 alkyl, dC 3 haloalkyl group, _NHCH 2 CF 3, -. U, CH2C o 2 CH 3 -CH (C0 2 Et) 2, -CH 2 CH (OCH 3) 2 Or a CHR 6 (CH 2 ) nX ; when B is not hydrogen, R 5 may also be selected from a cyano-substituted dC 3 alkyl group;
  • Re is selected from hydrogen or methyl
  • n is selected from 0, an integer from 1 to 10;
  • X is selected from OR 7 , SR 7 , R 7 Rs;
  • R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, C 3 -C 6 alkynyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkane Alkylamino, dC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen, N0 2 , CN , C1-C3 alkyl, dC 3 haloalkyl, dC 3 alkoxy, dC 3 haloalkoxy; Q1-Q14 or one of the groups;
  • A is selected from N or CH;
  • B is selected from the group consisting of hydrogen, Cl, Br, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
  • C is selected from the group consisting of hydrogen, Cl, Br or F; Ri is selected from Cl, Br, I or CH 3 ;
  • R 2 is selected from Cl, Br, I or CN
  • R 3 is selected from the group consisting of Cl, Br, CH 3 , CF 3 CH 2 0;
  • R4 is selected from hydrogen or CC 3 alkyl
  • R 5 is selected from the group consisting of CN, C1-C4 alkyl, CH 2 CF 3 -CH 2 CH 2 C1, -HCH 2 CF 3 _N ⁇ °, -CH 2 C0 2 CH 3
  • R 5 is also selected from CH 2 CN;
  • R6 is selected from hydrogen or methyl
  • n is selected from 0, an integer from 1 to 10;
  • X is selected from OR 7 , SR 7 , R 7 Rs;
  • R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, propargyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkylamido, DC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups:
  • A is selected from N or CH;
  • B is selected from the group consisting of hydrogen, Cl, cyano, CH 3 or CF 3 ;
  • C is selected from hydrogen or C1;
  • Ri is selected from C1 or CH 3 ;
  • R 2 is selected from Cl, Br or CN
  • R 3 is selected from CI or Br
  • R4 is selected from hydrogen or CC 3 alkyl
  • R 5 is selected from the group consisting of CN, dC 4 alkyl, CH 2 CF 3 , -CH 2 CH 2 C1, -HCH 2 CF 3 _N ⁇ °, -CH 2 C0 2 CH 3 ⁇ -CHR 6 (CH 2 )nX .
  • ⁇ is not hydrogen, R 5 may also be selected from CH 2 CN;
  • Re is selected from hydrogen or methyl
  • n is selected from 0, an integer from 1 to 10;
  • X is selected from OR 7 , SR 7 , R 7 Rs;
  • R 7 is selected from the group consisting of hydrogen, CrC 3 alkyl, propargyl, CH 3 CO, C1CH 2 C0, CH 3 S0 2 , C 2 H 5 S0 2 , phenylcarbonyl, phenylsulfonyl, formylamino, propyl Thioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by a group: Cl, CF 3 , CF 3 O; or a Q 1 -Q 10 group One;
  • the number of substituents in the substituted amine group may be from 1 to 2.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl or t-butyl.
  • Haloalkyl a straight or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, a haloalkyl group such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl Base, difluoromethyl or trifluoromethyl.
  • Alkenyl straight or branched and may have a double bond at any position, such as a vinyl or allyl group.
  • Alkynyl straight or branched and may have a triple bond at any position, such as ethynyl or propargyl.
  • a stereoisomer can be formed due to a carbon-carbon double bond and a carbon-nitrogen double bond connecting different substituents (different configurations are represented by Z and E, respectively).
  • the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
  • the invention may be illustrated by the compounds listed in the following tables, but does not limit the invention.
  • the compound of formula I can be prepared by reacting an oxazinone compound of the formula II with a substituted amine:
  • the reaction is carried out in a solvent, and is suitably selected from, for example, acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, chloroform, ethyl acetate, dioxane, toluene and the like.
  • Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide.
  • the reaction temperature is between room temperature and the boiling point of the solvent, usually from 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • ⁇ ⁇ Formula II is a oxazinone compound prepared by reacting an anthranilic acid compound of the formula III with a carboxylic acid compound of the formula IV.
  • the anthranilic acid compound of the formula III can be obtained by a two-step reaction of an aromatic amine, and is referred to the following literature: Organic Syntheses, Coll. Vol. 10, p . 23 (2004) ; Vol . 79, p. 2002); Adv. Heterocycl. Chem. 1975, 18, 1-58; Journal of the Brazilian Chemical Society 2001, 12(3), 273-324; Angew.Chem.Int.Ed.Engl.1980, 19, 222- 223.
  • the compound of the formula I of the present invention exhibits high insecticidal activity against adults, larvae and eggs of harmful insects in the fields of agriculture, civil and animal technology. Some of the compounds showed better bactericidal activity. Accordingly, the present invention also encompasses the use of the compound of formula I as an insecticide and/or bactericide in agriculture and other fields.
  • the compounds of formula I are active against important pests of the following families and purposes: lepidopteran pests, stem borer, rice leaf roller, corn borer, tobacco leaf moth, small heartworm, diamondback moth, beet armyworm, twill night Moth and so on.
  • the present invention is more active against Plutella xylostella and Spodoptera exigua, and it can obtain good effects at very low doses; the present invention also has high activity against pests of the same wing, such as aphids; and at the same time, parts of the present invention
  • the compound also has good bactericidal activity and can be used for controlling rice blast, tomato late blight, vegetable gray mold, wheat powdery mildew, cucumber downy mildew, anthracnose, etc., especially for rice blast, cucumber downy mildew, Anthrax has good activity.
  • the compounds of formula I are less toxic to many beneficial insects and aphids, mammals, fish, birds, and are not phytotoxic.
  • the above compounds are advantageously used to protect important crops, livestock and stocks in the agricultural and horticultural industries, as well as the environment frequently experienced by humans from harmful insects and fungi.
  • the amount of the compound varies depending on various factors such as the compound to be used, the crop to be protected, the type of the pest, the degree of infection, the climatic conditions, the method of application, and the dosage form to be employed.
  • a dose of 10 grams to 1000 grams of compound per hectare provides adequate control.
  • a further object of the invention also relates to a method for controlling insects and/or phytopathogenic fungi in agricultural and horticulturally important crops and/or livestock and breeding stocks and/or environments frequented by humans by the application of the compounds of formula I .
  • the amount of the compound varies from 10 grams to 1000 grams per hectare.
  • composition comprising one or more compounds of formula I. Therefore, another object of the invention relates to insecticidal and insecticidal compounds containing one or more compounds of formula I as active ingredients
  • the active ingredient in the composition is present in an amount of from 0.1 to 99% by weight.
  • the composition may be used in the form of a dry powder, a wettable powder, an emulsifiable concentrate, a microemulsion, a paste, a granule, a solution, a suspension, etc.:
  • the choice of the type of composition depends on the particular application.
  • composition is prepared in a known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, optionally in the presence of a surfactant.
  • Useful solid diluents or carriers are, for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite, etc. .
  • useful liquid diluents include, for example, aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffin (petroleum), alcohols (methanol, propanol, butanol, octane). Alcohol, glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides ( ⁇ , ⁇ -dimethylformamide, ⁇ -methylpyrrolidone, etc.).
  • aromatic organic solvents mixture of xylene or alkylbenzenes, chlorobenzene, etc.
  • paraffin paraffin
  • alcohols methanol, propanol, butanol, octane
  • Alcohol glycerol
  • esters ethyl acetate, is
  • Usable surfactants are sodium, calcium, triethylamine, such as alkyl sulfonates, alkyl aryl sulfonates, polyoxyethylene alkyl phenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like. Or triethanolamine salt.
  • composition may also contain special additives for specific purposes, such as containing a binder such as acacia, polyvinyl alcohol, polyvinylpyrrolidone and the like.
  • a binder such as acacia, polyvinyl alcohol, polyvinylpyrrolidone and the like.
  • the concentration of the active ingredient in the above composition may vary widely depending on the active ingredient, the purpose of use, the environmental conditions, and the type of preparation employed.
  • the concentration of the active ingredient is usually in the range of from 0.5 to 90%, preferably from 5 to 60%.
  • compositions may be added to the compositions, such as other acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers.
  • suspending agent The active ingredient content in the commonly used formula is 5% - 35%.
  • the water, the main drug, the dispersing agent, the suspending agent and the antifreezing agent are added to a sand mill and ground to prepare a suspension.
  • Preparation of water emulsion The original drug, solvent and emulsifier are added together to dissolve into a uniform oil phase. Water, antifreeze, and the like are mixed together to form a uniform aqueous phase. The aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase under high-speed agitation to form a water emulsion having good dispersibility.
  • the aqueous emulsion active ingredient of the present invention is generally present in an amount of from 5% to 15%.
  • the compound of the present invention can be dissolved in one or several mixed solvents, and an emulsifier is added to enhance the dispersion of the compound in water.
  • Preparation of wettable powder According to the formulation requirements, the original drug, various surfactants and solid diluents are thoroughly mixed and pulverized by an ultrafine pulverizer to obtain a wettable property of a predetermined content (for example, 10% to 60%). Powder products.
  • the compound of the present invention can be combined with a finely divided solid powder such as clay, A mixture of organic silicates, carbonates, and wetting agents, binders, and/or dispersants.
  • Preparation of water-dispersible granules Mix and pulverize the original drug with powdered solid diluent, wetting spreader and binder, add water and knead, and then add it to a granulator equipped with a certain size sieve. Granulation, then drying and sieving (by screen area).
  • the original drug, dispersing agent, disintegrating agent and wetting agent and solid diluent may also be added to a sand mill, ground with water as a suspending agent, and then spray-dried and granulated, usually in a content of 20%. — 30% granulated product.
  • hydrazine - hydrazine 0.5 g was placed in a 50 ml reaction flask, 25 ml of acetonitrile was added, and 1 ml of aminoethanol was added thereto with stirring, and the mixture was heated under reflux for 15 hours.
  • 50 ml of saturated brine was poured into the reaction flask, and extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.40 g, that is, a compound. 2-2.
  • Example 3 Preparation of Compound 2-5 Take 0.5 g of 2-2 in a 50 ml reaction flask, add 25 ml of dichloromethane, and add 0.17 g of methanesulfonyl chloride and 0.11 g of triethylamine in dichloromethane under ice bath, and add to room temperature. Reaction for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, the reaction flask was poured into 50 ml of saturated brine, extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.39 g. 2-5.
  • ⁇ -I 0.5 g of ⁇ -I was placed in a 50 ml reaction flask, 25 ml of acetonitrile was added, and 1 ml of ethylenediamine was added thereto with stirring, and the mixture was heated under reflux for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, the reaction flask was poured into 50 ml of saturated brine, extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.38 g. 2-18.
  • Compound 2-70 Melting point 211-213 °C. Sppm 2.19(6H, s), 1.28(4H, s), 1.40(4H, s), 3.12(4H, s), 7.30(2H, s), 7.32(2H, s), 7.33(2H, s), 7.55(2H, s), 8.04(2H, d), 8.44(2H, s).
  • Compound 2-75 Melting point 212-214 ° C. ⁇ 2.16(6H, s), 1.24(6H, s), 1.25(6H, s), 1.41(4H, s), 3.30(4H, s), 7.27(2H, s), 7.37(2H, s), 7.50 (2H, m), 8.06 (2H, d), 8.23 (2H, m), 8.43 (2H, d).
  • Compound 2-77 Melting point 191-193 °C. ⁇ 1.60(2H, m), 2.17(6H, s), 3.10(4H, m), 7.30(2H, m), 7.33(2H, s), 7.48(2H, m), 7.58(2H, m), 8.14(2H, m), 8.47(2H, m).
  • Compound 2-80 5ppm 2.19(6H, s), 3.20(4H, m), 7.40(2H, s), 7.54(2H, s), 7.56(2H, m), 8.10(2H, d), 8.25( 2H, s), 8.45 (2H, d).
  • Compound 2-48 and other components are thoroughly mixed and pulverized by an ultrafine pulverizer to obtain a 30% wettable powder product.
  • the compound Table 2-71 and the other components are thoroughly mixed, and the thus obtained suspension concentrate is diluted with water to obtain a diluent of any desired concentration.
  • Example 8 60% water dispersible granules
  • Kaolin is made up to 100%
  • the compound 2-48 and the other components are mixed and pulverized, kneaded by water, and then granulated by a 10-100 mesh sieve granulator, followed by drying and sieving (screen size).
  • Example 9 Determination of insecticidal and acaricidal activity
  • test compound is dissolved in a mixed solvent of acetone/methanol (1:1), it is diluted with water containing 0.1% Tween 80 to a desired concentration.
  • the insecticidal activity was determined by airbrush spray method with P. xylostella, beet armyworm and cotton aphid as targets.
  • the cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher.
  • the airbrush spray treatment pressure was 10 psi (about 0.7 kg/cm 2 ), and the spray was applied to the front and back of each leaf disc.
  • the spray volume was 0.5 ml.
  • 10 test insects (2 years old) were added per treatment, and each treatment was repeated 3 times. After the treatment, the cells were cultured at 24 ° C, relative humidity of 60% to 70%, and without light. After 96 hours, the number of viable animals was investigated, and the mortality was calculated.
  • the concentration of the chemical solution is 1 ppm
  • the mortality rate of 105 et al. was 100%.
  • the compounds 2-48, 2-71, 2-72 and the like have a mortality rate of more than 80% against beet armyworm.
  • the concentration of the chemical solution is 0.1 ppm
  • the mortality of the compounds 2-48, 2-71, 2-72 and the like against Spodoptera exigua is more than 60%.
  • Chlorpyramid, a control drug At a dose of 0.1 ppm, the mortality rate of Spodoptera exigua is 50%.
  • Chloramphenicol home made: melting point 229-230 ° C o 1H NMR (300 MHz, CDC1 3 ) ⁇ 10.10 (s, IH, Ph-H), 8.45 (dd, IH, Pyridin-6-H), 7.85 (dd , IH, Pyridin-4-H), 7.37 (dd, IH, Pyridin-5-H), 7.23 (d, IH, Ph-3-H), 7.21 (d, IH, Ph-5-H), 7.13 (s, IH, Pyrazole), 6.20 (d, IH, H), 2.94 (d, 3H, CH 3 ), 2.17 (s, 3H, Ph-CH 3 ).
  • the chemical structure is as follows:
  • the test method is as follows: Determination of in vitro bactericidal activity: The molten AEA medium is cooled to 60 ° C to 70 ° C, and the quantitative agent is added according to the set concentration to prepare a toxic medium containing different doses. After it was sufficiently cooled, the inoculum of 0.5 cm in diameter was inoculated and placed in an incubator for cultivation. The culture was carried out for 10 days in an incubator, and the growth diameter of each treated colony was measured and the inhibition rate was calculated.
  • Determination of in vivo protective activity A live pot assay was used. The test compound was first dissolved in a small amount of acetone and diluted to the desired concentration with water containing 0.1% Tween 80. The spray was applied to the plant test material, and the disease was inoculated 24 hours later. After inoculation, place the plants in a constant temperature and humidity incubator to continue the infection, after the control is fully ill (usually Conduct an assessment survey for a week).
  • In vitro antibacterial activity assay When the concentration of the drug solution is 25 ppm, the inhibition rate of rice blast by compounds 1-4, 2-10, 2-18, 2-31, etc. is more than 50%. The inhibition rate of rice blast with the control agent chlorantranil at 25 ppm was . .
  • the control agent chlorantranil had a control effect on cucumber downy mildew and anthracnose at a dose of 400 ppm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
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  • Plural Heterocyclic Compounds (AREA)

Abstract

Anthranilamide compounds of formula I with broad-spectrum insecticide activity, wherein the substituents are as defined in the specification. The present compounds have good activity against lepidoptera pests at low dosage, including European corn borer, sugar cane snout moth, apple roller moth, apple budworm, tussock moth, rice leaf roller, maize borer, tabacco moth, small budworm, small plutellid, beet armyworm, tabacoo cutworm and the like, especially small plutellid and beet armyworm. The present compounds also have high activity against homoptera pests, such as aphides. Furthermore, some of said compounds have potent activity as bactericides, and can be useful in controlling rice blast, tomato later blight, cucumber downy mildew and vegetable gray mold.

Description

g甲酰氨基苯甲酰胺类化合物及其应用 技术领域  G-formylaminobenzamide compound and application thereof
本发明属农用杀虫、杀菌剂领域。具体地涉及一种邻甲酰氨基苯甲酰胺类化合物 和组合物， 以及使用它们在农业或其他领域中作为杀虫、 杀菌剂的应用。 背景技术  The invention belongs to the field of agricultural insecticides and fungicides. In particular, it relates to an orthoformylbenzamide compound and composition, and the use thereof as an insecticidal or bactericidal agent in agriculture or other fields. Background technique
无脊椎动物害虫的防治在实现高种植效率中极为重要。无脊椎动物害虫对生长和 贮存的农作物的损害会引起生产率的显著降低， 并因此导致消费者的花费增加。用于 这些目的的许多产品是可购买的， 但是仍然需要更有效、 低成本、 低毒型、 对环境安 全或具有不同作用方式的新化合物。邻甲酰氨基苯甲酰胺类化合物（鱼尼丁受体抑制 剂类） 是近几年开发的防治无脊椎动物害虫的有效杀虫剂。  The control of invertebrate pests is extremely important in achieving high planting efficiency. Damage to growing and stored crops by invertebrate pests can cause a significant reduction in productivity and, consequently, an increase in consumer spending. Many of the products used for these purposes are commercially available, but new compounds that are more efficient, low cost, low toxic, environmentally safe or have different modes of action are still needed. O-formylaminobenzamides (Finedine Receptor Inhibitors) are effective insecticides for the prevention and treatment of invertebrate pests in recent years.
专利 WO03015519中公开了如下具有杀虫活性的化合物：  The following compounds having insecticidal activity are disclosed in the patent WO03015519:
Figure imgf000003_0001
Figure imgf000003_0001
R=CF3,Cl,Br R=CF 3 ,Cl,Br
专利 WO2004033468中公开了如下具有杀虫活性的化合物:  The following compounds having insecticidal activity are disclosed in WO2004033468:
中公开了如下具有杀虫活性的化合物: The following compounds having insecticidal activity are disclosed:
Figure imgf000003_0002
Figure imgf000003_0002
上述专利中所有公开的化合物虽与本发明化合物有一定的相似之处，但结构仍存 在显著的不同， 且文献中所涉及的化合物均未见具有杀菌活性的报道。 发明内容  Although all of the compounds disclosed in the above patents have some similarities with the compounds of the present invention, there are still significant differences in structure, and no reports of bactericidal activity have been reported for the compounds involved in the literature. Summary of the invention
本发明的目的在于提供- -种在很小的剂量下就可以控制各种病虫害的邻氨基苯 甲酸类化合物， 它可应用于农业上以防治作物的病害和虫害。 The object of the present invention is to provide an anthranilic benzene which can control various pests and diseases at a small dose. Formic acid compounds, which can be applied to agriculture to control crop diseases and insect pests.
本发明的技术方案如下：  The technical solution of the present invention is as follows:
本发明提供一种邻甲酰氨基苯甲酰胺类化合物， 如通式 I所示:  The present invention provides an o-formylaminobenzamide compound, as shown in Formula I:
Figure imgf000004_0001
Figure imgf000004_0001
I  I
式中：  In the formula:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 卤素、 氰基、 硝基、 d-C6烷基、 C2-C6烯基、 C2-C6炔基、 卤代 d-C6 烷基、 d-C6烷氧基、 d-C6烷硫基、 d-C6烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基 d-C6烷基、 d-C6烷氧基羰基、 d-C6烷氧基羰基 d-C6烷基或 ^代 d-C6烷氧基 d-C6 烷基； B is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated dC 6 alkyl, dC 6 alkoxy, dC 6 alkane Thio group, dC 6 alkylsulfonyl group, dC 6 alkylcarbonyl group, dC 6 alkoxy dC 6 alkyl group, dC 6 alkoxycarbonyl group, dC 6 alkoxycarbonyl dC 6 alkyl group or ^dC 6 alkoxy group dC 6 alkyl;
C选自氢或卤素；  C is selected from hydrogen or halogen;
« 选自氢、卤素、氰基、硝基、 d-C6烷基、卤代 d-C6烷基、 d-C6烷氧基、 Ci-C6 烷硫基、 d-C6烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基 d-C6烷基、 d-C6烷氧基羰 基、 d-C6烷氧基羰基 d-C6烷基、 卤代 d-C6烷氧基 d-C6烷基、 未取代的或被以下 基团取代的氨基、 氨基 d-C6烷基、 芳基、 芳氧基、 芳基 d-C6烷基、 芳 d-C6烷基 氧基、 杂芳基、 杂芳基 d-C6烷基、 杂芳基 d-C6烷氧基： 卤素、 硝基、 氰基、 d-C6 烷基、 卤代 C C6烷基、 d-C6烷氧基、 卤代 d-C6烷氧基、 d-C6烷硫基或 d-C6烷 基羰基； «Selected from hydrogen, halogen, cyano, nitro, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, Ci-C 6 alkylthio, dC 6 alkylsulfonyl, dC 6 alkylcarbonyl , dC 6 alkoxy dC 6 alkyl, dC 6 alkoxycarbonyl, dC 6 alkoxycarbonyl dC 6 alkyl, halo dC 6 alkoxy dC 6 alkyl, unsubstituted or substituted by Amino, amino dC 6 alkyl, aryl, aryloxy, aryl dC 6 alkyl, aryl dC 6 alkyloxy, heteroaryl, heteroaryl dC 6 alkyl, heteroaryl dC 6 alkoxy Base: halogen, nitro, cyano, dC 6 alkyl, halo CC 6 alkyl, dC 6 alkoxy, halo dC 6 alkoxy, dC 6 alkylthio or dC 6 alkylcarbonyl;
NH  NH
Jl .CH3 Jl .CH 3
R2选自氢、卤素、 CN、N02、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、 ^ \ 未取代的或被以下基团取代的氨基： 甲基、 二甲基、 乙酰基、 甲磺酰基； R 2 is selected from the group consisting of hydrogen, halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, ^ \ unsubstituted or substituted by the following groups: methyl, dimethyl Base, acetyl, methylsulfonyl;
R3选自卤素、 CS H2、 OCH2CN、 d-C6烷基、 卤代 d-C6烷基、 d-C6烷氧基、 卤代 d-C6烷氧基、 d-C6烷硫基、 卤代 d-C6烷硫基、 d-C6烷磺酰基、 卤代 d-C6 烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基肟基、 d-C6烷氧基 d-C6烷基、 卤代 d-C6 烷氧基 d-C6烷基、 卤代 d-C6烷氧基 d-C6烷氧基、 d-C6烷硫基 d-C6烷基、 卤代 d-C6烷硫基 d-C6烷基、 C2-C6烯氧基、 卤代 C2-C6烯氧基、 OCH2Ph、 d-C6烷基氨 ¾ Ci-C6 \ ί Ci-C6¾¾¾ ¾ Ci-C6 Ci-C6 ¾υ¾ ¾ \ ί Ci-C6 ¾¾ 基氨基、 d-C6烷磺酰基氨基、 ¾代 d-C6烷磺酰基氨基； R4选自氢、 d-C6烷基、 氯代吡啶甲基、 氯代噻唑甲基、 四氢呋喃甲基；R 3 is selected from the group consisting of halogen, CS H 2 , OCH 2 CN, dC 6 alkyl, halogenated dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 alkoxy, dC 6 alkylthio, halogenated dC 6 Alkylthio, dC 6 alkylsulfonyl, halogenated dC 6 alkylsulfonyl, dC 6 alkylcarbonyl, dC 6 alkoxyfluorenyl, dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkoxy, dC 6 alkylthio dC 6 alkyl, halogenated dC 6 alkylthio dC 6 alkyl, C 2 -C 6 alkenyloxy, halogenated C 2 -C 6 alkenyloxy, OCH 2 Ph, dC 6 alkylamine 3⁄4 Ci-C 6 \ ί Ci-C63⁄43⁄43⁄4 3⁄4 Ci-C 6 Ci-C 6 3⁄4υ3⁄4 3⁄4 \ ί Ci-C 6 3⁄43⁄4 ylamino, dC 6 alkylsulfonylamino, 3⁄4 generation dC 6 alkylsulfonylamino; R4 is selected from hydrogen, dC 6 alkyl, chloropyridine, chloromethyl methyl thiazole, methyl tetrahydrofuran;
R5选自 CN d-C4烷基、 卤代 d-C6烷基、 -NHCOCH2CN - HCOCF3 H2CF3 - 0 —CH2C02CH3 -CH(C02Et)2 C¾C即 CH3)2 - CHR6(CH2)nX 当 B不为氢时， R5还可选自氰基取代的 d-C6烷基；R 5 is selected from the group consisting of CN dC 4 alkyl, halogenated dC 6 alkyl, -NHCOCH 2 CN - HCOCF3 H 2 CF 3 - 0 -CH 2 C0 2 CH 3 -CH(C0 2 Et) 2 C3⁄4C ie CH 3)2 - CHR 6 (CH 2 ) nX When B is not hydrogen, R 5 may also be selected from a cyano-substituted dC 6 alkyl group;
¾R5可组成五圆或六圆环； 3⁄4R 5 can form a five or six ring;
选自氢或 C C3烷基； Is selected from hydrogen or CC 3 alkyl;
n选自 0 1-10的整数；  n is selected from an integer of 0 1-10;
X选自 OR7 SR7或 R7R8; X is selected from OR 7 SR 7 or R 7 R 8 ;
R7选自氢、 d-C6烷基、 d-C6卤代烷基、 C3-C6烯基、 C3-C6炔基、 d-C6烷基羰 基、 d-C3卤代烷基羰基、 C2-C6烷氧基羰基、 苯基羰基、 d-C3烷基磺酰基、 d-C3 卤烷基磺酰基、 苯基磺酰基、 d-C6烷基酰氨基、 d-C6烷基硫代酰氨基、 苯基酰氨基 或苯基硫代酰氨基； 所述的苯基的环上的氢还可以被以下基团进一步取代： 卤素、R 7 is selected from the group consisting of hydrogen, dC 6 alkyl, dC 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, dC 6 alkylcarbonyl, dC 3 haloalkylcarbonyl, C 2 -C 6 alkane Oxycarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, dC 3 haloalkylsulfonyl, phenylsulfonyl, dC 6 alkylamido, dC 6 alkylthioamido, phenylamido or benzene a thioamido group; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen,
N02 CN d-C3烷基、 Ci-C3卤代烷基、 C3-C6环烷基、 C3-C6烯基、 C3-C6炔基、 Ci-C6 烷氧烷基、 d-C3烷氧基、 d-C3卤代烷氧基、 d-C6烷基羰基、 d-C6烷氧羰基、 d-C3 烷氨基、 d-C6烷基酰基氨基、 d-C3烷硫基、 d-C3烷基亚磺酰基或 d-C3烷基磺酰 基； 或 Q1-Q14基团之一： N0 2 CN dC 3 alkyl, Ci-C 3 haloalkyl, C 3 -C 6 cycloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, Ci-C 6 alkoxyalkyl, dC 3 alkoxy, dC 3 haloalkoxy, dC 6 alkylcarbonyl, dC 6 alkoxycarbonyl, dC 3 alkylamino, dC 6 alkyl acylamino, dC 3 alkylthio, dC 3 alkylsulfinyl or dC a 3 alkylsulfonyl group; or one of the Q1-Q14 groups:
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0001
Figure imgf000005_0002
Figure imgf000005_0003
Figure imgf000006_0001
Figure imgf000005_0003
Figure imgf000006_0001
Ql l Q12 Q13 Q14 选自氢或 C C3烷基。 Ql l Q12 Q13 Q14 is selected from hydrogen or CC 3 alkyl.
本发明中较为优选的化合物为： 通式 I中  Preferred compounds in the present invention are:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 卤素、 氰基、 d-C3烷基或卤代 d-C3烷基； B is selected from the group consisting of hydrogen, halogen, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
C选自氢或卤素；  C is selected from hydrogen or halogen;
选自卤素、 d-C3烷基或卤代 d-C3烷基； Selected from halogen, dC 3 alkyl or halogenated dC 3 alkyl;
NH  NH
Jl .CH3 Jl .CH 3
R2选自卤素、 CN、N02、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、 ^ \ 未取代的或被以下基团取代的氨基： 甲基、 二甲基、 乙酰基或甲磺酰基； R 2 is selected from halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl, ^ \ unsubstituted or substituted by the following groups: methyl, dimethyl, Acetyl or mesyl;
R3选自卤素、 d-C3烷基、 卤代 d-C3烷基或卤代 d-C3烷氧基； R 3 is selected from halogen, dC 3 alkyl, halogenated dC 3 alkyl or halogenated dC 3 alkoxy;
选自氢或 C C3烷基； Selected from hydrogen or CC 3 alkyl;
_ /~  _ /~
R5选自 CN、 d-C4烷基、 卤代 d-C3烷基、 _NHCH2CF3、 — U、 .CH2Co2CH3 -CH(C02Et)2、 -CH2CH(OCH3)2 或一 CHR6(CH2)nX ; 当 B不为氢时， R5还可选自氰基 取代的 d-C3烷基； R 5 is selected from CN, dC 4 alkyl, dC 3 haloalkyl group, _NHCH 2 CF 3, -. U, CH2C o 2 CH 3 -CH (C0 2 Et) 2, -CH 2 CH (OCH 3) 2 Or a CHR 6 (CH 2 ) nX ; when B is not hydrogen, R 5 may also be selected from a cyano-substituted dC 3 alkyl group;
Re选自氢或甲基；  Re is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 d-C3烷基、 C3-C6炔基、 d-C3烷基羰基、 d-C3卤代烷基羰基、 苯 基羰基、 d-C3烷基磺酰基、 苯基磺酰基、 d-C4烷基酰氨基、 d-C4烷基硫代酰氨基、 苯基酰氨基或苯基硫代酰氨基； 所述的苯基的环上的氢还可以被以下基团进一步取 代： 卤素、 N02、 CN、 C1-C3烷基、 d-C3卤代烷基、 d-C3烷氧基、 d-C3卤代烷氧 基； 或 Q1-Q14基团之一； R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, C 3 -C 6 alkynyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkane Alkylamino, dC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen, N0 2 , CN , C1-C3 alkyl, dC 3 haloalkyl, dC 3 alkoxy, dC 3 haloalkoxy; Q1-Q14 or one of the groups;
选自氢或 C C3烷基。 Selected from hydrogen or CC 3 alkyl.
本发明进一步优选的化合物为： 通式 I中  Further preferred compounds of the invention are:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 Cl、 Br、 氰基、 d-C3烷基或卤代 d-C3烷基； B is selected from the group consisting of hydrogen, Cl, Br, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
C选自氢、 Cl、 Br或 F; Ri选自 Cl、 Br、 I或 CH3 ; C is selected from the group consisting of hydrogen, Cl, Br or F; Ri is selected from Cl, Br, I or CH 3 ;
R2选自 Cl、 Br、 I或 CN; R 2 is selected from Cl, Br, I or CN;
R3选自 Cl、 Br、 CH3、 CF3CH20; R 3 is selected from the group consisting of Cl, Br, CH 3 , CF 3 CH 2 0;
R4选自氢或 C C3烷基； R4 is selected from hydrogen or CC 3 alkyl;
_ /~  _ /~
R5选自 CN、 C1-C4烷基、 CH2CF3 -CH2CH2C1、 - HCH2CF3 _N^°、 -CH2C02CH3 R 5 is selected from the group consisting of CN, C1-C4 alkyl, CH 2 CF 3 -CH 2 CH 2 C1, -HCH 2 CF 3 _N ^°, -CH 2 C0 2 CH 3
^ -CHR6(CH2)nX . 当 β不为氢时， R5还选自 CH2CN; ^ -CHR 6 (CH 2 )nX . When β is not hydrogen, R 5 is also selected from CH 2 CN;
R6选自氢或甲基；  R6 is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 d-C3烷基、 炔丙基、 d-C3烷基羰基、 d-C3卤代烷基羰基、 苯基羰 基、 d-C3烷基磺酰基、 苯基磺酰基、 d-C4烷基酰氨基、 d-C4烷基硫代酰氨基、 苯 基酰氨基或苯基硫代酰氨基； 所述的苯基的环上的氢还可以被以下基团进一步取代：R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, propargyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkylamido, DC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups:
Cl、 CN、 CF3、 CF3O; 或 Q1-Q10基团之一； Cl, CN, CF 3 , CF3O; or one of the Q1-Q10 groups;
选自氢或甲基。  Selected from hydrogen or methyl.
本发明更进一步优选的化合物为： 通式 I中  Further preferred compounds of the invention are:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 Cl、 氰基、 CH3或 CF3 ; B is selected from the group consisting of hydrogen, Cl, cyano, CH 3 or CF 3 ;
C选自氢或 C1;  C is selected from hydrogen or C1;
Ri选自 C1或 CH3 ; Ri is selected from C1 or CH 3 ;
R2选自 Cl、 Br或 CN; R 2 is selected from Cl, Br or CN;
R3选自 CI或 Br; R 3 is selected from CI or Br;
R4选自氢或 C C3烷基； R4 is selected from hydrogen or CC 3 alkyl;
_ /~\  _ /~\
R5选自 CN、 d-C4烷基、 CH2CF3、 -CH2CH2C1、 - HCH2CF3 _N^°、 -CH2C02CH3 ^ -CHR6(CH2)nX . 当 β不为氢时， R5还可选自 CH2CN; R 5 is selected from the group consisting of CN, dC 4 alkyl, CH 2 CF 3 , -CH 2 CH 2 C1, -HCH 2 CF 3 _N ^°, -CH 2 C0 2 CH 3 ^ -CHR 6 (CH 2 )nX . When β is not hydrogen, R 5 may also be selected from CH 2 CN;
Re选自氢或甲基；  Re is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 CrC3烷基、 炔丙基、 CH3CO、 C1CH2C0、 CH3S02、 C2H5S02、 苯基 羰基、 苯基磺酰基、 甲酰氨基、 丙基硫代酰氨基、 苯基酰氨基或苯基硫代酰氨基； 所 述的苯基的环上的氢还可以被以下基团进一步取代： Cl、 CF3、 CF3O; 或 Q1-Q10基 团之一； R 7 is selected from the group consisting of hydrogen, CrC 3 alkyl, propargyl, CH 3 CO, C1CH 2 C0, CH 3 S0 2 , C 2 H 5 S0 2 , phenylcarbonyl, phenylsulfonyl, formylamino, propyl Thioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by a group: Cl, CF 3 , CF 3 O; or a Q 1 -Q 10 group One;
选自氢或甲基。  Selected from hydrogen or methyl.
上面给出的通式 I化合物的定义中， 汇集所用术语一般定义如下： 未取代表示所有取代基都为氢。 In the definitions of the compounds of formula I given above, the terms used in the collection are generally defined as follows: Unsubstituted means that all substituents are hydrogen.
取代的胺基中取代基的数目可为 1~2。  The number of substituents in the substituted amine group may be from 1 to 2.
卤： 指氟、 氯、 溴或碘。  Halogen: Refers to fluorine, chlorine, bromine or iodine.
烷基： 直链或支链烷基， 例如甲基、 乙基、 丙基、 异丙基或叔丁基。  Alkyl: a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl or t-butyl.
卤代烷基： 直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤原子所取 代， 例如， 卤代烷基诸如氯甲基、 二氯甲基、 三氯甲基、 氟甲基、 二氟甲基或三氟甲 基。  Haloalkyl: a straight or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, a haloalkyl group such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl Base, difluoromethyl or trifluoromethyl.
烯基： 直链或支链并可在任何位置上存在有双键， 例如乙烯基或烯丙基。  Alkenyl: straight or branched and may have a double bond at any position, such as a vinyl or allyl group.
炔基： 直链或支链并可在任何位置上存在有三键， 例如乙炔基或炔丙基。  Alkynyl: straight or branched and may have a triple bond at any position, such as ethynyl or propargyl.
在本发明的化合物中， 由于碳-碳双键和碳-氮双键连接不同的取代基而可以形成 立体异构体 (分别以 Z和 E来表示不同的构型)。本发明包括 Z型异构体和 E型异构体 及其任何比例的混合物。  In the compound of the present invention, a stereoisomer can be formed due to a carbon-carbon double bond and a carbon-nitrogen double bond connecting different substituents (different configurations are represented by Z and E, respectively). The present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
可以用下面表中列出的化合物来说明本发明， 但并不限定本发明。  The invention may be illustrated by the compounds listed in the following tables, but does not limit the invention.
表 1 部分通式 I化合物的结构  Table 1 Structure of some of the compounds of formula I
(A=N, R5不为 _CH R6(CH2)nX时） (A=N, R 5 is not _ CH R 6( CH 2) nX )
Figure imgf000008_0001
Figure imgf000008_0001
编号 Ri R2 R3 R4 R5 B C Number Ri R 2 R 3 R4 R 5 BC
CH3 H CI H CN H HCH 3 H CI H CN HH
CH3 H Br H CN H HCH 3 H Br H CN HH
CH3 CI CI H CN H HCH 3 CI CI H CN HH
CH3 CI Br H CN H HCH 3 CI Br H CN HH
CH3 CI CF3 H CN H HCH 3 CI CF 3 H CN HH
CH3 Br CI H CN H HCH 3 Br CI H CN HH
CH3 Br Br H CN H HCH 3 Br Br H CN HH
CH3 I CI H CN H HCH 3 I CI H CN HH
CH3 I Br H CN H HCH 3 I Br H CN HH
CH3 CN CI H CN H H CH 3 CN CI H CN HH
Figure imgf000009_0001
Figure imgf000009_0001
Figure imgf000010_0001
Figure imgf000010_0001
CH3 CI Br H CH3 CI HCH 3 CI Br H CH 3 CI H
CH3 CI CI H i-Pr CI HCH 3 CI CI H i-Pr CI H
CH3 CI Br H i-Pr CI HCH 3 CI Br H i-Pr CI H
CH3 CI CI H CN CI HCH 3 CI CI H CN CI H
CH3 CI Br H CN CI HCH 3 CI Br H CN CI H
CH3 CI CI H CH3 CI CICH 3 CI CI H CH 3 CI CI
CH3 CI Br H CH3 CI CICH 3 CI Br H CH 3 CI CI
CH3 CI CI H i-Pr CI CICH 3 CI CI H i-Pr CI CI
CH3 CI Br H i-Pr CI CICH 3 CI Br H i-Pr CI CI
CH3 CI CI H CN CI CICH 3 CI CI H CN CI CI
CH3 CI Br H CN CI CICH 3 CI Br H CN CI CI
CH3 CI CI H CH2CF3 CI CICH 3 CI CI H CH 2 CF 3 CI CI
CH3 CI Br H CH2CF3 CI CICH 3 CI Br H CH 2 CF 3 CI CI
CH3 CI CI H CH2CN CI CICH 3 CI CI H CH 2 CN CI CI
CH3 CI Br H CH2CN CI CICH 3 CI Br H CH 2 CN CI CI
CH3 CN CI H CH3 CI CICH 3 CN CI H CH 3 CI CI
CH3 CN Br H CH3 CI CICH 3 CN Br H CH 3 CI CI
CH3 CI CI H CH3 CN HCH 3 CI CI H CH 3 CN H
CH3 CI Br H CH3 CN HCH 3 CI Br H CH 3 CN H
CH3 CI CI H i-Pr CN HCH 3 CI CI H i-Pr CN H
CH3 CI Br H i-Pr CN HCH 3 CI Br H i-Pr CN H
CH3 CI CI H CN CN HCH 3 CI CI H CN CN H
CH3 CI Br H CN CN HCH 3 CI Br H CN CN H
CH3 CI CI H CH2CF3 CN HCH 3 CI CI H CH 2 CF 3 CN H
CH3 CI Br H CH2CF3 CN HCH 3 CI Br H CH 2 CF 3 CN H
CH3 CI CI H CH2CN CN HCH 3 CI CI H CH 2 CN CN H
CH3 CI Br H CH2CN CN HCH 3 CI Br H CH 2 CN CN H
CH3 CI CI H CH3 CH3 HCH 3 CI CI H CH 3 CH 3 H
CH3 CI Br H CH3 CH3 HCH 3 CI Br H CH 3 CH 3 H
CH3 CI CI H i-Pr CH3 HCH 3 CI CI H i-Pr CH 3 H
CH3 CI Br H i-Pr CH3 HCH 3 CI Br H i-Pr CH 3 H
CH3 CI CI H CN CH3 HCH 3 CI CI H CN CH 3 H
CH3 CI Br H CN CH3 HCH 3 CI Br H CN CH 3 H
CH3 CI CI H CH2CF3 CH3 H CH3 CI Br H CH2CF3 CH3 HCH 3 CI CI H CH 2 CF 3 CH 3 H CH 3 CI Br H CH 2 CF 3 CH 3 H
CH3 CI CI H CH2CN CH3 HCH 3 CI CI H CH 2 CN CH 3 H
CH3 CI Br H CH2CN CH3 HCH 3 CI Br H CH 2 CN CH 3 H
CH3 CN Br H CH3 CH3 HCH 3 CN Br H CH 3 CH 3 H
CH3 CN Br H CH3 CH3 H 表 2 部分通式 I化合物的结构 CH 3 CN Br H CH 3 CH 3 H Table 2 Structure of the compound of formula I
(A=N, B和 C都为氢， R5为 _CHR6(CH2)nX时） (A=N, B and C are both hydrogen, and R 5 is _CHR 6 (CH 2 )nX)
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
CH3 CN Br H H 1 NHQ9
Figure imgf000014_0001
CH 3 CN Br HH 1 NHQ 9
CH3 CN Br H H 5 NHQ9 CH 3 CN Br HH 5 NHQ 9
CH3 CN Br H H 1 NHQ10 CH 3 CN Br HH 1 NHQ 10
CH3 CN Br H H 5 NHQ10 CH 3 CN Br HH 5 NHQ 10
CH3 CN Br H H 1 NHQ2 CH 3 CN Br HH 1 NHQ 2
CH3 CN Br H H 2 NHQ2 CH 3 CN Br HH 2 NHQ 2
CH3 CN Br H H 3 NHQ2 CH 3 CN Br HH 3 NHQ 2
CH3 CN Br H H 4 NHQ2 CH 3 CN Br HH 4 NHQ 2
CH3 CN Br H H 5 NHQ2 CH 3 CN Br HH 5 NHQ 2
CH3 CN Br H H 6 NHQ2 CH 3 CN Br HH 6 NHQ 2
CH3 CN Br H H 7 NHQ2 CH 3 CN Br HH 7 NHQ 2
CH3 CN Br H H 8 NHQ2 CH 3 CN Br HH 8 NHQ 2
CH3 CN Br H H 9 NHQ2 CH 3 CN Br HH 9 NHQ 2
CI CI Br H H 1 NHQ5 CI CI Br HH 1 NHQ 5
CI CI Br H H 3 NHQ5 CI CI Br HH 3 NHQ 5
CI CI Br H H 4 NHQ5 CI CI Br HH 4 NHQ 5
CI CI Br H H 5 NHQ5 CI CI Br HH 5 NHQ 5
CH3 CI Br H H 2 NHQ2 CH 3 CI Br HH 2 NHQ 2
CH3 CI Br H H 3 NHQ2 CH 3 CI Br HH 3 NHQ 2
CH3 CI Br H H 4 NHQ2 CH 3 CI Br HH 4 NHQ 2
CH3 CI Br H H 6 NHQ2 CH 3 CI Br HH 6 NHQ 2
CH3 CI Br H H 7 NHQ2 CH 3 CI Br HH 7 NHQ 2
CH3 CI Br H H 2 NHQ3 CH 3 CI Br HH 2 NHQ 3
CH3 CI Br H H 3 NHQ3 CH 3 CI Br HH 3 NHQ 3
CH3 CI Br H H 4 NHQ3 CH 3 CI Br HH 4 NHQ 3
CH3 CI Br H H 6 NHQ3 CH 3 CI Br HH 6 NHQ 3
CH3 CI Br H H 7 NHQ3 CH 3 CI Br HH 7 NHQ 3
CH3 CI Br H H 2 NHQ4 CH 3 CI Br HH 2 NHQ 4
CH3 CI Br H H 3 NHQ4 CH 3 CI Br HH 3 NHQ 4
CH3 CI Br H H 4 NHQ4 CH 3 CI Br HH 4 NHQ 4
CH3 CI Br H H 6 NHQ4 CH 3 CI Br HH 6 NHQ 4
CH3 CI Br H H 7 NHQ4 CH 3 CI Br HH 7 NHQ 4
CH3 CI Br H H 2 NHQ5 CH 3 CI Br HH 2 NHQ 5
CH3 CI Br H H 3 NHQ5 CH3 CI Br H H 4 NHQ5 CH 3 CI Br HH 3 NHQ 5 CH 3 CI Br HH 4 NHQ 5
CH3 CI Br H H 6 NHQ5 CH 3 CI Br HH 6 NHQ 5
CH3 CI Br H H 7 NHQ5 CH 3 CI Br HH 7 NHQ 5
CH3 CI Br H H 2 NHQ6 CH 3 CI Br HH 2 NHQ 6
CH3 CI Br H H 3 NHQ6 CH 3 CI Br HH 3 NHQ 6
CH3 CI Br H H 4 NHQ6 CH 3 CI Br HH 4 NHQ 6
CH3 CI Br H H 6 NHQ6 CH 3 CI Br HH 6 NHQ 6
CH3 CI Br H H 7 NHQ6 CH 3 CI Br HH 7 NHQ 6
CH3 CI Br H H 2 NHQ7 CH 3 CI Br HH 2 NHQ 7
CH3 CI Br H H 3 NHQ7 CH 3 CI Br HH 3 NHQ 7
CH3 CI Br H H 4 NHQ7 CH 3 CI Br HH 4 NHQ 7
CH3 CI Br H H 6 NHQ7 CH 3 CI Br HH 6 NHQ 7
CH3 CI Br H H 7 NHQ7 CH 3 CI Br HH 7 NHQ 7
CH3 CI Br H H 2 NHQ8 CH 3 CI Br HH 2 NHQ 8
CH3 CI Br H H 3 NHQ8 CH 3 CI Br HH 3 NHQ 8
CH3 CI Br H H 4 NHQ8 CH 3 CI Br HH 4 NHQ 8
CH3 CI Br H H 6 NHQ8 CH 3 CI Br HH 6 NHQ 8
CH3 CI Br H H 7 NHQ8 CH 3 CI Br HH 7 NHQ 8
CH3 CI Br H H 2 NHQ9 CH 3 CI Br HH 2 NHQ 9
CH3 CI Br H H 3 NHQ9 CH 3 CI Br HH 3 NHQ 9
CH3 CI Br H H 4 NHQ9 CH 3 CI Br HH 4 NHQ 9
CH3 CI Br H H 6 NHQ9 CH 3 CI Br HH 6 NHQ 9
CH3 CI Br H H 7 NHQ9 CH 3 CI Br HH 7 NHQ 9
CH3 CI Br H H 2 NHQ10 CH 3 CI Br HH 2 NHQ 10
CH3 CI Br H H 3 NHQ10 CH 3 CI Br HH 3 NHQ 10
CH3 CI Br H H 4 NHQ10 CH 3 CI Br HH 4 NHQ 10
CH3 CI Br H H 6 NHQ10 CH 3 CI Br HH 6 NHQ 10
CH3 CI Br H H 7 NHQ10 CH 3 CI Br HH 7 NHQ 10
CH3 CN Br H H 1 NHQ3 CH 3 CN Br HH 1 NHQ 3
CH3 CN Br H H 2 NHQ3 CH 3 CN Br HH 2 NHQ 3
CH3 CN Br H H 3 NHQ3 CH 3 CN Br HH 3 NHQ 3
CH3 CN Br H H 4 NHQ3 CH 3 CN Br HH 4 NHQ 3
CH3 CN Br H H 5 NHQ3 CH 3 CN Br HH 5 NHQ 3
CH3 CN Br H H 6 NHQ3 CH3 CN Br H H 7 NHQ3 CH 3 CN Br HH 6 NHQ 3 CH 3 CN Br HH 7 NHQ 3
CH3 CN Br H H 1 NHQ4 CH 3 CN Br HH 1 NHQ 4
CH3 CN Br H H 2 NHQ4 CH 3 CN Br HH 2 NHQ 4
CH3 CN Br H H 3 NHQ4 CH 3 CN Br HH 3 NHQ 4
CH3 CN Br H H 4 NHQ4 CH 3 CN Br HH 4 NHQ 4
CH3 CN Br H H 5 NHQ4 CH 3 CN Br HH 5 NHQ 4
CH3 CN Br H H 6 NHQ4 CH 3 CN Br HH 6 NHQ 4
CH3 CN Br H H 7 NHQ4 CH 3 CN Br HH 7 NHQ 4
CH3 CN Br H H 2 NHQ5 CH 3 CN Br HH 2 NHQ 5
CH3 CN Br H H 3 NHQ5 CH 3 CN Br HH 3 NHQ 5
CH3 CN Br H H 4 NHQ5 CH 3 CN Br HH 4 NHQ 5
CH3 CN Br H H 6 NHQ5 CH 3 CN Br HH 6 NHQ 5
CH3 CN Br H H 7 NHQ5 CH 3 CN Br HH 7 NHQ 5
CH3 CN Br H H 2 NHQ6 CH 3 CN Br HH 2 NHQ 6
CH3 CN Br H H 3 NHQ6 CH 3 CN Br HH 3 NHQ 6
CH3 CN Br H H 4 NHQ6 CH 3 CN Br HH 4 NHQ 6
CH3 CN Br H H 6 NHQ6 CH 3 CN Br HH 6 NHQ 6
CH3 CN Br H H 7 NHQ6 CH 3 CN Br HH 7 NHQ 6
CH3 CN Br H H 2 NHQ6 CH 3 CN Br HH 2 NHQ 6
CH3 CN Br H H 3 NHQ6 CH 3 CN Br HH 3 NHQ 6
CH3 CN Br H H 4 NHQ6 CH 3 CN Br HH 4 NHQ 6
CH3 CN Br H H 6 NHQ6 CH 3 CN Br HH 6 NHQ 6
CH3 CN Br H H 7 NHQ6 CH 3 CN Br HH 7 NHQ 6
CH3 CN Br H H 2 NHQ7 CH 3 CN Br HH 2 NHQ 7
CH3 CN Br H H 3 NHQ7 CH 3 CN Br HH 3 NHQ 7
CH3 CN Br H H 4 NHQ7 CH 3 CN Br HH 4 NHQ 7
CH3 CN Br H H 6 NHQ7 CH 3 CN Br HH 6 NHQ 7
CH3 CN Br H H 7 NHQ7 CH 3 CN Br HH 7 NHQ 7
CH3 CN Br H H 2 NHQ8 CH 3 CN Br HH 2 NHQ 8
CH3 CN Br H H 3 NHQ8 CH 3 CN Br HH 3 NHQ 8
CH3 CN Br H H 4 NHQ8 CH 3 CN Br HH 4 NHQ 8
CH3 CN Br H H 6 NHQ8 CH 3 CN Br HH 6 NHQ 8
CH3 CN Br H H 7 NHQ8 CH 3 CN Br HH 7 NHQ 8
CH3 CN Br H H 2 NHQ9
Figure imgf000018_0001
Figure imgf000019_0001
本发明的通式 I化合物可以按照以下方法制备： CH 3 CN Br HH 2 NHQ 9
Figure imgf000018_0001
Figure imgf000019_0001
The compounds of formula I of the present invention can be prepared as follows:
路线 1 : 通式 I化合物可由通式 II所示的恶嗪酮类化合物与取代的胺反应制得:  Route 1 : The compound of formula I can be prepared by reacting an oxazinone compound of the formula II with a substituted amine:
Figure imgf000020_0001
Figure imgf000020_0001
路线 2: 当通式 I化合物中 X为 OR7、 SR7或 NR7R8， 且 R7、 R8都为氢时， 化合 物 I可通过如下反应制得： Scheme 2: When X in the compound of Formula I is OR 7 , SR 7 or NR 7 R 8 , and R 7 and R 8 are both hydrogen, Compound I can be prepared by the following reaction:
Figure imgf000020_0002
Figure imgf000020_0002
Π 路线 3 : 当通式 I化合物中 X为 OR7、 SR7或 NR7R8， 且 为氢、 R7为含羰基、 磺酰基或 Q1-Q14之一时， 还可以由通式 I (X=OH、 SH、 H2) 和对应的酰卤或磺 酰卤 （L是离去基团） 在碱性条件下反应制得： 路线 Route 3: When X in the compound of formula I is OR 7 , SR 7 or NR 7 R 8 and is hydrogen, and R 7 is one of a carbonyl group, a sulfonyl group or a Q1-Q14 , it can also be derived from the formula I (X). =OH, SH, H2) and the corresponding acid halide or sulfonyl halide (L is a leaving group) are obtained by reaction under basic conditions:
nX
Figure imgf000020_0003
nX
Figure imgf000020_0003
X=OH, SH, NH2  X=OH, SH, NH2
I I 反应式中的通式化合物各基团的定义除另有注明外， 同前。  The definitions of the groups of the formulae in the I I reaction formula are as defined above, unless otherwise noted.
反应在溶剂中进行， 适宜的选自如乙腈、 四氢呋喃、 乙醚、 二氯甲烷、 氯仿、 乙 酸乙酯、 二氧六环、 甲苯等。  The reaction is carried out in a solvent, and is suitably selected from, for example, acetonitrile, tetrahydrofuran, diethyl ether, dichloromethane, chloroform, ethyl acetate, dioxane, toluene and the like.
适宜的碱可选自如氢氧化钾、 氢氧化钠、 碳酸钠、 碳酸钾、 碳酸氢钠、 三乙胺、 吡啶、 甲醇钠、 乙醇钠、 氢化钠、 叔丁醇钾或叔丁醇钠等。 反应温度在室温至溶剂沸点温度之间， 通常为 20~100°C。 Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, sodium hydride, potassium t-butoxide or sodium t-butoxide. The reaction temperature is between room temperature and the boiling point of the solvent, usually from 20 to 100 °C.
反应时间为 30分钟至 20小时， 通常 1~10小时。  The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
上述制备方法中所涉及的原料中间体及来源如下：  The raw material intermediates and sources involved in the above preparation methods are as follows:
Figure imgf000021_0001
Figure imgf000021_0001
Π ΠΙ 通式 II为恶嗪酮类化合物由通式 III所示的邻氨基苯甲酸类化合物与通式 IV所示 的羧酸化合物反应制得， 相关综述见 Biorganic and Medicinal Chemistry 2000, 8, 2095-2103.和 J. Heterocyclic Chemistry 1999, 36, 563-588 , 其制备方法参照 WO03015519、 WO2005118552。  Π ΠΙ Formula II is a oxazinone compound prepared by reacting an anthranilic acid compound of the formula III with a carboxylic acid compound of the formula IV. For a review, see Biorganic and Medicinal Chemistry 2000, 8, 2095 -2103. and J. Heterocyclic Chemistry 1999, 36, 563-588, the preparation of which is described in WO03015519, WO2005118552.
通式 III所示的邻氨基苯甲酸类化合物可由芳胺经两步反应制得， 参照如下文献： Organic Syntheses, Coll. Vol.10,p.23(2004); Vol.79,p.196(2002)； Adv. Heterocycl. Chem. 1975, 18, 1-58； Journal of the Brazilian Chemical Society 2001, 12(3), 273-324； Angew.Chem.Int.Ed.Engl.1980, 19, 222-223。 The anthranilic acid compound of the formula III can be obtained by a two-step reaction of an aromatic amine, and is referred to the following literature: Organic Syntheses, Coll. Vol. 10, p . 23 (2004) ; Vol . 79, p. 2002); Adv. Heterocycl. Chem. 1975, 18, 1-58; Journal of the Brazilian Chemical Society 2001, 12(3), 273-324; Angew.Chem.Int.Ed.Engl.1980, 19, 222- 223.
通式 IV所示的羧酸化合物的制备方法参照 WO2006062978、 WO03015519。  For the preparation of the carboxylic acid compound represented by the formula IV, reference is made to WO2006062978 and WO03015519.
本发明的通式 I化合物对农业、 民用和动物技术领域中有害昆虫的成虫、幼虫和 卵都显示出高杀虫活性。 部分化合物表现出较好的杀菌活性。 因此， 本发明还包括通 式 I化合物在农业和其他领域中用作杀虫剂和 /或杀菌剂的应用。  The compound of the formula I of the present invention exhibits high insecticidal activity against adults, larvae and eggs of harmful insects in the fields of agriculture, civil and animal technology. Some of the compounds showed better bactericidal activity. Accordingly, the present invention also encompasses the use of the compound of formula I as an insecticide and/or bactericide in agriculture and other fields.
尤其是， 通式 I化合物对下列科和目的重要害虫有活性： 鳞翅目害虫， 二化螟、 稻纵卷叶螟、 玉米螟、 烟叶蛾、 小食心虫、 小菜蛾、 甜菜夜蛾、 斜纹夜蛾等。 特别是 对小菜蛾、甜菜夜蛾活性更好， 在很低的剂量下就可以获得很好的效果； 本发明对同 翅目的害虫如蚜虫等也具有很高的活性； 同时，本发明的部分化合物还具有很好的杀 菌活性， 可用于防治水稻稻瘟病、 番茄晚疫病、 蔬菜灰霉病、 小麦白粉病、 黄瓜霜霉 病、 炭疽病等， 特别是对水稻稻瘟病、 黄瓜霜霉病、 炭疽病有很好的活性。  In particular, the compounds of formula I are active against important pests of the following families and purposes: lepidopteran pests, stem borer, rice leaf roller, corn borer, tobacco leaf moth, small heartworm, diamondback moth, beet armyworm, twill night Moth and so on. In particular, it is more active against Plutella xylostella and Spodoptera exigua, and it can obtain good effects at very low doses; the present invention also has high activity against pests of the same wing, such as aphids; and at the same time, parts of the present invention The compound also has good bactericidal activity and can be used for controlling rice blast, tomato late blight, vegetable gray mold, wheat powdery mildew, cucumber downy mildew, anthracnose, etc., especially for rice blast, cucumber downy mildew, Anthrax has good activity.
同时， 通式 I化合物对许多有益的昆虫和螨虫、 哺乳动物、 鱼、 鸟具有低毒性， 而且没有植物毒性。  At the same time, the compounds of formula I are less toxic to many beneficial insects and aphids, mammals, fish, birds, and are not phytotoxic.
由于良好的性能， 上述化合物可有利地用于保护农业和园艺业重要的作物、家畜 和种畜， 以及人类常去的环境免于有害昆虫和真菌的伤害。  Due to good performance, the above compounds are advantageously used to protect important crops, livestock and stocks in the agricultural and horticultural industries, as well as the environment frequently experienced by humans from harmful insects and fungi.
为获得理想效果， 化合物的用量因各种因素而改变， 例如所用化合物、被保护的 作物、 有害生物的类型、 感染程度、 气候条件、 施药方法、 采用的剂型。  In order to obtain the desired effect, the amount of the compound varies depending on various factors such as the compound to be used, the crop to be protected, the type of the pest, the degree of infection, the climatic conditions, the method of application, and the dosage form to be employed.
每公顷 10克一 1000克的化合物剂量能提供充分的防治。 本发明的另一目的还涉及通过施用通式 I化合物，防治农业和园艺业重要的作物 和 /或家畜和种畜和 /或人类常去的环境中的昆虫和 /或植物致病性真菌的方法。 尤其 是， 化合物的用量在每公顷 10克一 1000克内变化。 A dose of 10 grams to 1000 grams of compound per hectare provides adequate control. A further object of the invention also relates to a method for controlling insects and/or phytopathogenic fungi in agricultural and horticulturally important crops and/or livestock and breeding stocks and/or environments frequented by humans by the application of the compounds of formula I . In particular, the amount of the compound varies from 10 grams to 1000 grams per hectare.
为了实际应用于农业， 使用含一种或多种通式 I化合物的组合物通常是有益的。 因此，本发明的另一目的涉及含一种或多种通式 I化合物作为活性成分的杀虫和 For practical application in agriculture, it is generally advantageous to use a composition comprising one or more compounds of formula I. Therefore, another object of the invention relates to insecticidal and insecticidal compounds containing one or more compounds of formula I as active ingredients
/或杀菌组合物， 组合物中活性成分的重量百分含量为 0.1-99%。 / or bactericidal composition, the active ingredient in the composition is present in an amount of from 0.1 to 99% by weight.
组合物的使用形式可以是干粉、 可湿性粉剂、 乳油、 微乳剂、 糊剂、 颗粒剂、 溶 液、 悬浮剂等： 组合物类型的选择取决于具体的应用。  The composition may be used in the form of a dry powder, a wettable powder, an emulsifiable concentrate, a microemulsion, a paste, a granule, a solution, a suspension, etc.: The choice of the type of composition depends on the particular application.
组合物是以已知方法制备的，例如任选在表面活性剂的存在下，通过用溶剂介质 和 /或固体稀释剂稀释或溶解活性物质。  The composition is prepared in a known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, optionally in the presence of a surfactant.
可用的固体稀释剂或载体是例如： 二氧化硅、 高岭土、 膨润土、 滑石、 硅藻土、 白云石、 碳酸钙、 氧化镁、 白垩、 粘土、 合成硅酸盐、 硅镁土、 海泡石等。  Useful solid diluents or carriers are, for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicate, attapulgite, sepiolite, etc. .
除水以外，可用的液体稀释剂还包括如芳族有机溶剂（二甲苯或烷基苯的混合物、 氯苯等）， 石蜡 （石油熘分）， 醇类 （甲醇、 丙醇、 丁醇、 辛醇、 甘油）， 酯类 （乙酸 乙酯、 乙酸异丁酯等）， 酮类 （环己酮、 丙酮、 苯乙酮、 异佛尔酮、 乙基戊基酮等）， 酰胺类 （Ν,Ν-二甲基甲酰胺、 Ν-甲基吡咯烷酮等）。  In addition to water, useful liquid diluents include, for example, aromatic organic solvents (mixtures of xylene or alkylbenzenes, chlorobenzene, etc.), paraffin (petroleum), alcohols (methanol, propanol, butanol, octane). Alcohol, glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (Ν, Ν-dimethylformamide, Ν-methylpyrrolidone, etc.).
可用的表面活性剂是烷基磺酸盐、烷基芳基磺酸盐、聚氧乙烯烷基酚、 山梨醇的 聚氧乙烯酯、 木质素磺酸盐等的钠、 钙、 三乙基胺或三乙醇胺盐。  Usable surfactants are sodium, calcium, triethylamine, such as alkyl sulfonates, alkyl aryl sulfonates, polyoxyethylene alkyl phenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like. Or triethanolamine salt.
组合物还可含特殊的添加剂用于特定的目的，例如含有粘合剂如阿拉伯胶、聚乙 烯醇、 聚乙烯吡咯烷酮等。  The composition may also contain special additives for specific purposes, such as containing a binder such as acacia, polyvinyl alcohol, polyvinylpyrrolidone and the like.
上述组合物中活性成分的浓度可根据活性成分、使用目的、环境条件和采用的制 剂类型而在宽范围内改变。 活性成分的浓度范围通常为 0.5— 90 %， 优选 5— 60 %。  The concentration of the active ingredient in the above composition may vary widely depending on the active ingredient, the purpose of use, the environmental conditions, and the type of preparation employed. The concentration of the active ingredient is usually in the range of from 0.5 to 90%, preferably from 5 to 60%.
如果需要，可以向组合物中添加能与通式 I化合物兼容的其他活性成分，例如其 他杀螨剂 /杀虫剂、 杀真菌剂、 植物生长调节剂、 抗生素、 除草剂、 肥料。  If desired, other active ingredients compatible with the compounds of formula I may be added to the compositions, such as other acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers.
几种常见剂型的配制方法举例如下：  Examples of preparation methods for several common dosage forms are as follows:
悬浮剂的配制： 常用配方中活性组分含量为 5%— 35%。 以水为介质， 将原药、 分散剂、 助悬剂和抗冻剂等加入砂磨机中， 进行研磨， 制成悬浮剂。  Preparation of suspending agent: The active ingredient content in the commonly used formula is 5% - 35%. The water, the main drug, the dispersing agent, the suspending agent and the antifreezing agent are added to a sand mill and ground to prepare a suspension.
水乳剂的配制： 将原药、 溶剂和乳化剂加在一起， 使溶解成均匀油相。 将水、 抗 冻剂等混合一起， 成为均一水相。在高速搅拌下， 将水相加入到油相或将油相加入到 水相， 形成分散性良好的水乳剂。 本发明的水乳剂活性组分含量一般为 5%— 15%。 为制备浓乳剂，本发明的化合物可溶解于一种或数种混合溶剂， 再加入乳化剂来增强 化合物在水中的分散效果。  Preparation of water emulsion: The original drug, solvent and emulsifier are added together to dissolve into a uniform oil phase. Water, antifreeze, and the like are mixed together to form a uniform aqueous phase. The aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase under high-speed agitation to form a water emulsion having good dispersibility. The aqueous emulsion active ingredient of the present invention is generally present in an amount of from 5% to 15%. To prepare a concentrated emulsion, the compound of the present invention can be dissolved in one or several mixed solvents, and an emulsifier is added to enhance the dispersion of the compound in water.
可湿性粉剂的配制： 按配方要求， 将原药、各种表面活性剂及固体稀释剂等充分 混合， 经超细粉碎机粉碎后， 即得到预定含量（例如 10%— 60%)的可湿性粉剂产品。 为制备适于喷洒用的可湿性粉剂，本发明的化合物可以和研细的固体粉末如粘土、无 机硅酸盐、 碳酸盐以及润湿剂、 粘合剂和 /或分散剂组成混合物。 Preparation of wettable powder: According to the formulation requirements, the original drug, various surfactants and solid diluents are thoroughly mixed and pulverized by an ultrafine pulverizer to obtain a wettable property of a predetermined content (for example, 10% to 60%). Powder products. In order to prepare a wettable powder suitable for spraying, the compound of the present invention can be combined with a finely divided solid powder such as clay, A mixture of organic silicates, carbonates, and wetting agents, binders, and/or dispersants.
水分散性粒剂的配制： 将原药和粉状固体稀释剂、润湿展着剂及粘合剂等进行混 合粉碎，再加水捏合后，加入装有一定规格筛网的造粒机中进行造粒，然后再经干燥、 筛分 (按筛网范围)。 也可将原药、 分散剂、 崩解剂和润湿剂及固体稀释剂加入砂磨机 中， 以水为介质研磨， 制成悬浮剂， 然后进行喷雾干燥造粒， 通常配制含量为 20%— 30%颗粒状产品。 具体实施方式  Preparation of water-dispersible granules: Mix and pulverize the original drug with powdered solid diluent, wetting spreader and binder, add water and knead, and then add it to a granulator equipped with a certain size sieve. Granulation, then drying and sieving (by screen area). The original drug, dispersing agent, disintegrating agent and wetting agent and solid diluent may also be added to a sand mill, ground with water as a suspending agent, and then spray-dried and granulated, usually in a content of 20%. — 30% granulated product. detailed description
以下具体实施例用来进一步说明本发明， 但本发明绝非仅限于这些例子- 合成实施例  The following specific examples are intended to further illustrate the invention, but the invention is in no way limited to these examples - synthetic examples
实例 1 : 化合物 1-4的制备  Example 1 : Preparation of Compound 1-4
Figure imgf000023_0001
Figure imgf000023_0001
取 0.23克氢化钠于 100毫升反应瓶中，石油醚洗涤两次，加入 40毫升四氢呋喃， 搅拌下加入 H2CN，反应至无气泡放出，再升温至 35°C反应 10分钟，加入 0.5克 II - I (制备见 WO03015519), 搅拌反应 3小时。 TLC监测反应完毕后， 减压脱溶后， 向 反应瓶中倒入 50毫升饱和食盐水，用 60毫升乙酸乙酯分三次进行萃取，干燥，脱溶， 柱层析得产品 0.45克， 即化合物 1-4。 Take 0.23 g of sodium hydride in a 100 ml reaction flask, wash twice with petroleum ether, add 40 ml of tetrahydrofuran, add H 2 CN with stirring, react until no bubbles are released, then heat to 35 ° C for 10 minutes, add 0.5 g II - I (preparation see WO03015519), the reaction was stirred for 3 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, 50 ml of saturated brine was poured into the reaction flask, and extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain 0.45 g of a product. 1-4.
实例 2: 化合物 2-2的制备  Example 2: Preparation of Compound 2-2
Figure imgf000023_0002
Figure imgf000023_0002
II -1 2-2  II -1 2-2
取 0.5克 Π - Ι于 50毫升反应瓶中，加入 25毫升乙腈，搅拌下加入 1毫升的氨基 乙醇， 升温回流反应 15小时。 TLC监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水中， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得 产品 0.40克， 即化合物 2-2。  0.5 g of hydrazine - hydrazine was placed in a 50 ml reaction flask, 25 ml of acetonitrile was added, and 1 ml of aminoethanol was added thereto with stirring, and the mixture was heated under reflux for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, 50 ml of saturated brine was poured into the reaction flask, and extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.40 g, that is, a compound. 2-2.
实例 3 : 化合物 2-5的制备
Figure imgf000024_0001
取 0.5克 2-2于 50毫升反应瓶中， 加入 25毫升二氯甲烷， 冰浴下逐滴加入 0.17 克甲基磺酰氯和 0.11克三乙胺的二氯甲烷混合液， 加毕于室温下反应 15小时。 TLC 监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50毫升饱和食盐水中， 用 60毫升乙 酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得产品 0.39克， 即化合物 2-5。 Example 3: Preparation of Compound 2-5
Figure imgf000024_0001
Take 0.5 g of 2-2 in a 50 ml reaction flask, add 25 ml of dichloromethane, and add 0.17 g of methanesulfonyl chloride and 0.11 g of triethylamine in dichloromethane under ice bath, and add to room temperature. Reaction for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, the reaction flask was poured into 50 ml of saturated brine, extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.39 g. 2-5.
实例 4: 化合物 2-18的制备  Example 4: Preparation of Compound 2-18
Figure imgf000024_0002
Figure imgf000024_0002
取 0.5克 Π - I于 50毫升反应瓶中，加入 25毫升乙腈，搅拌下加入 1毫升的乙二 胺， 升温回流反应 15小时。 TLC监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50 毫升饱和食盐水中， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得产 品 0.38克， 即化合物 2-18。  0.5 g of Π-I was placed in a 50 ml reaction flask, 25 ml of acetonitrile was added, and 1 ml of ethylenediamine was added thereto with stirring, and the mixture was heated under reflux for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, the reaction flask was poured into 50 ml of saturated brine, extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to obtain a product of 0.38 g. 2-18.
实例 5: 化合物 2-48的制备  Example 5: Preparation of Compound 2-48
Figure imgf000024_0003
Figure imgf000024_0003
II -1 2-48 取 0.5克 Π - Ι于 50毫升反应瓶中， 加入 25毫升乙腈， 搅拌下加入 0.03克乙二 ， 升温回流反应 15小时。 TLC监测反应完毕后， 减压脱溶后， 向反应瓶中倒入 50 升饱和食盐水中， 用 60毫升乙酸乙酯分三次进行萃取， 干燥， 脱溶， 柱层析得产 0.32克， 即化合物 2-48。  II -1 2-48 Take 0.5 g of hydrazine - hydrazine in a 50 ml reaction flask, add 25 ml of acetonitrile, add 0.03 g of ethylenediene with stirring, and reflux under reflux for 15 hours. After the TLC monitoring reaction was completed, after decomposing under reduced pressure, 50 L of saturated brine was poured into the reaction flask, and extracted with three times of 60 ml of ethyl acetate, dried, desolvated, and subjected to column chromatography to yield 0.32 g of a compound. 2-48.
通式 I的其他化合物可以用本发明提供的制备方法制得。  Other compounds of formula I can be prepared by the preparation methods provided herein.
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Z£80Z.0/800ZN3/X3d 化合物 2-68：熔点 112-114°C o 5ppm 2.19(6H, s), 1.89(2H, m), 3.20(4H, m), 7.37(2H, s), 7.56(2H, s), 7.60(2H, m), 8.06(2H, d), 8.24(2H, s), 8.45(2H, d)。 Z£80Z.0/800ZN3/X3d Compound 2-68: melting point 112-114 ° C o 5 ppm 2.19 (6H, s), 1.89 (2H, m), 3.20 (4H, m), 7.37 (2H, s), 7.56 (2H, s), 7.60 ( 2H, m), 8.06(2H, d), 8.24(2H, s), 8.45(2H, d).
化合物 2-69：熔点 258-260 °C o 5ppm 2.18(6H, s), 1.42(4H, m), 3.20(4H, m), 7.35(2H, s), 7.52(2H, s)， 7.54(2H, m), 8.06(2H, d), 8.24(2H, s), 8.43(2H, d)。  Compound 2-69: mp 258-260 ° C o 5 ppm 2.18 (6H, s), 1.42 (4H, m), 3.20 (4H, m), 7.35 (2H, s), 7.52 (2H, s), 7.54 ( 2H, m), 8.06(2H, d), 8.24(2H, s), 8.43(2H, d).
化合物 2-70： 熔点 211-213 °C。 Sppm 2.19(6H, s)， 1.28(4H, s), 1.40(4H, s), 3.12(4H, s), 7.30(2H, s), 7.32(2H, s), 7.33(2H, s), 7.55(2H, s), 8.04(2H, d), 8.44(2H, s)。  Compound 2-70: Melting point 211-213 °C. Sppm 2.19(6H, s), 1.28(4H, s), 1.40(4H, s), 3.12(4H, s), 7.30(2H, s), 7.32(2H, s), 7.33(2H, s), 7.55(2H, s), 8.04(2H, d), 8.44(2H, s).
化合物 2-71： 熔点 174-176°C。 5ppm 1.24(4H, s), 1.39(4H, s), 2.16(6H, s), 3.33(4H, s), 7.30(2H, s)， 7.42(2H, s), 7.56(2H, m)， 8.09(2H, d), 8.11(2H, s), 8.45(2H, d)。  Compound 2-71: mp 174-176 ° C. 5ppm 1.24(4H, s), 1.39(4H, s), 2.16(6H, s), 3.33(4H, s), 7.30(2H, s), 7.42(2H, s), 7.56(2H, m), 8.09 (2H, d), 8.11 (2H, s), 8.45 (2H, d).
化合物 2-72：熔点 162-164°C o 5ppm 1.25(6H, s),1.42(4H, s)， 2.18(6H,s), 3.13(4H, s), 7.20(2H, s)， 7.32(2H, s), 7.56(2H, s)， 8.04(2H, d), 8.22(2H, m)， 8.44(2H, s)。  Compound 2-72: mp 162-164 ° C o 5 ppm 1.25 (6H, s), 1.42 (4H, s), 2.18 (6H, s), 3.13 (4H, s), 7.20 (2H, s), 7.32 ( 2H, s), 7.56 (2H, s), 8.04 (2H, d), 8.22 (2H, m), 8.44 (2H, s).
化合物 2-73 : 5ppm 2.18(6H, s)， 1.25(8H, s), 1.43(4H, s)， 3.13(4H, s), 7.29(2H, s), 7.30(2H, s), 7.34(2H, s), 7.56(2H, m), 8.02(2H, d), 8.43(2H, d)。  Compound 2-73: 5ppm 2.18(6H, s), 1.25(8H, s), 1.43(4H, s), 3.13(4H, s), 7.29(2H, s), 7.30(2H, s), 7.34( 2H, s), 7.56(2H, m), 8.02(2H, d), 8.43(2H, d).
化合物 2-74: 207-210°C o 5ppm 1.24(8H, s), 1.42(4H, s)， 2.17(6H, s), 3.14(4H, s), 7.19(2H, s), 7.36(2H, s), 7.56(2H, s), 8.04(2H, d), 8.22(2H, m), 8.43(2H, s)。  Compound 2-74: 207-210°C o 5ppm 1.24(8H, s), 1.42(4H, s), 2.17(6H, s), 3.14(4H, s), 7.19(2H, s), 7.36(2H , s), 7.56(2H, s), 8.04(2H, d), 8.22(2H, m), 8.43(2H, s).
化合物 2-75： 熔点 212-214°C。 δρριη 2.16(6H, s), 1.24(6H, s), 1.25(6H, s), 1.41(4H, s), 3.30(4H, s)， 7.27(2H, s), 7.37(2H, s)， 7.50(2H, m), 8.06(2H, d), 8.23(2H, m), 8.43(2H, d)。  Compound 2-75: Melting point 212-214 ° C. Δρριη 2.16(6H, s), 1.24(6H, s), 1.25(6H, s), 1.41(4H, s), 3.30(4H, s), 7.27(2H, s), 7.37(2H, s), 7.50 (2H, m), 8.06 (2H, d), 8.23 (2H, m), 8.43 (2H, d).
化合物 2-76:熔点 250-252Ό。 Sppm 2.20(6H, s), 3.46(4H, m), 6.91(2H, s)， 6.70(2H， s), 7.14(2H, m), 7.21(2H, m), 7.24(2H, m), 7.77(2H, m), 8.29(2H, m), 9.90(s, 2H)。  Compound 2-76: m.p. 250-252. Sppm 2.20(6H, s), 3.46(4H, m), 6.91(2H, s), 6.70(2H, s), 7.14(2H, m), 7.21(2H, m), 7.24(2H, m), 7.77 (2H, m), 8.29 (2H, m), 9.90 (s, 2H).
化合物 2-77:熔点 191-193 °C。δρρηι 1.60(2H, m), 2.17(6H, s), 3.10(4H, m), 7.30(2H, m), 7.33(2H, s), 7.48(2H, m), 7.58(2H, m), 8.14(2H, m), 8.47(2H, m)。  Compound 2-77: Melting point 191-193 °C. Δρρηι 1.60(2H, m), 2.17(6H, s), 3.10(4H, m), 7.30(2H, m), 7.33(2H, s), 7.48(2H, m), 7.58(2H, m), 8.14(2H, m), 8.47(2H, m).
化合物 2-78：熔点 187-190°C o 5ppm 1.38(4H, m), 2.17(6H, s), 3.07(4H, m), 7.32(2H, m), 7.33 (2H, s), 7.48(2H, m), 7.58(2H, m), 8.15(2H, m), 8.47(2H, m)。  Compound 2-78: mp 187-190 ° C o 5 ppm 1.38 (4H, m), 2.17 (6H, s), 3.07 (4H, m), 7.32 (2H, m), 7.33 (2H, s), 7.48 ( 2H, m), 7.58(2H, m), 8.15(2H, m), 8.47(2H, m).
化合物 2-80： 5ppm 2.19(6H, s)， 3.20(4H, m), 7.40(2H, s)， 7.54(2H, s), 7.56(2H, m)， 8.10(2H, d), 8.25(2H, s), 8.45(2H, d)。  Compound 2-80: 5ppm 2.19(6H, s), 3.20(4H, m), 7.40(2H, s), 7.54(2H, s), 7.56(2H, m), 8.10(2H, d), 8.25( 2H, s), 8.45 (2H, d).
化合物 2-97: 5ppm 1.40(4H, s)， 1.28(4H, s), 2.19(6H, s), 3.36(4H, s), 7.34(2H, s), 7.44(2H, s), 7.60(2H, m), 8.11(2H, d), 8.14(2H, s), 8.49(2H, d)。  Compound 2-97: 5ppm 1.40(4H, s), 1.28(4H, s), 2.19(6H, s), 3.36(4H, s), 7.34(2H, s), 7.44(2H, s), 7.60( 2H, m), 8.11(2H, d), 8.14(2H, s), 8.49(2H, d).
化合物 2-105 : 熔点 171-176°C。 5ppm 1.18 (4H, m), 1.33(4H, m), 3.07(4H, m)， 7.43(2H, s)， 7.46(2H, d), 7.58(2H, m)， 7.84(2H, d), 8.14(2H, d)， 8.47(2H, d)。  Compound 2-105 : melting point 171-176 ° C. 5ppm 1.18 (4H, m), 1.33(4H, m), 3.07(4H, m), 7.43(2H, s), 7.46(2H, d), 7.58(2H, m), 7.84(2H, d), 8.14(2H, d), 8.47(2H, d).
制剂实施例 （各组分加入量均为重量百分含量， 活性化合物折百后计量加入） 实例 6: 30 %可湿性粉剂  Formulation examples (The components are added in a weight percentage, and the active compound is metered in.) Example 6: 30% wettable powder
化合物 2-48 30%  Compound 2-48 30%
十二烷基硫酸钠 2 %  Sodium lauryl sulfate 2 %
木质素磺酸钠 3%  Sodium lignosulfonate 3%
萘磺酸甲醛缩合物 5 % 轻质碳酸钙 补足至 100% Naphthalenesulfonic acid formaldehyde condensate 5% Light calcium carbonate to 100%
将化合物 2-48及其他组分充分混合， 经超细粉碎机粉碎后， 即得到 30%的可湿 性粉剂产品。  Compound 2-48 and other components are thoroughly mixed and pulverized by an ultrafine pulverizer to obtain a 30% wettable powder product.
实例 7: 40%浓悬浮剂  Example 7: 40% concentrated suspending agent
化合物 2-71活性成分 40%  Compound 2-71 Active Ingredient 40%
乙二醇 10%  Ethylene glycol 10%
壬基苯酚聚乙二醇醚 6%  Nonylphenol polyglycol ether 6%
木质素磺酸钠 10%  Sodium lignosulfonate 10%
羧甲基纤维素 1 %  Carboxymethyl cellulose 1 %
37%甲醛水溶液 0.2%  37% formaldehyde solution 0.2%
75 %硅油水乳液 0.8 %  75 % silicone oil emulsion 0.8 %
水 补足至 32%  Water to 32%
化合物表 2-71及其他组分充分混合， 由此得到的浓悬浮剂， 用水稀释所得悬浮 剂可得到任何所需浓度的稀释液。  The compound Table 2-71 and the other components are thoroughly mixed, and the thus obtained suspension concentrate is diluted with water to obtain a diluent of any desired concentration.
实例 8: 60%水分散性粒剂  Example 8: 60% water dispersible granules
化合物 2-48 60%  Compound 2-48 60%
萘磺酸钠甲醛缩合物 12%  Sodium naphthalene sulfonate formaldehyde condensate 12%
N-甲基- N-油酰基-牛磺酸钠 8%  N-methyl-N-oleoyl-taurate sodium 8%
聚乙烯吡咯烷酮 2%  Polyvinylpyrrolidone 2%
羧甲基纤维素 2%  Carboxymethyl cellulose 2%
高岭土 补足至 100%  Kaolin is made up to 100%
将化合物 2-48 及其他组分混合粉碎， 再加水捏合后， 加入 10-100目筛网的造粒 机中进行造粒， 然后再经干燥、 筛分 （筛网范围）。  The compound 2-48 and the other components are mixed and pulverized, kneaded by water, and then granulated by a 10-100 mesh sieve granulator, followed by drying and sieving (screen size).
生物活性测定实施例  Biological activity assay example
实例 9 杀虫杀螨活性测定  Example 9 Determination of insecticidal and acaricidal activity
用本发明化合物对几种昆虫和螨类进行了杀虫活性测定试验。 测定的方法如下： 待测化合物用丙酮 /甲醇（1 : 1 )的混合溶剂溶解后， 用含有 0.1%吐温 80的水稀 释至所需的浓度。  Several insects and mites were tested for insecticidal activity using the compounds of the present invention. The method of measurement is as follows: After the test compound is dissolved in a mixed solvent of acetone/methanol (1:1), it is diluted with water containing 0.1% Tween 80 to a desired concentration.
以小菜蛾、 甜菜夜蛾、 棉蚜为靶标， 采用 airbrush喷雾法进行杀虫活性测定。 将 甘蓝叶片用打孔器打成直径 1 厘米的叶碟， airbrush 喷雾处理的压力为 10 psi (约合 0.7 kg/cm2), 每叶碟正反面喷雾， 喷液量为 0.5毫升。阴干后每处理接入 10头试虫（2 龄）， 每处理 3次重复。处理后放入 24°C、相对湿度 60%〜70%、无光照的室内培养， 96小时后调查存活虫数， 计算死亡率。 The insecticidal activity was determined by airbrush spray method with P. xylostella, beet armyworm and cotton aphid as targets. The cabbage leaves were punched into a 1 cm diameter leaf disc with a puncher. The airbrush spray treatment pressure was 10 psi (about 0.7 kg/cm 2 ), and the spray was applied to the front and back of each leaf disc. The spray volume was 0.5 ml. After the dryness, 10 test insects (2 years old) were added per treatment, and each treatment was repeated 3 times. After the treatment, the cells were cultured at 24 ° C, relative humidity of 60% to 70%, and without light. After 96 hours, the number of viable animals was investigated, and the mortality was calculated.
部分测试结果如下：  Some test results are as follows:
药液浓度为 600ppm时， 化合物 1-4、 1-15、 1-17、 1-19、 1-22、 1-24、 1-30、 1-32、 1- 33、 1-34、 1-51、 1-52、 1-65、 1-66、 2-2、 2-4、 2-5、 2-8、 2-10、 2-17、 2-18、 2-20When the concentration of the chemical solution is 600 ppm, the compounds 1-4, 1-15, 1-17, 1-19, 1-22, 1-24, 1-30, 1-32 1-33, 1-34, 1-51, 1-52, 1-65, 1-66, 2-2, 2-4, 2-5, 2-8, 2-10, 2-17, 2- 18, 2-20
2- 22 2-23 2-24、 2-26 2-29、 2-30、 2-31、 2-35、 2-39、 2-41、 2-48、 2-59、 2-61、 2-63 2-65、 2-67、 2-68、 2-69、 2-70、 2-71、 2-72、 2-73、 2-74、 2-75、 2-80、 2-97、 2-105等对小菜蛾和甜菜夜蛾的死亡率达 100%; 化合物 2-80、 2-97等对棉蚜的死亡 率达 100%。 2- 22 2-23 2-24, 2-26 2-29, 2-30, 2-31, 2-35, 2-39, 2-41, 2-48, 2-59, 2-61, 2 -63 2-65, 2-67, 2-68, 2-69, 2-70, 2-71, 2-72, 2-73, 2-74, 2-75, 2-80, 2-97, The mortality rate of 2-105 et al against Plutella xylostella and Spodoptera exigua is 100%; the mortality of compound 2-80, 2-97 and the like on cotton aphid is 100%.
药液浓度为 lOppm时， 化合物 1-30、 2-2、 2-18等对小菜蛾的死亡率达 100%; 化合物 1-15、 1-19、 1-22、 1-24、 1-32、 2-4 2-8 2-17、 2-65 2-67 2-69 2-70 2-72、 2-105等对甜菜夜蛾的死亡率达 100%。  When the concentration of the drug solution is 10 ppm, the mortality of compounds 1-30, 2-2, 2-18, etc. against Plutella xylostella is 100%; Compounds 1-15, 1-19, 1-22, 1-24, 1-32 2-4 2-8 2-17, 2-65 2-67 2-69 2-70 2-72, 2-105, etc. The mortality rate of beet armyworm is 100%.
药液浓度为 lppm时， 化合物 1-15、 1-19、 1-22、 1-24、 1-32、 2-4、 2-8、 2-67、 2-69、 2-72、 2-105等对甜菜夜蛾的死亡率达 100%。  When the concentration of the chemical solution is 1 ppm, the compounds 1-15, 1-19, 1-22, 1-24, 1-32, 2-4, 2-8, 2-67, 2-69, 2-72, 2- The mortality rate of 105 et al. was 100%.
药液浓度为 0.2ppm时， 化合物 2-48、 2-71、 2-72等对甜菜夜蛾的死亡率在 80% 以上。  When the concentration of the chemical solution is 0.2 ppm, the compounds 2-48, 2-71, 2-72 and the like have a mortality rate of more than 80% against beet armyworm.
药液浓度为 O. lppm时， 化合物 2-48、 2-71、 2-72等对甜菜夜蛾的死亡率在 60% 以上。  When the concentration of the chemical solution is 0.1 ppm, the mortality of the compounds 2-48, 2-71, 2-72 and the like against Spodoptera exigua is more than 60%.
对照药剂氯虫酰胺： 在 O. lppm剂量下， 对甜菜夜蛾的死亡率为 50%。 氯虫酰胺 (自制） ： 熔点 229-230°C o 1HNMR (300 MHz, CDC13) δ 10.10 (s, IH, Ph- H), 8.45 (dd, IH, Pyridin-6-H), 7.85 (dd, IH, Pyridin-4-H), 7.37 (dd, IH, Pyridin-5-H), 7.23 (d, IH, Ph-3-H), 7.21 (d, IH, Ph-5-H), 7.13 (s, IH, Pyrazole), 6.20 (d, IH, H), 2.94 (d, 3H, CH3), 2.17 (s, 3H, Ph-CH3)。 化学结构如下： Chlorpyramid, a control drug: At a dose of 0.1 ppm, the mortality rate of Spodoptera exigua is 50%. Chloramphenicol (home made): melting point 229-230 ° C o 1H NMR (300 MHz, CDC1 3 ) δ 10.10 (s, IH, Ph-H), 8.45 (dd, IH, Pyridin-6-H), 7.85 (dd , IH, Pyridin-4-H), 7.37 (dd, IH, Pyridin-5-H), 7.23 (d, IH, Ph-3-H), 7.21 (d, IH, Ph-5-H), 7.13 (s, IH, Pyrazole), 6.20 (d, IH, H), 2.94 (d, 3H, CH 3 ), 2.17 (s, 3H, Ph-CH 3 ). The chemical structure is as follows:
Figure imgf000029_0001
Figure imgf000029_0001
实例 10 杀菌活性测定  Example 10 Determination of bactericidal activity
用本发明化合物对植物的各种菌病害进行了试验。 试验的方法如下： 离体杀菌活性的测定： 将熔好的 AEA培养基冷却至 60°C〜70°C , 按所设浓度加 入定量药剂， 制成含有不同药量的含毒培养基， 待其充分冷却后， 接种直径为 0.5cm 的病菌菌片， 放置培养箱中培养。 在培养箱中培养 10天后进行调查， 调查时分别测 量每个处理的菌落生长直径， 并计算抑菌率。  Various bacterial diseases of plants were tested using the compounds of the present invention. The test method is as follows: Determination of in vitro bactericidal activity: The molten AEA medium is cooled to 60 ° C to 70 ° C, and the quantitative agent is added according to the set concentration to prepare a toxic medium containing different doses. After it was sufficiently cooled, the inoculum of 0.5 cm in diameter was inoculated and placed in an incubator for cultivation. The culture was carried out for 10 days in an incubator, and the growth diameter of each treated colony was measured and the inhibition rate was calculated.
活体保护活性测定： 采用活体盆栽测定方法。 待测化合物原药用少量丙酮溶解， 用 含有 0.1%吐温 80的水稀释至所需的浓度。 喷雾施药到植物试材上， 24小时后进行病害 接种。 接种后， 将植物放在恒温恒湿培养箱中， 使感染继续， 待对照充分发病后 （通常 为一周时间）进行评估调查。 Determination of in vivo protective activity: A live pot assay was used. The test compound was first dissolved in a small amount of acetone and diluted to the desired concentration with water containing 0.1% Tween 80. The spray was applied to the plant test material, and the disease was inoculated 24 hours later. After inoculation, place the plants in a constant temperature and humidity incubator to continue the infection, after the control is fully ill (usually Conduct an assessment survey for a week).
部分测试结果如下：  Some test results are as follows:
离体抑菌活性测定： 药液浓度为 25ppm时， 化合物 1-4、 2-10、 2-18、 2-31等对水稻 稻瘟病的抑制率达 50%以上。 对照药剂氯虫酰胺在 25ppm剂量下对水稻稻瘟病的抑制率 为。。  In vitro antibacterial activity assay: When the concentration of the drug solution is 25 ppm, the inhibition rate of rice blast by compounds 1-4, 2-10, 2-18, 2-31, etc. is more than 50%. The inhibition rate of rice blast with the control agent chlorantranil at 25 ppm was . .
活体保护活性测定： 药液浓度为 400ppm时， 化合物 2-24、 2-26、 2-67、 2-74等对黄 應霉病防效在 80%以上； 化合物 2-24、 2-26、 2-68、 2-69、 2-74等对炭疽病防效大于 90 Determination of the activity of living body protection: When the concentration of the drug solution is 400 ppm, the compounds 2-24, 2-26, 2-67, 2-74 and the like have a control effect against yellow mold disease of more than 80%; compounds 2-24, 2-26, 2-68, 2-69, 2-74, etc. have an effect on anthrax greater than 90
%。 %.
对照药剂氯虫酰胺在 400ppm剂量下对黄瓜霜霉病、 炭疽病的防效为 0。  The control agent chlorantranil had a control effect on cucumber downy mildew and anthracnose at a dose of 400 ppm.

Claims

种邻甲酰氨基苯甲酰胺类化合物， 如通式 I所示: An o-formylaminobenzamide compound, as shown in Formula I:
Figure imgf000031_0001
Figure imgf000031_0001
I  I
式中：  In the formula:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 卤素、 氰基、 硝基、 d-C6烷基、 C2-C6烯基、 C2-C6炔基、 卤代 d-C6烷 基、 d-C6烷氧基、 d-C6焼硫基、 d-C6烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基 Ci-C6 烷基、 Ci-C6烷氧基羰基、 Ci-C6烷氧基羰基 Ci-C6烷基或卤代 Ci-C6烷氧基 Ci-C6烷基； C选自氢或卤素； B is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 6 alkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, halogenated dC 6 alkyl, dC 6 alkoxy, dC 6焼Thio group, dC 6 alkylsulfonyl group, dC 6 alkylcarbonyl group, dC 6 alkoxy Ci-C 6 alkyl group, Ci-C 6 alkoxycarbonyl group, Ci-C 6 alkoxycarbonyl Ci-C 6 alkyl group Or halogenated Ci-C 6 alkoxy Ci-C 6 alkyl; C is selected from hydrogen or halogen;
选自氢、 卤素、 氰基、 硝基、 d-C6烷基、 卤代 d-C6烷基、 d-C6烷氧基、 d-C6 烷硫基、 d-C6烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基 d-C6烷基、 d-C6烷氧基羰基、 Ci-C6烷氧基羰基 Ci-C6烷基、 卤代 Ci-C6烷氧基 d-C6烷基、未取代的或被以下基团取代 的氨基、 氨基 d-C6烷基、 芳基、 芳氧基、 芳基 d-C6烷基、 芳 d-C6烷基氧基、 杂芳基、 杂芳基 d-C6烷基、 杂芳基 d-C6烷氧基： 卤素、 硝基、 氰基、 d-C6烷基、 卤代 d-C6烷 基、 d-C6烷氧基、 卤代 d-C6烷氧基、 d-C6焼硫基或 d-C6烷基羰基； Selected from hydrogen, halogen, cyano, nitro, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, dC 6 alkylthio, dC 6 alkylsulfonyl, dC 6 alkylcarbonyl, dC 6 Alkoxy dC 6 alkyl, dC 6 alkoxycarbonyl, Ci-C 6 alkoxycarbonyl Ci-C 6 alkyl, halogenated Ci-C 6 alkoxy dC 6 alkyl, unsubstituted or by Substituted amino, amino dC 6 alkyl, aryl, aryloxy, aryl dC 6 alkyl, aryl dC 6 alkyloxy, heteroaryl, heteroaryl dC 6 alkyl, heteroaryl dC 6 alkoxy: halogen, nitro, cyano, dC 6 alkyl, halogenated dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 alkoxy, dC 6 thiol or dC 6 alkylcarbonyl ;
R2选自氢、卤素、 CN、N02、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、
Figure imgf000031_0002
未取代的或被以下基团取代的氨基： 甲基、 二甲基、 乙酰基、 甲磺酰基； R 2 is selected from the group consisting of hydrogen, halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl,
Figure imgf000031_0002
An amino group which is unsubstituted or substituted by the following groups: methyl, dimethyl, acetyl, methylsulfonyl;
R3选自卤素、 CS H2、 OCH2CN、 d-C6烷基、 卤代 d-C6烷基、 d-C6烷氧基、 卤代 d-C6烷氧基、 d-C6烷硫基、 卤代 d-C6烷硫基、 d-C6烷磺酰基、 卤代 d-C6 烷磺酰基、 d-C6烷基羰基、 d-C6烷氧基肟基、 d-C6烷氧基 d-C6烷基、 卤代 d-C6 烷氧基 d-C6烷基、 卤代 d-C6烷氧基 d-C6烷氧基、 d-C6烷硫基 d-C6烷基、 卤代 d-C6烷硫基 d-C6烷基、 C2-C6烯氧基、 卤代 C2-C6烯氧基、 OCH2Ph、 d-C6烷基氨 ¾ Ci-C6 \ ί Ci-C6¾¾¾ ¾ Ci-C6 Ci-C6 ¾υ¾ ¾ \ ί Ci-C6 ¾¾ 基氨基、 d-C6烷磺酰基氨基、 卤代 d-C6烷磺酰基氨基； R 3 is selected from the group consisting of halogen, CS H 2 , OCH 2 CN, dC 6 alkyl, halogenated dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 alkoxy, dC 6 alkylthio, halogenated dC 6 Alkylthio, dC 6 alkylsulfonyl, halogenated dC 6 alkylsulfonyl, dC 6 alkylcarbonyl, dC 6 alkoxyfluorenyl, dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkyl, halogenated dC 6 alkoxy dC 6 alkoxy, dC 6 alkylthio dC 6 alkyl, halogenated dC 6 alkylthio dC 6 alkyl, C 2 -C 6 alkenyloxy, halogenated C 2 -C 6 alkenyloxy, OCH 2 Ph, dC 6 alkylamine 3⁄4 Ci-C 6 \ ί Ci-C63⁄43⁄43⁄4 3⁄4 Ci-C 6 Ci-C 6 3⁄4υ3⁄4 3⁄4 \ ί Ci-C 6 3⁄43⁄4 ylamino, dC 6 alkylsulfonylamino, halogenated dC 6 alkylsulfonylamino;
选自氢、 d-C6烷基、 氯代吡啶甲基、 氯代噻唑甲基、 四氢呋喃甲基； Selected from hydrogen, dC 6 alkyl, chloropyridylmethyl, chlorothiazole methyl, tetrahydrofuranmethyl;
R5选自 CN、 d-C4烷基、 卤代 d-C6烷基、 -NHCOCH2CN、 - HCOCF3 H2CF3 CH2C02CH -CH2CH(OCH3)2 — CHR6(CH2)nX ; 当 B不为氢时， R5还可选自氰基取代的 d-C6烷基；R 5 is selected from the group consisting of CN, dC 4 alkyl, halogenated dC 6 alkyl, -NHCOCH 2 CN, - HCOCF 3 H 2 CF 3 CH 2 CO 2 C H —CH 2 CH(OCH 3 ) 2 — CHR 6 (CH 2 ) nX ; When B is not hydrogen, R 5 may also be selected from a cyano-substituted dC 6 alkyl group;
¾R5可组成五圆或六圆环； 3⁄4R 5 can form a five or six ring;
选自氢或 C C3烷基； Is selected from hydrogen or CC 3 alkyl;
n选自 0 1-10的整数；  n is selected from an integer of 0 1-10;
X选自 OR7 SR7或 R7R8; X is selected from OR 7 SR 7 or R 7 R 8 ;
R7选自氢、 d-C6烷基、 d-C6卤代烷基、 C3-C6烯基、 C3-C6炔基、 d-C6烷基羰基、 Ci- 卤代烷基羰基、 C2-C6烷氧基羰基、苯基羰基、 d-C3烷基磺酰基、 d-C3卤烷基磺酰 基、苯基磺酰基、 d-C6烷基酰氨基、 d-C6烷基硫代酰氨基、苯基酰氨基或苯基硫代酰氨 基； 所述的苯基的环上的氢还可以被以下基团进一步取代： 卤素、 N02 CN d-C3烷基、 Ci- 卤代烷基、 C3-C6环烷基、 C3-C6烯基、 C3-C6炔基、 d-C6烷氧烷基、 d-C3烷氧基、 Ci- 卤代烷氧基、 d-C6烷基羰基、 d-C6烷氧羰基、 d-C3烷氨基、 d-C6烷基酰基氨基、 Ci-C3焼硫基、 d-C3烷基亚磺酰基或 d-C3烷基磺酰基； 或 Q1-Q14基团之一： R 7 is selected from the group consisting of hydrogen, dC 6 alkyl, dC 6 haloalkyl, C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, dC 6 alkylcarbonyl, Ci-haloalkylcarbonyl, C 2 -C 6 alkane Oxycarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, dC 3 haloalkylsulfonyl, phenylsulfonyl, dC 6 alkylamido, dC 6 alkylthioamido, phenylamido or benzene The thiolamino group; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen, NO 2 CN dC 3 alkyl, Ci-haloalkyl, C 3 -C 6 cycloalkyl, C 3- C 6 alkenyl, C 3 -C 6 alkynyl, dC 6 alkoxyalkyl, dC 3 alkoxy, Ci-haloalkoxy, dC 6 alkylcarbonyl, dC 6 alkoxycarbonyl, dC 3 alkylamino , dC 6 alkyl acylamino, Ci-C 3 thiol, dC 3 alkylsulfinyl or dC 3 alkylsulfonyl; or one of Q1-Q14 groups:
Figure imgf000032_0001
Figure imgf000032_0001
Q4 Q5 Q6 Q4 Q5 Q6
Figure imgf000032_0002
Figure imgf000033_0001
Figure imgf000032_0002
Figure imgf000033_0001
Ql l Q12 Q13 Q14 选自氢或 C C3烷基。 Ql l Q12 Q13 Q14 is selected from hydrogen or CC 3 alkyl.
2、 根据权利要求 1所述的化合物， 其特征在于： 通式 I中  2. A compound according to claim 1 wherein:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 卤素、 氰基、 d-C3烷基或卤代 d-C3烷基； B is selected from the group consisting of hydrogen, halogen, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
C选自氢或卤素；  C is selected from hydrogen or halogen;
选自卤素、 d-C3烷基或卤代 d-C3烷基； Selected from halogen, dC 3 alkyl or halogenated dC 3 alkyl;
R2选自卤素、 CN、N02、甲硫基、甲磺酰基、甲氧基羰基、甲胺基羰基、
Figure imgf000033_0002
未取代的或被以下基团取代的氨基： 甲基、 二甲基、 乙酰基或甲磺酰基； R 2 is selected from the group consisting of halogen, CN, NO 2 , methylthio, methylsulfonyl, methoxycarbonyl, methylaminocarbonyl,
Figure imgf000033_0002
An amino group which is unsubstituted or substituted by a group: methyl, dimethyl, acetyl or mesyl;
R3选自卤素、 d-C3烷基、 卤代 d-C3烷基或卤代 d-C3烷氧基； R 3 is selected from halogen, dC 3 alkyl, halogenated dC 3 alkyl or halogenated dC 3 alkoxy;
选自氢或 C C3烷基； Is selected from hydrogen or CC 3 alkyl;
R5选自 CN、 d-C4烷基、 卤代 d-C3烷基、 _NHCH2CF3、 — U、 .CH2Co2CH3 -CH(C02Et)2、 -CH2CH(OCH3)2 或一 CHR6(CH2)nX ; 当 B不为氢时， R5还可选自氰基 取代的 d-C3烷基； R 5 is selected from CN, dC 4 alkyl, dC 3 haloalkyl group, _NHCH 2 CF 3, -. U, CH2C o 2 CH 3 -CH (C0 2 Et) 2, -CH 2 CH (OCH 3) 2 Or a CHR 6 (CH 2 ) nX ; when B is not hydrogen, R 5 may also be selected from a cyano-substituted dC 3 alkyl group;
Re选自氢或甲基；  Re is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 d-C3烷基、 C3-C6炔基、 d-C3烷基羰基、 d-C3卤代烷基羰基、 苯 基羰基、 d-C3烷基磺酰基、 苯基磺酰基、 d-C4烷基酰氨基、 d-C4烷基硫代酰氨基、 苯基酰氨基或苯基硫代酰氨基； 所述的苯基的环上的氢还可以被以下基团进一步取 代： 卤素、 N02、 CN、 C1-C3烷基、 d-C3卤代烷基、 d-C3烷氧基、 d-C3卤代烷氧 基； 或 Q1-Q14基团之一； R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, C 3 -C 6 alkynyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkane Alkylamino, dC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups: halogen, N0 2 , CN , C1-C3 alkyl, dC 3 haloalkyl, dC 3 alkoxy, dC 3 haloalkoxy; Q1-Q14 or one of the groups;
选自氢或 C C3烷基。 Selected from hydrogen or CC 3 alkyl.
3、 根据权利要求 2所述的化合物， 其特征在于： 通式 I中  3. A compound according to claim 2, characterized by:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 Cl、 Br、 氰基、 d-C3烷基或卤代 d-C3烷基； B is selected from the group consisting of hydrogen, Cl, Br, cyano, dC 3 alkyl or halogenated dC 3 alkyl;
C选自氢、 Cl、 Br或 F;  C is selected from the group consisting of hydrogen, Cl, Br or F;
Ri选自 Cl、 Br、 I或 CH3 ; R2选自 Cl、 Br、 I或 CN; Ri is selected from Cl, Br, I or CH 3 ; R 2 is selected from Cl, Br, I or CN;
R3选自 Cl、 Br、 CH3、 CF3CH20; R 3 is selected from the group consisting of Cl, Br, CH 3 , CF 3 CH 2 0;
R4选自氢或 C C3烷基； R4 is selected from hydrogen or CC 3 alkyl;
_ /~  _ /~
R5选自 CN、 d-C4烷基、 CH2CF3、 -CH2CH2C1、 - HCH2CF3 _N^°、 -CH2C02CH3 i¾-CHR6(CH2)nX . 当 β不为氢时， R5还选自 CH2CN; R 5 is selected from the group consisting of CN, dC 4 alkyl, CH 2 CF 3 , -CH 2 CH 2 C1, -HCH 2 CF 3 _N ^°, -CH 2 C0 2 CH 3 i3⁄4-CHR 6 (CH 2 )nX . When β is not hydrogen, R 5 is further selected from CH 2 CN;
R6选自氢或甲基；  R6 is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 d-C3烷基、 炔丙基、 d-C3烷基羰基、 d-C3卤代烷基羰基、 苯基羰 基、 d-C3烷基磺酰基、 苯基磺酰基、 d-C4烷基酰氨基、 d-C4烷基硫代酰氨基、 苯 基酰氨基或苯基硫代酰氨基； 所述的苯基的环上的氢还可以被以下基团进一步取代：R 7 is selected from the group consisting of hydrogen, dC 3 alkyl, propargyl, dC 3 alkylcarbonyl, dC 3 haloalkylcarbonyl, phenylcarbonyl, dC 3 alkylsulfonyl, phenylsulfonyl, dC 4 alkylamido, DC 4 alkylthioamido, phenylamido or phenylthioamido; the hydrogen on the ring of the phenyl group may be further substituted by the following groups:
Cl、 CN、 CF3、 CF3O; 或 Q1-Q10基团之一； Cl, CN, CF 3 , CF3O; or one of the Q1-Q10 groups;
选自氢或甲基。  Selected from hydrogen or methyl.
4、 根据权利要求 3所述的化合物， 其特征在于： 通式 I中  4. A compound according to claim 3, characterized by:
A选自 N或 CH;  A is selected from N or CH;
B选自氢、 Cl、 氰基、 CH3或 CF3 ; B is selected from the group consisting of hydrogen, Cl, cyano, CH 3 or CF 3 ;
C选自氢或 C1;  C is selected from hydrogen or C1;
Ri选自 C1或 CH3 ; Ri is selected from C1 or CH 3 ;
R2选自 Cl、 Br或 CN; R 2 is selected from Cl, Br or CN;
R3选自 CI或 Br; R 3 is selected from CI or Br;
R4选自氢或 C C3烷基； R4 is selected from hydrogen or CC 3 alkyl;
_ /~\  _ /~\
R5选自 CN、 d-C4烷基、 CH2CF3、 -CH2CH2C1、 - HCH2CF3 _N^°、 -CH2C02CH3 ^-CHR6(CH2)nX . 当 β不为氢时， R5还可选自 CH2CN; R 5 is selected from the group consisting of CN, dC 4 alkyl, CH 2 CF 3 , -CH 2 CH 2 C1, -HCH 2 CF 3 _N ^°, -CH 2 C0 2 CH 3 ^-CHR 6 (CH 2 )nX . When β is not hydrogen, R 5 may also be selected from CH 2 CN;
R6选自氢或甲基；  R6 is selected from hydrogen or methyl;
n选自 0、 1-10的整数；  n is selected from 0, an integer from 1 to 10;
X选自 OR7、 SR7、 R7Rs; X is selected from OR 7 , SR 7 , R 7 Rs;
R7选自氢、 CrC3烷基、炔丙基、 CH3CO、 C1CH2C0、 CH3S02、 C2H5S02、苯基羰基、 苯基磺酰基、 甲酰氨基、丙基硫代酰氨基、苯基酰氨基或苯基硫代酰氨基； 所述的苯基的 环上的氢还可以被以下基团进一步取代： Cl、 CF3、 CF3O; 或 Q1-Q10基团之一； R 7 is selected from the group consisting of hydrogen, CrC 3 alkyl, propargyl, CH 3 CO, C1CH 2 C0, CH 3 S0 2 , C 2 H 5 S0 2 , phenylcarbonyl, phenylsulfonyl, formylamino, propyl a thioamido, phenylamido or phenylthioamido group; the hydrogen on the ring of the phenyl group may be further substituted by a group: Cl, CF 3 , CF 3 O; or a Q 1 -Q 10 group One;
选自氢或甲基。  Selected from hydrogen or methyl.
5、 一种按照权利要求 1所述的通式 I化合物在农业或其他领域中防治病菌的应用。 5. Use of a compound of formula I according to claim 1 for controlling pathogens in agriculture or other fields.
6、 一种按照权利要求 1所述的通式 I化合物在农业或其他领域中防治害虫的应用。6. Use of a compound of formula I according to claim 1 for controlling pests in agriculture or other fields.
7、 一种杀虫、 杀菌组合物， 其特征在于： 含有如权利要求 1所述的通式 I化合 物和农业上可接受的载体，组合物中作为活性成分的通式 I化合物的重量百分含量为 0.1-99%。 7. An insecticidal and bactericidal composition, characterized by comprising: a compound of the formula I according to claim 1 and an agriculturally acceptable carrier, the weight percentage of the compound of the formula I as an active ingredient in the composition The content is 0.1-99%.
PCT/CN2008/070832 2007-04-30 2008-04-28 Anthranilamide compounds and the use thereof WO2008134970A1 (en)

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CN2007100111786A CN101298435B (en) 2007-04-30 2007-04-30 O-formammidotiazol-benzamide compounds and use thereof
CN 200710011176 CN101298451B (en) 2007-04-30 2007-04-30 Benzamide compounds and use thereof
CN200710011176.7 2007-04-30
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CN2008100571021A CN101497602B (en) 2008-01-30 2008-01-30 Anthranilic acid compound and use thereof

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