WO2012034472A1 - 一种含氰基的邻苯二甲酰胺类化合物、制备方法和作为农用化学品杀虫剂的用途 - Google Patents

一种含氰基的邻苯二甲酰胺类化合物、制备方法和作为农用化学品杀虫剂的用途 Download PDF

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WO2012034472A1
WO2012034472A1 PCT/CN2011/078711 CN2011078711W WO2012034472A1 WO 2012034472 A1 WO2012034472 A1 WO 2012034472A1 CN 2011078711 W CN2011078711 W CN 2011078711W WO 2012034472 A1 WO2012034472 A1 WO 2012034472A1
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group
substituted
hydrogen
cyano
formula
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PCT/CN2011/078711
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English (en)
French (fr)
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朱冰春
邢家华
许天明
郑志文
陈杰
彭伟立
许勇华
孔小林
魏优昌
董德臻
袁静
韦伟
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中化蓝天集团有限公司
浙江省化工研究院有限公司
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Publication of WO2012034472A1 publication Critical patent/WO2012034472A1/zh

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    • 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
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/34—Nitriles
    • 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
    • A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
    • A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
    • A01N41/10—Sulfones; Sulfoxides
    • 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
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/24—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton
    • C07C255/29—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms containing cyano groups and singly-bound nitrogen atoms, not being further bound to other hetero atoms, bound to the same saturated acyclic carbon skeleton containing cyano groups and acylated amino groups bound to the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C317/00—Sulfones; Sulfoxides
    • C07C317/44—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton
    • C07C317/48—Sulfones; Sulfoxides having sulfone or sulfoxide groups and carboxyl groups bound to the same carbon skeleton the carbon skeleton being further substituted by singly-bound nitrogen atoms, not being part of nitro or nitroso groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
    • C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
    • C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
    • C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
    • C07D307/77—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom ortho- or peri-condensed with carbocyclic rings or ring systems
    • C07D307/87—Benzo [c] furans; Hydrogenated benzo [c] furans
    • C07D307/90—Benzo [c] furans; Hydrogenated benzo [c] furans with an oxygen atom in position 1 and a nitrogen atom in position 3, or vice versa

Definitions

  • the present invention relates to a phthalic acid amide compound, a preparation method and use as an agrochemical insecticide.
  • phthalamide compounds are known to have insecticidal activity (see EP0919542A2, W02004/018410AK W02010/012442A2), in which phthalate is jointly developed by the Japanese pesticide company and Bayer.
  • the formamide compound flubendiamide has good insecticidal activity against a variety of agricultural and horticultural lepidopteran pests (J. Pesticide Sci., 2005, 30(4): 354-360).
  • the replacement of phthalamides as pesticides has caused widespread concern among researchers of pesticide creation and has become a hot spot in the research of new insecticides.
  • An object of the present invention is to provide a cyano group-containing phthalic acid amide compound which can control various pests and diseases at a small dose, and which can be applied to agriculture to control crop diseases and insect pests.
  • the present invention provides the following technical solutions:
  • RR 2 is independently selected from hydrogen, dC 6 ortho, cycloalkyl, C 2 -C 6 alkenyl or ⁇ -alkynyl, and the hydrogen on the group may also be halogen, cyano, nitro, dC a 6- methoxy group, a phenyl group, a substituted phenyl group, a phenoxy group, a substituted phenoxy group, an alkylthio group, an alkylsulfinyl group or a decylsulfonyl group;
  • R 1 and R 2 together with the attached carbon form a cycloalkyl group
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC 6 fluorenyl, halogenated dC 6 fluorenyl, dC 6 decyloxy or halodecyloxy;
  • R 4 is selected from hydrogen or ( ⁇ -(: 6 fluorenyl);
  • X is selected from a methylene group, a dC 6 alkyl group, a cyano substituted methylene group or a direct bond;
  • X and R 4 are bonded to the N to form a three-membered ring, a four-membered ring, a five-membered ring, a six-membered ring, a five-membered heterocyclic ring or a six-membered heterocyclic ring;
  • Y is selected from the group consisting of hydrogen, halogen, cyano, nitro, a hydroxy group, a dC 6 alkyl group, a halogenated dC 6 fluorenyl group, a dC 3 decyloxy group, a halogenated dC 3 decyloxy group, a phenyl group, a substituted phenyl group, a heterocyclic aryl group or a substituted heterocyclic aryl group;
  • A is CH or N
  • n is an integer from 0 to 4.
  • RR 2 is independently selected from hydrogen, alkyl, C 3 -C 6 cyclodecyl or ( 2 -(: 3 alkenyl), phenyl, substituted phenoxy which may also be substituted by hydrogen on the group Further substituted with thiol, decylsulfinyl or decylsulfonyl;
  • R 1 and R 2 together with the attached carbon form a cyclohexyl group
  • R 3 is selected from hydrogen or halogen
  • R 4 is selected from hydrogen or ⁇ - ⁇ fluorenyl
  • X and R 4 are bonded to the N to form a five-membered heterocyclic ring or a six-membered heterocyclic ring;
  • Y is selected from hydrogen, a halogen atom, nitro, hydroxy, burning dC 3-yl, fluorinated alkyl with dC 3, dC 3 alkoxy or fluoro - embankment group;
  • n is an integer of 1 to 3.
  • RR 2 is independently selected from hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allylic.
  • the hydrogen on the group can also be a group such as a substituted phenyl group, a substituted phenoxy group, a methylthio group, a methylsulfinyl group, a methylsulfonyl group or the like;
  • R 3 is selected from fluorine, chlorine, bromine or iodine, and R 3 is at the 3 or 4 position of the benzene ring;
  • R 4 is hydrogen or methyl
  • X is a methylene group, a methyl group, a cyano substituted methylene group or a direct bond
  • X and R 4 are bonded to the N to form an oxygen-containing six-membered heterocyclic ring;
  • Y is selected from the group consisting of hydrogen, fluorine, chlorine, nitro, hydroxy, methyl, methoxy, trifluoromethyl, trifluoromethoxy or heptafluoroisopropyl.
  • the structural formula of the cyano group-containing phthalamide compound represented by the above (I) is:
  • RR 2 , R 3 , R ⁇ A, X, Y and m are defined as a fluorenyl group, which is a linear or branched form, for example, a Bases such as ethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl and the like.
  • Cyclodecyl is meant to include cyclic chain forms such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl and the like.
  • Alkenyl means straight-chain or branched form, such as ethenyl, 1-propenyl, allyl, isopropenyl, 1-butenyl, 1, 3-butadienyl, 1-hexenyl, etc. Group.
  • An alkynyl group means a straight or branched chain form such as an ethynyl group, a 2-butynyl group, a 2-pentynyl group, a 3-hexynyl group or the like.
  • Halogenated fluorenyl refers to a group wherein the fluorenyl group is substituted by one or more halogen atoms.
  • the methoxy group means a group having an oxygen atom bonded to the terminal of the oxime group, for example, a methoxy group, an ethoxy group, a n-propoxy group, an isopropoxy group, a tetrabutoxy group or the like.
  • the haloalkoxy group means a group in which a mercapto group is substituted by one or more halogen atoms and an oxygen atom is bonded to the terminal.
  • the thiol group is a group having a sulfur atom attached to the end of the thiol group, such as a methylthio group, an ethylthio group or the like.
  • the mercaptosulfinyl group means a group having a terminal group of (S0-), such as a methylsulfinyl group.
  • the mercaptosulfonyl group means a group having a terminal (S0 2 - ) at the alkyl group, such as a methylsulfonyl group.
  • Halogen means fluorine, chlorine, bromine or iodine.
  • the cyano group-containing phthalamide compound represented by the formula (I) of the present invention may have, in some cases, one or more asymmetric centers in its structural formula, and in some cases, two or more optical isomerisms. Bulk and diastereomers. The invention also includes all individual optical isomers and mixtures of these isomers in any ratio.
  • the present invention also provides an intermediate for preparing a cyano group-containing phthalamide compound represented by the formula (I), which has the following formula (II) or (III):
  • RR 2 is independently selected from hydrogen, d-alkyl, C 3 -C 6 cyclodecyl, C 2 -C 6 alkenyl or C 2 -C 6 alkynyl, and the hydrogen on the group may also be halogen , cyano, nitro, ( ⁇ -[: 6 methoxy, phenyl, substituted phenyl, phenoxy, substituted phenoxy, alkylthio, alkylsulfinyl or decylsulfonyl further Replace
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, aryl, ester, dC 6 alkyl, halogenated d-Ce fluorenyl, alkoxy or halo-c decyloxy.
  • RR 2 is independently selected from hydrogen, dC 3 fluorenyl, C 3 -C 6 cyclodecyl or C 2 -C 3 alkenyl, and the hydrogen on the group may also be substituted phenyl, substituted phenoxy Further substituted with a thiol group, a fluorenylsulfinyl group or an alkylsulfonyl group;
  • R 1 and R 2 together with the attached carbon form a cyclohexyl group
  • R 3 is selected from hydrogen or halogen.
  • RR 2 are independently selected from hydrogen, methyl, ethyl, isopropyl, cyclopropyl or allyl, hydrogens on the group may also be substituted phenyl, substituted phenoxy, methylthio a group such as a methylsulfinyl group or a methylsulfonyl group;
  • R 3 is selected from fluorine, chlorine, bromine or iodine, and R 3 is located at the 3 or 4 position of the benzene ring.
  • the cyano group-containing phthalamide compound represented by (I) of the present invention can be produced by the following method:
  • RR 2 , R 3 , R 4 , Y and m define a cyano group-containing phthalamide compound represented by the above structural formula (I).
  • the inert solvent in the above step (1) is selected from the group consisting of tetrahydrofuran, acetonitrile, 1, 4-dioxane, hydrazine, hydrazine-dimethylformamide, hydrazine, hydrazine-dimethylacetamide.
  • the base comprising an organic base and an inorganic base, the organic base being selected from the group consisting of triethylamine, pyridine or 3-methylpyridine, the inorganic base being selected From potassium carbonate, sodium hydrogencarbonate, sodium hydroxide or anhydrous sodium acetate;
  • the inert solvent in the above step (2) is selected from the group consisting of toluene, 1,2-dichloroethane, ethyl acetate, tetrahydrofuran, acetonitrile, 1, One or a combination of two or more of 4-dioxane or dichloromethane, the acylating reagent being methyl chloroformate, acetic anhydride or trifluoroacetic anhydride, for each mole of the amide of the formula ( ⁇ )
  • the benzoic acid, the acylating agent may be used in an amount of from 1 mole to the excess mole; the iner
  • the acid includes an organic acid selected from the group consisting of acetic acid, trifluoroacetic acid or p-toluenesulfonic acid, and the inorganic acid is hydrochloric acid or sulfuric acid; the reaction temperature is 0° C. Between the boiling points of the inert solvent used.
  • the reaction time varies depending on the reaction scale and the reaction temperature, and is preferably 2 to 12 hours.
  • the product of the formula (I) can be separated from the reaction mixture by a conventional filtration or the like, and if necessary, separation means such as recrystallization or column chromatography can be used.
  • the product in the above step (1) is acidified, extracted, and concentrated to precipitate a solid, which is washed with a solvent, filtered, and then separated.
  • the substituted phthalic anhydride represented by the formula (VI) used in the above production method is a known compound which can be produced by a number of known methods.
  • Typical compounds represented by the formula (I) of the present invention are listed in the index table 1 and the index table 2, but they are in no way intended to limit the scope of the invention.
  • a typical compound represented by the formula (I) when R 4 is hydrogen and X is a direct bond, a typical compound such as Da) shows:
  • Table 3 shows the nuclear magnetic data of some of the compounds described in Index Table 1 and Index Table 2.
  • the cyano group-containing phthalamide compound represented by the formula (I) of the present invention or an agriculturally applicable salt thereof can be used for an agrochemical insecticide.
  • the agricultural and horticultural pest control agent containing the compound of the present invention is particularly effective for agricultural pests and the like.
  • the agricultural and horticultural pest control agent containing the cyano group-containing phthalamide compound represented by the formula (I) of the present invention is used for controlling organophosphorus, carbamate, pyrethroid, and benzoic acid. Resistant pests such as ureide are effective. Further, the cyano group-containing phthalamide compound represented by the formula (I) of the present invention has excellent osmotic transfer property, and therefore contains a cyano group represented by the formula (I) according to the present invention.
  • the phthalate-based agricultural and horticultural pest control agent is used to treat the soil, and the pests of the stems and leaves can also be controlled while controlling the soil harmful insects, mites and the like.
  • pest control agent containing the cyano group-containing phthalamide compound represented by the formula (I) of the present invention include comprehensive control of the plant parasitic mites and agricultural pests. , pest control agents for agricultural and horticultural use such as soil pests.
  • the cyano group-containing phthalic acid amide compound represented by the formula (I) of the present invention can be used as an active component of a chemical pesticide for pesticides, and is formulated into various liquid preparations, emulsifiable concentrates, suspension concentrates, aqueous suspensions, Microemulsions, (water) emulsions, powders, wettable powders, soluble powders, (water-dispersible) granules or capsules, for pest control of crops such as rice, soybeans, wheat, cotton, corn, vegetables and canola.
  • the weight percentage of the active component that is, the weight percentage of the cyano group-containing phthalamide compound represented by the formula (I) of the present invention is preferably 0. 001%-99. 99% by weight, the balance being an agriculturally acceptable carrier.
  • the carrier can be a solid or a liquid.
  • Suitable solid carriers include natural or synthetic clays and silicates such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminosilicates such as kaolinite, kaolin, montmorillonite and mica; , calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylenediamine.
  • the liquid carrier includes water and an organic solvent, and when water is used as a solvent or a diluent, the organic solvent can also be used as an adjuvant or an antifreezing additive.
  • Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc.; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, Methylene chloride or the like; aliphatic hydrocarbons such as petroleum distillate, cyclohexane, light mineral oil; alcohols such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol; and ethers and esters thereof There are also ketones such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
  • aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, trichloromethane, Methylene chloride or the like
  • aliphatic hydrocarbons such as petroleum distillate, cyclohexane, light
  • the carrier can also be a surfactant.
  • Suitable surfactants can be emulsifiers, dispersants or wetting agents; they can be ionic or nonionic.
  • Nonionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: agricultural milk 2201B, agricultural milk 0203B, agricultural milk 10 (f, agricultural milk 50 ( f, agricultural milk 600 agricultural milk 600- 2 # , agricultural milk 1601, agricultural milk 2201, agricultural milk NP-10, agricultural milk NP- 15, agricultural milk 507*, agricultural milk 0X- 635, agricultural milk 0X-622, agriculture Milk 0X-653, agricultural milk 0X-667, Ning milk 36 s .
  • Dispersing agent includes sodium lignosulfonate, pull-up powder, calcium lignosulfonate, methylnaphthalenesulfonic acid formaldehyde condensate, etc.
  • Wetting agent laurel Sodium sulphate, sodium dodecyl benzene sulfonate, sodium decyl naphthalene sulfonate, and the like.
  • the above pesticide chemical pesticides can be prepared by a general method.
  • the active substance may be mixed with a liquid solvent and/or a solid carrier, and a surfactant such as an emulsifier, a dispersant, a stabilizer, a wetting agent may be added, and other auxiliary agents such as a binder, an antifoaming agent, an oxidizing agent may also be added. Wait.
  • the cyano group-containing phthalamide compound of the present invention can also be used in combination with herbicides, fungicides, nematicides, plant growth regulators, fertilizers, and other pesticides or other agricultural chemicals. .
  • the pesticide preparation of the present invention when applied to a pest to be controlled or a medium for growth thereof, wherein the active component is a cyano group-containing phthalamide represented by formula (I)
  • the effective amount of the compound is from 10 grams to 1000 grams per hectare.
  • the cyano group-containing phthalamide compound represented by the formula (I) of the present invention or an agriculturally applicable salt thereof and a preparation thereof have the following advantages over the prior art:
  • the present invention introduces an ⁇ -amino nitrile functional group in the structure of phthalic acid for the first time, and the structure of the compound is novel;
  • the compound of the present invention and its preparation have an extremely high insecticidal activity: a good effect on lepidopteran pests at a dose of 0.16 mg/L;
  • the compound of the present invention and its preparation have excellent safety, and are safe to some crops such as wheat, soybean, cotton, corn, rice, etc., and are environmentally friendly.
  • the compound of the present invention and its preparation have reasonable toxicity, ecotoxicity and environmental compatibility, and are low-toxic environmentally friendly pesticides. detailed description
  • Step 1 Synthesis of 3-iodo-N-(1methyl-l-cyanoethyl)-amidobenzoic acid
  • Step 2 Synthesis 3-Iodo-N-(1methyl-monocyanoethyl) phthalimide
  • Trifluoroacetic anhydride (0.76 g, 3. 6 mmol) was added to 3-iodo-N-(1methyl-l-cyanoethyl)-amidobenzoic acid (1.07 g, 3 mmol) in 10 mL of toluene In the suspension, the reaction mixture was stirred at room temperature for 30 min. The solvent was removed under reduced pressure to give the title compound.
  • Step 3 Synthesis of 3-iodo-N 1 -(2methyl-tetrafluoropentylphenyl) N 2 —(1methyl-l-cyanoethyl)phthalamide
  • Step 2 Synthesis of 4-chloro-N (1 methyl-mono-cyanoethyl) phthalimide
  • Trifluoroacetic anhydride (1.0 g, 4. 8 mmol) was added to a suspension of 4-chloro-N (1methyl-l-cyanoethyl)-amidobenzoic acid (1. 06 g, 4 mmol) in 12 ml of toluene. The mixture was stirred at room temperature for 30 min. The solvent was removed under reduced pressure to give aq.
  • Step 3 Synthesis of 4-chloro-N 1 - ( 2, 4 - dichlorophenyl) N 2 (1 methyl- 1 - cyanoethyl) phthalic acid amide
  • Example 5 granule formula
  • the insecticidal activity evaluation test was carried out according to the following methods:
  • the screening concentration was from 500, 100, 20, 4.0. 8, 0. 16, 0. 032 mg / L, and the amount of the drug treatment solution was lOmL.
  • the test target was oriental worm (i 'mg separa ta), cotton bollworm (Helico this armigera), Aphis medicagini, PI u tell a xylostella, oofe ⁇ 's litura Spodopterem frugiperda).
  • the corn leaves are fully infiltrated in the liquid, and then dried naturally. They are placed in a petri dish, and the 3rd instar larvae are picked up and placed in the observation room. The test was repeated 4 times. The results were checked after 72 hours. The brush is lightly touched by the worm, and no reaction is considered to be dead.
  • Potted cotton (2-3 leaf age) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the leaves were cut with scissors, placed in a ⁇ 9cm plastic petri dish, and the larvae of the genus Spodoptera or Helicoverpa armigera were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days.
  • Potted cotton (2-3 leaf age) was sprayed with the drug and allowed to dry. Put in the culture room and continue normal culture. After 5, 12, 19d, the leaves were cut with scissors, placed in a ⁇ 9cm plastic petri dish, and the larvae of the genus Spodoptera or Helicoverpa armigera were placed, and a filter paper was placed and capped. Place in the observation room and check the results after 6 days.
  • the numbers described in the biological activity assay examples correspond to the compound numbers described in Index Table 1, Index Table 2, and Table 3.
  • Test Statistics The number of dead insects and live insects in each treatment was counted, and the mortality was calculated.
  • Dead IT rate (%) , x lOO
  • the CK control mortality was ⁇ 20%, the test results were credible, the test results were corrected, and the CK control mortality was ⁇ 5%.
  • the results of the bioassay test indicate that the compound of the present invention has good insecticidal activity, especially for lepidopteran pests such as oriental armyworm, cotton bollworm, diamondback moth, Spodoptera litura, and Spodoptera litura. Active, also has a certain insecticidal activity against Homoptera pests. "mg/L" refers to each mg of active substance per liter.
  • compounds 23, 24, 32, 33, 34, 40, 46, 47, 48, 137 have a mortality rate of more than 80% against Plutella xylostella, and at a concentration of 100 mg/L, compounds 23, 24, 33, 34 46, 47, 48, 137 have a mortality rate of more than 80% against Plutella xylostella.
  • the mortality of compounds 23, 24, 34, 46, 47, 48 against Plutella xylostella is greater than 80%, and the concentration of 4 mg/L is higher.
  • the mortality rate of compound 23, 24, 34, 47, 48 against Plutella xylostella is more than 80%, and the mortality rate of compound 23, 24, 47 against Plutella xylostella is greater than 80%, 0. 16mg/ At the L concentration, the mortality of compounds 24, 47 against Plutella xylostella was 100%.
  • the mortality rate of compounds 23 and 24 against Spodoptera frugiperda was greater than 80%.
  • the mortality rate of compound 24 against Spodoptera frugiperda was 100%.
  • Compound 24 had a mortality rate of 100% against Spodoptera litura.
  • Table 4 shows that compared with the existing compound flubendiamide, when the concentration is greater than 0.16 mg / L, the compound of the present invention has substantially the same insecticidal activity against Plutella xylostella, and exerts a high insecticidal action against Spodoptera litura. Especially at low application rates (0.032 Mg/L), the compounds of the invention are superior to the existing compounds and much higher than the activity of chlorpyrifos and cypermethrin. Based on the structural similarity of these compounds, the result of this increase is unexpected.
  • Compound 24 was subjected to a greenhouse residual activity test, and the results are shown in Table 5. The test results showed that: at 0. 8mg/L, the compound 24 was treated with the test insects 19 days after the drug, and the mortality rate of Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera was still 100%; at 0. 16mg/L, With the prolongation of treatment time, the efficacy was reduced. After 12 days, the drug could still reach 100%. After 19 days, the mortality of Plutella xylostella, Spodoptera frugiperda and Helicoverpa armigera decreased to 60%, 55 % and 80 %, respectively. At 0. 032 mg/L, the efficacy against all three test insects was low. It has a high residual activity on compound 24. Table 5 Compound 24 residual activity test results

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Description

一种含氰基的邻苯二甲酰胺类化合物、 制备方法和 作为农用化学品杀虫剂的用途 技术领域
本发明涉及一种邻苯二甲酰胺类化合物、 制备方法和作为农用化学品杀虫剂的用途。
说
背景技术
目前对病害和虫害防治剂在生态上和经济上的书要求不断提高， 特别是对于施用量、 残留 物的组成、 选择性、 毒性和生产方法的要求不断提高。 由于杀虫剂、 杀菌剂在使用一段时间 后， 害虫、 病菌会对其产生抗性， 因此， 需要开发新颖的具有杀虫、 杀菌活性的化合物和组 合物。
已知多种邻苯二甲酰胺类化合物 （鱼尼丁受体抑制剂类） 具有杀虫活性 （参见 EP0919542A2, W02004/018410AK W02010/012442A2) , 其中由日本农药公司与拜耳公司联合 开发的邻苯二甲酰胺类化合物氟虫酰胺（flubendiamide)对多种农业与园艺鳞翅目害虫有很 好的杀虫活性 (J. Pesticide Sci.， 2005, 30 (4) : 354-360)。 目前， 取代的邻苯二甲酰胺 类化合物作为农药， 已引起农药创制科研人员的普遍关注， 成为新杀虫剂创制研究的热点。
在现有技术中， 如本发明所示的含氰基的邻苯二甲酰胺类化合物的制备及其杀虫活性 未见公开。 发明内容
本发明的目的在于提供一种在很小的剂量下就可以控制各种病虫害的含氰基的邻苯 二甲酰胺类化合物， 它可应用于农业上以防治作物的病害和虫害。
为实现上述目的， 本发明提供如下技术方案：
一种式 （I ) 表示的含氰基的邻苯二甲酰胺类化合物或其农业上适用的盐，
Figure imgf000004_0001
其中：
R R2独立地选自氢、 d-C6院基、 环垸基、 C2-C6链烯基或^- 炔基， 所述基团上的 氢还可以被卤素、 氰基、 硝基、 d-C6垸氧基、 苯基、 取代的苯基、 苯氧基、 取代的苯氧基、 烷硫基、 烷基亚磺酰基或垸基磺酰基进一歩取代；
或者 R1和 R2同所连接的碳一起形成环烷基；
R3选自氢、 卤素、 氰基、 硝基、 芳基、 酯基、 d-C6垸基、 卤代 d-C6垸基、 d-C6垸氧基或 卤代 垸氧基；
R4选自氢或(^-(：6垸基；
X选自亚甲基、 d-C6烷基、 氰基取代的亚甲基或直接键；
或者 X和 R4同所连接的 N组成三元环、四元环、五元环、六元环、五元杂环或六元杂环； Y选自氢、 卤素、氰基、硝基、羟基、 d-C6烷基、 卤代 d-C6垸基、 d-C3垸氧基、 卤代 d-C3 垸氧基、 苯基、 取代的苯基、 杂环芳基或取代的杂环芳基；
A为 CH或 N;
m为 0〜4的整数。
作为优选的实施方式， 上述 （I )表示的含氰基的邻苯二甲酰胺类化合物中：
R R2独立地选自氢、 烷基、 C3-C6环垸基或 ( 2-(：3链烯基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 垸硫基、 垸基亚磺酰基或垸基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环己基；
R3选自氢或卤素；
R4选自氢或^-^垸基；
或者 X和 R4同所连接的 N组成五元杂环或六元杂环；
Y选自氢、 卤素原子、 硝基、羟基、 d-C3烧基、 氟代 d-C3垸基、 d-C3烷氧基或氟代 - 垸氧基；
m为 1〜3的整数。
作为进一步优选的实施方式， 上述 （I )表示的含氰基的邻苯二甲酰胺类化合物中： R R2独立地选自氢、 甲基、 乙基、异丙基、 环丙基或烯丙基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 甲硫基、 甲基亚磺酰基、 甲基磺酰基等基团进一步取代；
R3选自氟、 氯、 溴或碘， R3位于苯环的 3位或 4位；
R4为氢或甲基；
X为亚甲基、 甲基、 氰基取代的亚甲基或直接键；
或者 X和 R4同所连接的 N组成含氧六元杂环；
Y选自氢、 氟、 氯、 硝基、 羟基、 甲基、 甲氧基、 三氟甲基、 三氟甲氧基或七氟异丙基。 作为最为优选的实施方式， 上述（I )表示的含氰基的邻苯二甲酰胺类化合物的结构式为:
Figure imgf000005_0001
或其盐。
上述式 （I ) 表示的含氰基的邻苯二甲酰胺类化合物中 R R2、 R3、 R\ A、 X、 Y和 m定义 中- 垸基是指直链或支链形式， 例如甲基、 乙基、 正丙基、 异丙基、 正丁基、 异丁基、 仲丁 基、 特丁基、 正戊基、 异戊基、 正己基等基团。 环垸基是指包括环状链形式， 例如环丙基、 环丁基、 环戊基、 环己基等基团。 链烯基是指直链或支链形式， 例如乙烯基、 1-丙烯基、 烯 丙基、 异丙烯基、 1-丁烯基、 1， 3-丁二烯基、 1-己烯基等基团。 炔基是指直链或支链形式， 例如乙炔基、 2-丁炔基、 2-戊炔基、 3-己炔基等基团。 卤代垸基是指垸基被一个或多个卤原 子取代的基团。 垸氧基是指垸基末端连有氧原子的基团， 例如甲氧基、 乙氧基、 正丙氧基、 异丙氧基、 特丁氧基等。 卤代烷氧基是指垸基被一个或多个卤原子取代， 末端连有氧原子的 基团。 垸硫基是指垸基末端连有硫原子的基团， 如甲硫基、 乙硫基等。 垸基亚磺酰基是指垸 基末端为 （S0-) 的基团， 如甲基亚磺酰基。 垸基磺酰基是指烷基末端为 （S02- ) 的基团， 如 甲基磺酰基。 卤素是指氟、 氯、 溴、 碘。
本发明的式（I )表示的含氰基的邻苯二甲酰胺类化合物在有些情况下在其结构式中含有 一个或多个不对称中心， 在有些情况下具有两种或多种旋光异构体和非对映体。 本发明还包 括所有单独的旋光异构体和由这些异构体按任意比例组成的混合物。
本发明还提供用于制备式 （I )表示的含氰基的邻苯二甲酰胺类化合物的中间体， 具有如 下式 （I I ) 或 （I I I ) 结构式：
Figure imgf000006_0001
(II) (III)
其中：
R R2独立地选自氢、 d- 烧基、 C3-C6环垸基、 C2-C6链烯基或 C2-C6炔基， 所述基团上的 氢还可以被卤素、 氰基、 硝基、 （^-[：6垸氧基、 苯基、 取代的苯基、 苯氧基、 取代的苯氧基、 烷硫基、 烷基亚磺酰基或垸基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环垸基；
R3选自氢、 卤素、 氰基、 硝基、 芳基、 酯基、 d-C6烷基、 卤代 d-Ce垸基、 烷氧基或 卤代 -c垸氧基。
作为优选的实施方式， 上述式 （II) 或 （III) 表示的化合物结构式中：
R R2独立地选自氢、 d-C3焼基、 C3-C6环垸基或 C2-C3链烯基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 垸硫基、 垸基亚磺酰基或烷基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环己基；
R3选自氢或卤素。
作为进一步优选的实施方式， 上述式 （II) 或 （III)表示的化合物结构式中：
R R2独立地选自氢、 甲基、 乙基、异丙基、 环丙基或烯丙基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 甲硫基、 甲基亚磺酰基、 甲基磺酰基等基团进一步取代；
R3选自氟、 氯、 溴或碘， R3位于苯环的 3位或 4位。
本发明所述的 （I)表示的含氰基的邻苯二甲酰胺类化合物可以通过如下方法制备：
Figure imgf000006_0002
即包括如下步骤：
( 1 )在惰性溶剂， 在存在或不存在碱的情况下， 结构式 (VI)表示的取代的邻苯二甲 酸酐与结构式（V)表示的取代的氨基乙腈进 N-酰化反应得到结构式（I I I )表示的取代邻酰 胺基苯甲酸；
( 2 ) 在惰性溶剂， 结构式（I I I)表示的取代邻酰胺基苯甲酸与酰化试剂反应得到结 构式（I I)表示的取代的邻苯二甲酰异酰亚胺；
( 3 )在惰性溶剂中， 在存在或不存在酸的情况下， 结构式（I I)表示的取代的邻苯二 甲酰异酰亚胺与结构式（IV)表示的取代的胺反应得到结构式（I )表示的含氰基的邻苯二甲 酰胺类化合物；
其中结构式（IV)至（VI)表示的化合物中 R R2、 R3、 R4、、 Y和 m定义如上述结构式 ( I ) 表示的含氰基的邻苯二甲酰胺类化合物。
作为优选的实施方式， 上述步骤 （1 ) 中所述惰性溶剂选自四氢呋喃、 乙腈、 1， 4-二 氧六环、 Ν, Ν-二甲基甲酰胺、 Ν，Ν-二甲基乙酰胺、 甲苯或二氯甲垸中的一种或两种以上 组合， 所述碱包括有机碱和无机碱， 所述有机碱选自三乙胺、 吡啶或 3-甲基吡啶， 所述 无机碱选自碳酸钾、 碳酸氢钠、 氢氧化钠或无水乙酸钠； 上述步骤 （2 ) 中所述惰性溶剂 选自甲苯、 1， 2-二氯乙垸、 乙酸乙酯、 四氢呋喃、 乙腈、 1， 4-二氧六环或二氯甲烷中 的一种或两种以上组合， 所述酰化试剂为氯甲酸甲酯、 乙酸酐或三氟乙酸酐， 对于每摩 尔式（Ι Π)的邻酰胺基苯甲酸，酰化试剂的使用量可在 1摩尔至过量摩尔数范围内适当选 择； 上述步骤（3 ) 中所述惰性溶剂选自四氢呋喃、 二氯甲垸、 1， 2-二氯乙垸、 乙醚、 1， 4-二氧六环、 乙腈或甲苯中的一种或两种以上组合， 所述酸包括有机酸和无机酸， 所述 有机酸选自乙酸、 三氟乙酸或对甲基苯磺酸， 所述无机酸为盐酸或硫酸； 反应温度为在 0° C到所用惰性溶剂的沸点之间。
反应时间随反应规模与反应温度而异， 优选为 2〜12h。
反应结束后， 可以用常规的过滤等方法将式（I)所述产物从反应混合物中分离出来， 如 果需要， 可以使用重结晶、 柱色谱等分离手段。
上述歩骤（1 ) 中产物经酸化、 提取、 浓缩后会有固体析出， 用溶剂洗涤、 过滤后将其分 离。
上述制备方法中使用的式 (VI)表示的取代的邻苯二甲酸酐是一种已知化合物， 可以 通过许多已知方法进行制备。
本发明式（I )表示的典型化合物列在索引表 1和索引表 2中， 但是他们决不限制本发明的 范围。 在索引表 1中， 式 （I )表示的典型化合物， 当 R4为氢， X为直接键时， 典型化合物如式 da)所示：
Figure imgf000008_0001
化合物 熔点
R1 R2 R3 A Ym
编号 (° C)
1 C¾ i-C3H7 3- CI CH 2, 4-Cl2 187-190
2 CH3 i-C3H7 3- CI CH 3， 5- Cl2 229-231
3 c¾ i-C3H7 3- CI CH 2,6- (CH3)2- 4- CF(CF3)2 156-158
4 CH3 i- C3H7 3- CI CH 2- CH3- 4- CF(CF3)2 136-139
5 CH3 C2H5 3- CI CH 2-0H-4-CF (CF3)2 240-241
6 CH3 C2H6 3- CI CH 2,6- (CH3)2- 4- CF(CF3)2 168-170
7 CH3 C2H5 3- CI CH 2,5-(CH3)2-4-CF(CF3)2 193-195
8 CH3 CH3 3- CI CH 2-F 221-223
9 CH3 CH3 3- CI CH 2-CH3-4-CF(CF3)2 213-215
10 CH3 CH3 3- CI CH 2， 5- Cl2 196-198
11 c¾ CH3 3- CI CH 2,5— (C¾)2— 4— CF(CF3)2 248-250
12 C¾ CH3 3- CI CH 2-Cl-4-N02 205-207
13 CH3 CH3 3- CI CH 3-CH3-4-CF(CF3)2 233-235
14 c¾ CH3 3- CI CH 4-CF(CF3)2 268-271
15 CH3 CH2 (4-0CH3-Ph) 3- CI CH 2,6-(CH3)2-4-CF(CF3)2 119-121
16 CH3 CH3 3- CI CH 2- CI 178-180
17 CH3 CH3 3- CI CH 2-0CH3-4-CF(CF3)2 164-166
18 CH3 CH3 3- CI CH 2， 6- Cl2 155-157
19 CH3 CH3 3- CI CH 2,6- (CH3)2- 4- CF(CF3)2 259-261
20 CH3 CH3 3- CI CH 3, 5- Cl2 237-239
21 CH3 CH3 3- CI CH 2-OCH3 148-150
22 c¾ CH3 3- CI CH 2-0H-4-CF (CF3)2 209-211
23 C¾ CH3 3-1 CH 4-CF(CF3)2
24 CH3 CH3 3-1 CH 2-CH3-4-CF(CF3)2 243-245
25 c¾ CH3 3-1 CH 2-CH3 191-193
26 CH3 CH20(4-Cl-Ph) 3-1 CH 2-CH3-4-CF(CF3)2
27 CH3 CH(CH2)2 3-1 CH 2-CH3-4-CF(CF3)2
28 H C¾CH=C¾ 3-1 CH 2-CH3-4-CF(CF3)2
29 CH3 CH3 3-1 CH 2,5— (CH3)2— 4— CF(CF3)2
30 CH3 CH2SCH3 3-1 CH 2, 4- Cl2
31 CH3 C2H6 3-1 CH 3-CH3-4-CF(CF3)2 C¾ CH3 3-F CH 2,6-(CH3)2-4-CF(CF3)2 247-249
CH3 CH3 3-F CH 3, 5- Cl2 188-190
CH3 CH3 3-F CH 2-CH3-4-CF(CF3)2 214-216
(c¾)4 3-F CH 3-CH3-4-CF(CF3)2
CH3 CH2 (4- 0CH3-Ph) 3-F CH 2, 4- F2
CH3 CH(CH2)2 3-F CH 2， 4- Cl2
CH3 CH3 3-F CH 2,5— (CH3)2— 4— CF(CF3)2 227-229
CH3 CH3 3-N02 CH 3， 5- Cl2 202-204
CH3 CH3 3-N02 CH 3, 5- F2 186-188
CH3 CH3 3-N02 CH 2,6- (CH3)2- 4- CF(CF3)2 151-153
CH3 CH3 3-N02 CH 2， 4， 5-F3
H C¾CH=C¾ 3-N02 CH 2-F-5-CF3
CH3 i - C3 3-N02 CH 2-CH3-3-CF3
CH3 i~C3H7 3-N02 CH 4-CF(CF3)2
c¾ CH3 4- CI CH 2,6- (CH3)2- 4- CF(CF3)2 272-274
CH3 CH3 4- CI CH 2-CH3-4-CF(CF3)2 207-209
CH3 CH3 4- CI CH 2， 4- Cl2 176-178
CH3 CH3 4- CI CH 3, 5- Cl2 226-228
CH3 CH3 4- CI CH 4-CF(CF3)2 245-247 c¾ CH3 4- CI CH 2-0H-4-CF (CF3)2 217-218
CH3 CH3 4- CI CH 2,5— (CH3)2— 4— CF(CF3)2 166-168
CH3 CH3 4- CI CH 2- 0C¾- 4- CF(CF3)2 178-180 c¾ CH3 4- CI CH 3-CH3-4-CF(CF3)2 229-231
C¾ CH3 4- CI CH 2, 5- Cl2 205-207
CH3 CH3 4- CI CH 3, 4- F2 208-210 c¾ CH3 4- CI CH 2, 6- Cl2 246-248
CH3 CH3 4- CI CH 2, 4- F2 187-190
CH3 CH3 4- CI CH 2， 4, 5 188-191
CH3 CH3 4- CI CH 3-CF3 220-222
CH3 CH3 4- CI CH 2-CF3 239-241 c¾ CH3 4- CI CH 2-CH3-3-CF3 190-193
CH3 CH3 4- CI CH 2-F-5-CF3 219-221
CH3 CH3 4- CI CH 3, 5- F2 229-231 c¾ CH3 4- CI CH 4-CH3 221-223
C¾ CH3 4- CI CH 2-CH3 195-197
CH3 CH3 4- CI CH 2- CI 185-187 c¾ CH3 4- CI CH 3,4- (CH3)2 209-211
CH3 CH3 4- CI CH 2， 3- Cl2 190-192
CH3 CH3 4- CI CH 2-F 154-156
CH3 CH3 4- Br CH 4-CF(CF3)2 241-243
CH3 CH3 4- Br CH 2-0H-4-CF (CF3)2 225-227 c¾ CH3 4- Br CH 2,5— (C¾)2— 4— CF(CF3)2 227-229
CH3 CH3 4- Br CH 3-CH3-4-CF(CF3)2 226-228
CH3 CH3 4- Br CH 2， 4- Cl2 221-223 c¾ CH3 4- Br CH 2, 5- Cl2 188-190
Figure imgf000010_0001
122 CH3 4- CI CH 3-CH3-4-CF(CF3)2 213-215
123 CH3 I-C3H7 4- CI CH 2, 4-Cl2 202-204
124 CH3 i - C3 4- CI CH 2-0CH3-4-CF(CF3)2 194-196
125 CH3 c¾ 3-F CH 3-CH3-4-CF(CF3)2 262-264
126 CH3 CH3 3-F CH 3， 5- Cl2 206-208
127 c¾ CH3 3-F CH 2, 4- F2 199-201
128 CH3 CH3 3-F CH 2-0CH3-4-CF(CF3)2 191-193
129 CH3 CH3 3-F CH 2, 4-Cl2 188-190
130 c¾ C2H5 3-F CH 2,6- (C¾)2- 4- CF(CF3)2 245-247
131 CH3 C2H5 3-F CH 2-CH3-4-CF(CF3)2 210-212
132 CH3 C2H5 3-F CH 3- C - 4- CF(CF3)2 253-255 索引表 2中式 （I) 表示的典型化合物， 当 A为 CH， X为亚甲基、 甲基、 氰基取代的亚甲基 或 N XR4成环时， 典型化合物如式 （lb)所示：
Figure imgf000011_0001
索引表 2
Figure imgf000011_0002
以下表 3为索引表 1和索引表 2中所述部分化合物的核磁数据。
注： 表 3中所述化合物编号与表 1和表 2中所述化合物编号相对应。其中 s为单峰， brs 为宽单峰， d为双峰， dd为双二重峰， t为三重峰， q为四重峰， m为多重峰。 表 3化合物核磁数据
化合物编号 核磁（400MHz, DMS0- 4)
10.13-10.06 (1H, d), 8.80-8.75 (1H, d), 7.73-7.66 (4H, m) ,
1
7.61-7.58 (1H, m), 7.48- 7.46 (1H， d)， 2.40-2.35 (1H, m) , 1.53-1.52 (3H, d) , 1.07— L 05 (3H, dd) , 0.97—0· 95 (3H, dd)
10.71-10.68 (IH, d), 8.84-8.80 (IH, d), 7.78-7.60 (5H, m) , 7.32 (IH, s), 2.40-2.34 (IH, m), 1.54- 1.53 (3H， d) , 1.07-1.06 (3H, dd), 0.98-0.97 (3H， dd)
10.72-10.69 (IH, d), 8.84— 8· 82 (1H， d) , 7.78-7.53 (3H, m) , 7.40 (2H, s), 2.38 (6H, s) , 2.37-2.34 (IH, m),
1.53-1.52 (3H， d)， 1.08— L 06 (3H, dd)， 0.97-0· 96 (3H, dd)
10.82-10.79 (IH, d), 8.82-8.78 (IH, d), 7.79-7.54 (6H, m) , 2.39 (3H, s), 2.39-2.38 (IH, m), 1.54-1.52 (3H, d), 1.07-1.05 (3H, dd), 0.97-0.95 (3H, dd)
10.42 (IH, s), 9.69 (IH, s) , 8.83 (IH, s) , 8· 16- 8.10 (1H， m) , 7.77-7.59 (3H, m), 7.17-7.13 (2H, m), 1.96-1.86 (2H, m) , 1.57 (3H, s), 1.00-0.96 (3H, t)
10.09-10.03 (IH, d), 8.89- 8.86 (1H， d)， 7.87-7.58 (3H, m) , 7.41 (2H, s), 2.39 (6H, s) , 2.00-1.88 (2H, m),
1.59-1.58 (3H， d)， 1.03- L 00 (3H， t)
10.06-10.00 (IH, d), 8, 88— 8.83 (1H， d)， 7.77-7.57 (4H, m) , 7.33 (IH, s), 2.44-2.42 (3H, d), 2.32 (3H, s),
1.96-1.88 (2H, m), 1.60— 1.59 (3H， d) , 1.02-0.99(3H, t)
10.17-10.11 (IH, d), 8, 92- 8.86 (1H， d)， 7.81-7.58 (4H, m) , 7.29-7.21 (3H, m), 1.63— L 61 (6H， d)
10.08-10.03 (IH, d), 8.98-8.93 (IH, d), 7.79-7.62 (4H, m) , 7.54-7.50 (2H, m), 3.89 (3H, s), 1.63 (6H, s)
10.17-10.10 (IH, d), 8.98- 8.92 (1H， d)， 7.84 (IH, s),
7.72-7.62 (3H, m), 7.59-7.56 (IH, m), 7.35-7.32 (IH, m) , 1.65-1.64 (6H, d)
10.00 (IH, s), 8.98 (IH, s) , 7.70- 7.67 (3H， m)， 7.56 (IH, s), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.31 (3H, s), 1.65 (6H, s)
10.37-10.31 (IH, d), 9.00- 8.95 (1H， d)， 8.27- 8.16 (2H， m)，
7.76-7.66 (4H, m), L 64- 1.63 (6H， d)
10.65-10.62 (IH, d), 8.96- 8.92 (1H， d)， 7.73-7.61 (5H, m) , 7.51-7.49 (IH, m), 2.47-2.44 (3H, m), 1.62 (6H, s)
10.75 (lH，s)， 8.93 (IH, s) , 7.94-7.92 (2H, m) ,
7.75-7.62 (5H, m), 1.63— 1.62 (6H， d)
10.12-10.06 (IH, d), 8.96-8.93 (IH, d), 7.79-7.68 (2H, m) , 7.55-7.53 (IH, d), 7.41 (IH, s), 7.29-7.27 (2H, d), 6.90-6.84 (2H, m), 3.74 (3H, s), 3.26-3.18 (2H, m), 2.42-2.41 (6H, d), 1.51— L 50 (3H， d)
10.03-9.96 (IH, d) , 8.94- 8.89 (1H， d)， 7.71-7.59 (4H, m), 7.54-7.52 (IH, d), 7.38-7.26 (2H, m), 1.63- 1.62 (6H， d)
9.73-9.63 (IH, d) , 8.97-8.91 (IH, d), 8.26-8.24 (IH, d),
7.70-7.59 (3H, m), 7.29-7.27 (IH, d), 7.20 (IH, s), 3.91 (3H, s), 1.61-1.60 (6H, d)
10.45-10.37 (IH, d), 8.88— 8.84 (1H， d)， 7.89-7.56 (4H, m) , 7.42-7.37 (2H, m), 1.62- L 61 (6H， d)
10.08-10.01 (IH, d), 8· 98- 8.95 (1H， d) , 7.78-7.58 (3H, m) , 7.40 (2H, s), 2.38 (3H, s) , 1.63 (3H, s)
10.70-10.68 (IH, d), 8.99— 8.94 (IH, d) , 7.74-7.62 (5H, m) ,
20
7.32-7.31 (IH, m), 1.63 (6H, s)
9.39-9.29 (IH, d) , 8.95-8.88 (IH, d), 7.98-7.96 (IH, m),
21 7.65-7.56 (2H, m), 7.13-6.95 (4H, m), 3.83 (3H, s),
1.61 (6H, s)
10.45-10.40 (IH, d), 9.69— 9.57 (1H， d)， 8.99- 8.93 (1H， d)，
22 8.09-8.07 (IH, m), 7.76-7.59 (3H, m), 7.16-7.12 (2H, m) ,
1.61 (6H, s)
10.59 (IH, s), 8.96 (IH, s) , 8.05- 8, 03 (1H， d)，
23 7.93-7.92 (2H, d), 7.71-7.65 (3H, m), 7.30 (IH, t),
1.60 (6H, s)
9.85 (IH, s), 8.99 (IH, s), 8.05- 8.03 (1H， d) ,
24 7.79-7.77 (2H, d), 7.53-7.49 (2H, t), 7.33-7.29 (IH, t) ,
2.36 (3H, s), 1.61 (6H, s)
9.63 (IH, s), 8.92 (IH, s), 8.01 (IH, d), 7.75 (IH, m),
25
7.40-7.22 (5H, m), 2.25 (3H, s), 1.60 (6H, s)
10.02 (IH, s), 9.11 (IH, s) , 7.65-7.63 (2H, m),
32
7.49-7.45 (IH, m), 7.41 (2H, s) , 2.35 (6H, s), 1.61 (6H, s)
10.68 (IH, s), 9.13 (IH, s) , 7.77-7.61 (4H, m), 7.33 (2H, s),
33
1.62 (6H, s)
10.05 (IH, s), 9.13 (IH, s) , 7· 55— 7.45 (6H， m)， 2.38 (3H, s),
34
1.61 (6H, s)
10.79 (IH, s), 9.16 (IH, s) , 7.89-7.73 (4H, m),
39
7.37-7.34 (2H, m), 1.62 (6H, s)
10.86 (IH, s), 9.17 (IH, s) , 7.92- 7.80 (3H， m)，
40
7.30-7.25 (3H, m), 1.57 (6H, s)
10.32 (IH, s), 9.11 (IH, s) , 7.87-7.74 (2H, m), 7.74 (2H, s),
41
7.42 (lH，s)， 2.37 (6H, s), 1.58 (6H, s)
9.99 (IH, s), 9.08 (IH, s), 7.86-7.78 (IH, m) ,
46 7.73-7.69 (IH, t), 7.63-7.59 (IH, t) , 7.42 (2H, s) ,
2.35 (6H, s), 1.62 (6H, s)
9.97 (IH, s), 9.10 (IH, s), 7.78-7.72 (2H, m) ,
47
7.61-7.51 (4H, m), 2.38 (3H, s), 1.62 (6H, s)
9.96 (IH, s), 9.08 (IH, s), 7· 85— 7· 70 (4H， m)，
48
7.67-7.55 (IH, m), 7.49-7.41 (IH, m), 1.61 (6H, s)
10.63 (IH, s), 9.10(1H, s) , 7.77-7.70 (4H, m),
49
7.62-7.60 (IH, m), 7.34 (IH, s), 1.62 (6H, s)
10.66 (IH, s), 9.07 (IH, s) , 7.95-7.92 (2H, d),
50
7.72-7.64 (4H, m), 7.60-7.56 (IH, m), 1.60 (6H, s)
10.62(1H, s), 9.36 (IH, s) , 9.14 (IH, s) , 8· 17— 8.15 (IH, d) ,
51 7.73-7.69 (2H, m), 7.60- 7· 56 (1H， m)， 7· 16- 7· 12 (2H， m)，
1.58-1.56 (6H, d)
9.93 (IH, s), 9.10 (IH, s), 7.74-7.63 (2H, m) ,
52 7.60-7.55 (2H, m), 7.33 (IH, s), 2.44-2.42 (3H, m) ,
2.29 (3H, s), 1.62 (6H, s) '(ω 'H9)C9 'L-LL 'ί ' (s Ήΐ)80 "6 ' (s Ήΐ)80 Όΐ 69
(s 'Η9)ΐ9 'Τ '(Ρ 'Η9)02 Ύ-ΙΖ Ύ
'(Ρ 'Ηΐ)80 " -Οΐ Ί '(ω ¾)6C " -^ "Ζ '(ΐ ¾T)C9 "Ζ- 9 " 89
'(Ρ 'Η2)99 ·Ζ-Ζ9" '(δ 'Ηΐ)ΐΟ·6 ' (s Ήΐ)90 Όΐ
(s 'Η9)ΐ9 ·ΐ
'(ω 'Ηΐ)92 'ί-0£ 'ί ¾T)ZS " -Ο^ "Ζ ' ( 'ffi) ·Ζ- ΐ9 · L9
'(ω 'Ηδ)69 ' -9Z "Ζ '(s 'Ηΐ)90 '6 '(s 'Ηΐ)98 '6
(s 'Η9)ΐ9 ·ΐ
'(s ¾ε) 27 '(ω 'HC)CT 'ί-ΙΖ "Ζ ' (Ρ 'Ηΐ) 0 ·Ζ- ΐ 99
'(ω 'Ηδ)29 'L- L "Ζ '(s ¾ΐ)^0 '6 '(s ¾ΐ)9 "6
(s 'Η9) 09 ·ΐ
'(s 'Ηδ)8^ 'Ζ '(Ρ 'W,) "Ζ-9ΐ "Ζ '(ω ¾C)^9 'Z- 9 'Ζ 99
'(ω ¾)99 " -Ζ9 " ' (s Ήΐ)ΐΟ "6 ' (s Ήΐ)9Τ Όΐ
(s 'Η9) S9 ,ΐ
'(ω 'Ηΐ)½ "9-86 "9 ' (ω 'Η2) WZ— ·Ζ '(ω ¾ΐ)Ζ9 'Z-C9 "Ζ f9
'(ω 'HC)69 "Ζ-9Ζ " '(s 'HT)60'6 ' (s Ήΐ)89 Όΐ
(s 'Η9)Τ9 "ΐ '(ω 'HC)S9 "Z-29'Z ' (m 'ΗΖ)Ο ' -^ 'Ζ
S9
'(Ρ'1Π)ε2·8- ·8 '(s Ήΐ)80 "6 '(s Ήτ)εε Όΐ
(s 'Η9)ΐ9 ·ΐ
'(s 'HC) g "2 ' 'Ηΐ)ΐ Ζ— S Z ' (ω 'm) 99 'Z-69 ' 29
'(Ρ 'ΗΤ) Ζ - -8 ' '(s Ήΐ)ΖΟ "6 ' (s Ήΐ)ΖΟ Όΐ
(s 'Η9)ΐ9 "Τ '(ω 'Η2)ΐ9 'Ζ-½ 'Ζ
ΐ9
'(ω 'Η9)69 "Ζ-08 " ' (s ¾T)SO "6 ' (s 'Ηΐ)90 Όΐ
(s 'Η9) 09 ,ΐ
'(Ρ 'ΗΤ)^ 'L-9f Ί '(ω 'Η2)99 "Ζ-Τ9 'Ζ '(ω 'Η2)89 "Z-CZ 'Ζ 09
'(Ρ 'HT)T6 -Z-C6" '(s ¾ΐ)ετ "8 '(s Ήΐ)ΖΟ "6 ' (s Ήΐ)09 Όΐ
(s 'Η9)Τ9 "ΐ 'Ηΐ)99 "Z-6S 'Ζ '(ω 'HC)C9 'Ζ-ΟΖ 'Ζ
69
'(ω 'HT)S8 -Z-88" ' (s Ήΐ)90 "6 ' (s Ήΐ)ΐ2 Όΐ
(s 'Η9) 69 ·ΐ
'(ω 'Ηΐ)80 'Ζ '(™ 'Ηΐ)Ζ2 'Z-TC 'Ζ '(ω ¾ΐ)^9 'Z-89 ' 89
'(ω 'H0 9 - -Ο ' '(δ 'Ηΐ)ΐΟ·6 ' (s Ήΐ)£0 Όΐ
(s 'Η9) 69 ·ΐ
'(ω 'HT)9g " -6δ " '(ω ¾S) 99 "Ζ-09 'Ζ '(ω ¾ΐ)Ο "Z-CZ " Ζ9
'(ω 'HT)C8 - -g8" ' (s 'HT)^6"8 ' (s Ήΐ)82 Όΐ
(s 'Η9) 09 ·ΐ
'(ω ¾)8C Ί- 'ί '(m ¾ΐ)99 -Ζ-ΐ9 'Ζ '(ω 'Η2) 9 'Z-8Z ' 99
'(ω 'ΗΤ)08 ' -^8 " ' (s 'Ηΐ)90 "6 ' (s 'Ηΐ)ΐ9 Όΐ
(s 'Η9)ΐ9 'T-C9 ·ΐ
'(ω 'HT)Cg " -6S "Ζ '(ω ¾)Ζ9 "Ζ-Τ9 'Ζ '(ω 'Η2)69 "Ζ-8Ζ ' 99
'(ω 'HT)T8 ' -28" ' (s ¾ΐ)86 "6 ' (s ¾T)OS Όΐ
(s 'Η9)ΐ9 ·ΐ
'(ω 'Ηδ)^ - ^ '(Ρ 'Ηΐ)6^ "Ζ-Τ9 'Ζ '(ω ¾ΐ)99 'Ζ-ΐ9 "
'(ω ¾)89 " -ΖΖ " '(s Ήΐ)90 "6 ' (s Ήΐ)99 Όΐ
(s 'Η9) 91 '(s 'HC)26 "C
'(ω 'Η2)02 'ί-6Ζ " '(ΐ 'Ηΐ)99 "Ζ-09 'Ζ '(∞ ¾Ζ)69 'Ζ-ΐΖ 'Ζ
'(Ρ c )9Z "8-82 "8 '(s 'Ηΐ)^ΐ '6 '(s 'Ηΐ)9^ '6
ll.8.0/llOZN3/X3d Z^WO/ZIOZ OAV 7.43-7.39 (IH, t), 1.61 (6H, s)
10.00 (IH, s), 9.03 (IH, s) , 7.78-7.68 (3H, m),
70
7.59-7.55 (IH, t), 7.31-7.19 (3H, m), 1.61 (6H, s)
10.75 (IH, s), 8.93 (IH, s) , 8· 05- 8.03 (1H， d)，
71 7.95-7.92 (3H, m), 7.66-7.64 (IH, m), 7.60- 7.58 (2H， d)，
7.56-7.54 (IH, m), 1.62 (6H, s)
10.45-10.40 (IH, d), 9.82— 9.70 (1H， d)， 8.93 (IH, s),
72 8.09-8.07 (IH, m), 7.79 (IH, s), 7.76- 7.74 (1H， d)，
7.55-7.52 (IH, m), 7.16— 7.12 (2H， m)， 1.62-1.61 (6H, d)
10.05-9.99 (IH, d) , 8.98- 8, 94 (1H， d)， 7.82-7.79 (2H, m),
73 7.60-7.53 (2H, m), 7.33 (IH, s), 2.44-2.42 (3H, d),
2.31 (3H, s), 1.65-1.64 (6H, d)
10.66-10.63 (IH, d), 8, 98- 8· 93 (IH, d)， 7.86- 7.69 (4H， m) ,
74
7.61-7.52 (2H, m), 2.48-2.46 (3H, d), 1.64-1.63 (6H, d)
10.13-10.05 (IH, d), 8.96- 8.90 (1H， d) , 7.82-7.79 (2H, m) ,
75
7.73-7.69 (2H, m), 7.55- 7· 46 (2H， m)， 1.64-1.62 (6H, d)
10.19-10.11 (IH, d), 8.99— 8· 93 (1H， d) , 7.84-7.81 (3H, m) ,
76
7.59-7.55 (2H, m), 7.36-7.33 (IH, m), 1.65- 1.64 (6H， d)
10.71-10.68 (IH, d), 8.99- 8· 95 (1H， d)， 7.88-7.80 (2H, m) ,
77 7.74-7.72 (2H, m), 7.61-7.55 (IH, m), 7.32-7.31 (IH, m) ,
1.64-1.63 (6H, d)
9.75 (IH, s), 8.92 (IH, s), 8.26-8.24 (IH, d) ,
78 7.84-7.79 (2H, m), 7, 55- 7· 53 (1H， d)， 7.30-7.21 (2H, m) ,
3.92 (IH, s), 1.61 (6H, s)
10.20-10.13 (IH, d), 8.93-8.87 (IH, d), 7.85-7.77 (3H, m) ,
79 7.62-7.51 (IH, m), 7.35- 7· 30 (1H， t)， 7.11 (IH, s),
1.63-1.62 (6H, d)
10.60-10.57 (IH, d), 8.96— 8.91 (1H， d)， 7.85-7.79 (3H, m) ,
80
7.60-7.53 (IH, m), 7.47— 7.38 (2H， m)， L 63- 1· 62 (6H， d)
10.76-10.73 (IH, d), 8, 99— 8.94 (1H， d)， 7.87-7.81 (2H, m) ,
81 7.61-7.55 (IH, m), 7.42-7.39 (2H, d), 6.97-6.93 (IH, m) ,
1.64-1.63 (6H, d)
10.39-10.33 (IH, d), 8, 96— 8· 91 (IH, d)， 7.90-7.80 (3H, m) ,
82
7.69-7.54 (2H, m), 1.64- L 63 (6H， d)
10.52-10.46 (IH, d), 8.97— 8.92 (1H， d) , 8.36-8.25 (IH, m) ,
83
8.08-7.81 (3H, m), 7.61-7.52 (3H, m), 1.64-1.63 (6H, d)
10.45-10.37 (IH, d), 8.88— 8.83 (1H， d)， 7.79-7.72 (2H, m) ,
84
7.60-7.57 (2H, dd), 7.50-7.40 (2H, m) , 1.62- 1.61 (6H， d)
10.04 (IH, s), 8.91 (IH, s) , 7.84-7.76 (2H, m),
85
7.49-7.47 (IH, d), 7.36 (2H, s), 2.34 (6H, s), 1.58 (6H, s)
10.05-10.01 (IH, d), 8.94- 8· 89 (1H， d)， 7.78-7.76 (IH, m) ,
86 7.68-7.64 (2H, m), 7.57— 7.49 (2H， m)， 7.39 (IH, s),
1.60-1.59 (6H, d)
10.65-10.62 (IH, d), 8.93— 8.88 (1H， d)， 8.09-8.04 (IH, m) ,
87 7.85-7.75 (3H, m), 7.59-7.50 (2H, m), 7.42-7.40 (IH, m) ,
1.59-1.58 (6H, d) 9.82-9.76 (IH, d) , 8.89-8.84 (IH, d), 7.84-7.62 (2H, m),
88 7.47-7.37 (IH, m), 7.21-7.10 (3H, m), 6.88-6.82 (IH, m) ,
2.24 (3H, s), 1.59- 1.58 (6H，d)
10.18-10.09 (IH, d), 8.92— 8· 87 (1H， d)， 7.76-7.71 (4H, m) ,
89
7.58-7.47 (3H, m), 1.60- L 59 (6H， d)
9.85-9.78 (IH, d) , 8.94-8.90 (IH, d), 7.88-7.48 (3H, m) ,
90
7.10 (3H, s), 2.27 (6H, s) , 1.63- 1.62 (6H， d)
10.24-10.17 (IH, d), 8.97— 8.91 (1H， d)， 7.84-7.80 (2H, m) ,
91
7.69-7.51 (3H， m)， 7.43-7· 41 (1H， m)， 1.64-1.63 (6H, d)
10.05-9.96 (IH, d) , 8.95- 8.89 (1H， d)， 7.86-7.64 (3H, m),
92
7.55-7.52 (2H, d), 7.38-7.20 (2H, m), 1.64-1.63 (6H, d)
9.90-9.85 (IH, d) , 8.92-8.87 (IH, d), 7.89-7.74 (2H, m),
93 7.51-7.49 (1H， d)， 7.22-7.07 (3H, m)，
2.28 (3H， s)， 2.16 (3H, s) , 1.64—1.63 (6H， d)
10.19-10.12 (IH, d), 8.93— 8.87 (1H， d) , 7.81-7.77 (3H, m) ,
94
7.62-7.52 (IH, m), 7.28-7.22 (3H, m), 1.64- 1.62 (6H， d)
9.82-9.76 (IH, d) , 8.94-8.89 (IH, d), 7.88-7.50 (3H, m),
95 7.24 (IH, s), 7.13-7.12 (IH, d), 6.98- 6.96 (1H， d)，
2.28 (3H, s), 2.23 (3H, s) , 1.65- L 63 (6H， d)
10.39-10.32 (IH, d), 9.01- 8.96 (1H， d)， 8.40- 8.39 (1H， m)，
96 8.30-8.26 (IH, m), 8.19- 8.16 (1H， m) , 7.90-7.83 (2H, m) ,
7.68-7.59 (IH, m), 1.65- L 63 (6H， d)
10.25-10.17 (IH, d), 8, 99— 8· 94 (IH, d)， 8.29 (IH, s),
97 8.17-8.02 (IH, m), 7.88-7.76 (2H, m), 7.65-7.51 (2H, m) ,
1.66-1.64 (6H, d)
10.52-10.49 (IH, d), 8.96— 8· 91 (1H， d)， 7.86-7.79 (2H, m) ,
98 7.73-7.71 (2H, d), 7.62-7.53 (IH, m), 7.43-7.40 (2H, m) ,
1.64-1.63 (6H, d)
10.10-10.04 (IH, d), 9.00- 8.95(lH，d)， 7.92-7.78 (3H, m) ,
99
7.68-7.52 (3H, m), 2, 41- 2.40 (3H， d)， 1.66- 1.65 (6H， d)
9.42-9.30 (IH, d) , 8.97-8.89 (IH, d), 7.96-7.74 (3H, m),
100 7.63-7.50 (IH, m), 7.18-7.08 (2H, m), 6· 98- 6· 95 (IH, t)，
3.85-3.84 (3H, d), 1.62— 1.61 (6H， d)
10.28-10.24 (IH, d), 8.92- 8.86 (1H， d)， 7.81-7.76 (2H, m) ,
101 7.52-7.45 (2H, m), 7.23-7.19 (IH, m), 6.92-6.90 (IH, m) ,
6.43-6.37 (IH, m), 2.24 (3H, s), 1.62-1.61 (6H, d)
9.81 (IH, s), 9.03 (IH, s), 7.74-7.57 (3H, m) ,
109
7.18-7.08 (3H, m), 2.28 (3H, s), 2.14 (3H, s), 1.61 (6H, s)
9.16-9.12 (IH, d), 7.98-7.96 (IH, d), 7.69-7.54 (3H, m),
111 7.16-6.94 (3H, m), 6, 79- 6.51 (IH, m)， 3.84 (3H, s), 1.56
(6H, s)
10.41 (IH, s), 9.05 (IH, s) , 7.73-7.67 (4H, m),
112
7.59-7, 55 (1H， t)， 7, 42-7· 40 (2H, d)， 1.59 (6H， s)
10.06 (IH, s), 9.06 (IH, s) , 7.82-7.75 (IH, m),
113 7.69-7.53 (3H, m), 7.36-7.32 (2H, m), 7.28-7.22 (IH, m) ,
2.28 (3H, s), 1.59 (6H, s) 10.16 (IH, s), 9.02 (IH, s) , 7.66-7.45 (5H, m),
7.23-7.19 (IH, m), 6.92- 6.90 (1H， d)， 2.29 (3H, s),
1.60-1.57 (6H, d)
9.44 (IH, s), 9.01 (IH, s), 8.29-8.27 (IH, d) ,
7.70-7.69 (2H, d), 7.59- 7.55 (1H， t)， 7.29-7.20 (2H, m) 3.91 (3H, s), 1.90-1.78 (2H, m), 1.52 (3H, s),
0.96-0.92 (3H, t)
10.13-9.98 (IH, d) , 8.93— 8.78 (1H， d) , 7.78-7.53 (3H, m), 7.40-7.36 (2H, d), 2.45-2.42 (3H, d), 2.33 (3H, s), 1.97-1.81 (2H, m), 1, 57- L 56 (3H， d)， 1.03-Q.96 (3H, m)
10.10-9.92 (IH, d), 8.98— 8.79 (1H， d) , 7.73-7.56 (4H, m) , 7.33 (IH, s), 2.44-2.42 (3H, d), 2.34-2.29 (3H, d),
2.00-1.86 (2H, m), 1, 60- L 57 (3H， d)， 1.02-Q.98(3H, t) 10.57 (IH, s), 8.95 (IH, s) , 7.77-7.67 (4H, m),
7.59-7.49 (2H, m), 2.46-2.44 (3H, d), 1.97-1.83 (2H, m)
1.57 (3H, s), 1.02-0.98(3H,t)
10.16-9.94 (IH, d) , 8.94- 8, 71 (1H， d)， 7.74-7.55 (5H, m),
7.48-7.46 (IH, d), 1.97-1.82 (2H, m), 1.57-1.56 (3H, d)
1.01-0· 98 (3H, t)
10.14(1H, s), 8.75 (IH, s) , 7.71- 7.69 (IH, t) ,
7.56-7.55 (2H, d), 7.36 (2H, s), 2.46 (6H, s),
2.41-2.38 (IH, m), 1.51 (3H, s), 1.06— 1.04 (3H， d) ,
0.95-0.93 (3H, d)
10.12-9.92 (IH, d) , 8.92- 8, 76 (1H， d)， 7.72-7.53 (4H, m), 7.33 (IH, s), 2.44-2.42 (3H, d), 2.33-2.29 (3H, d), 2.27-2.24 (IH, m), 1.53— 1.52 (3H， d) , 1.07— 1.05 (3H， d) 0.98-0.95 (3H, t)
10.76-10.56 (IH, d), 8.89-8.74 (IH, d), 7.77-7.48 (6H, m) , 2.46-2.44 (3H, d), 2.29-2.24 (IH, m), 1.51- 1.49 (3H， d) 1.07-1.04 (3H, d), 0.97-0.92 (3H, t)
10.16-9.92 (IH, d) , 8.87— 8, 65 (1H， d)， 7.87-7.45 (6H, m),
2.40-2.23 (IH, m), 1.51 (3H, s), 1.07- 1.04 (3H， d)，
0.97-0.92 (3H, t)
8.83-8.76 (IH, d) , 8.66-8.58 (IH, m), 7.60- 7.58 (2H， m)， ~~ 7.52-7.49 (IH, m), 7.24-7.21 (IH, m), 6.55 (IH, s), 6.50-6.47 (IH, m), 4.32-4.30 (2H, d), 3.80 (3H, s),
3.75 (3H, s), 1.61- 1.59 (6H，d)
9.37-9.31 (IH, d) , 8.83- 8.78 (1H， d)， 7.65-7.45 (3H, m)
3.65 (4H, s), 2.86 (4H, s) , 1.65- L 64 (6H， d)
9.54 (IH, s), 8.80 (IH, s), 7.75-7.64 (2H, m) ,
7.56-7.46 (IH, m), 3, 67- 3· 65 (4H, t)， 2.88-2.86 (4H, t) ,
1.64 (6H, s)
8.84-8.77 (IH, d) , 8.66-8.58 (IH, dt), 7.74-7.65 (2H, m), 7.52-7.42 (IH, dd), 7.24-7.21 (IH, q) , 6.58- 6.47 (2H， m) : 4.32-4.31 (2H, d)， 3.81—3, 75 (6H, dd)， 1.61-1.60 (6H, d)
8.89 (IH, s), 8.84 (IH, s), 7.99 (IH, d), 7.55 (IH, d) 7. 23 (1H, t) , 1. 65 (12H, s) 将上述式（I )所示的邻苯二甲酰胺类化合物作为有效成分的有害生物防治剂， 在低药量 下对有害生物具有超高的防治效果。
本发明所述的式（I )表示的含氰基的邻苯二甲酰胺类化合物或其农业上适用的盐， 可以 用于农用化学杀虫剂。
具体地说， 对于防治小菜蛾、 甘蓝夜蛾、 斜纹夜蛾、 甜菜夜蛾、 草地贪夜蛾、 棉铃虫、 东方粘虫、 烟夜蛾、 烟毒蛾、 稻纵卷叶野螟、 稻褐带卷蛾、 苹果小卷蛾、 桃小实心蛾、 梨小 食心虫、 小地老虎、 马铃薯叶甲、 黄守瓜、 蚜虫类、 粉虱类、 蓟马类、 蝗虫类、 斑潜蝇类等 农业害虫类。 其中， 含有本发明化合物的农业园艺用有害生物防治剂， 对于农业害虫类等特 别有效。 另外， 含有本发明式（I )表示的含氰基的邻苯二甲酰胺类化合物的农业园艺用有害 生物防治剂， 对于防治对有机磷类、 氨基甲酸酯类、 合成除虫菊酯类、 苯甲酰脲类等已产生 抗性的害虫有效。进而， 本发明所述的式（I )表示的含氰基的邻苯二甲酰胺类化合物因为具 有优异的渗透转移性， 所以通过使用含有本发明所述的式（I )表示的含氰基的邻苯二甲酰胺 类化合物的农业园艺用有害生物防治剂来处理土壤， 在防治土壤有害昆虫类、 螨类等类的同 时也可防治茎叶部的害虫。
作为含有本发明所述的式（I )表示的含氰基的邻苯二甲酰胺类化合物的有害生物防治剂 的其他的优选形态， 可列举出综合防治上述植物寄生性螨类、 农业害虫类、 土壤害虫类等的 农业园艺用有害生物防治剂。
本发明所述的式（I )表示的含氰基的邻苯二甲酰胺类化合物可以作为农药化学杀虫剂的 活性组份， 配制成各种液剂、 乳油、 悬浮剂、 水悬剂、 微乳剂、 （水）乳剂、 粉剂、 可湿性粉 剂、 可溶性粉剂、 （水分散性） 颗粒剂或胶囊剂等,用于水稻、 大豆、 小麦、 棉花、 玉米、 蔬 菜和油菜等农作物的害虫防治。
当配置成农药化学杀虫剂时， 活性组分的重量百分含量即本发明所述的式（I )表示的含 氰基的邻苯二甲酰胺类化合物的重量百分含量优选为 0. 001%-99. 99% (重量）， 其余为农业上 可接受的载体。
载体可以是固体或液体。 合适的固体载体包括天然的或合成的粘土和硅酸盐， 例如天然 硅石和硅藻土； 硅酸镁例如滑石； 硅酸铝镁例如高岭石、 高岭土、 蒙脱土和云母； 白碳黑、 碳酸钙、 轻质碳酸钙； 硫酸钙； 石灰石； 硫酸钠； 胺盐如硫酸铵、 六甲撑二胺。 液体载体包 括水和有机溶剂， 当用水做溶剂或稀释剂时， 有机溶剂也能用做辅助剂或防冻添加剂。 合适 的有机溶剂包括芳烃例如苯、 二甲苯、 甲苯等； 氯代烃， 例如氯代苯、 氯乙烯、 三氯甲垸、 二氯甲烷等； 脂肪烃， 例如石油馏分、 环己烷、 轻质矿物油； 醇类， 例如异丙醇、 丁醇、 乙 二醇、 丙三醇和环己醇等； 以及它们的醚和酯； 还有酮类， 例如丙酮、 环己酮以及二甲基甲 酰胺和 N-甲基 -吡咯烷酮。
载体也可以是表面活性剂。 合适的表面活性剂可以是乳化剂、 分散剂或湿润剂； 可以是 离子型的或非离子型的。 非离子型乳化剂例如聚氧乙烯脂肪酸脂、 聚氧乙烯脂肪醇醚、 聚氧 乙烯脂肪氨， 以及市售的乳化剂： 农乳 2201B、农乳 0203B、农乳 10(f、农乳 50(f、农乳 600 农乳 600- 2#、 农乳 1601、 农乳 2201、 农乳 NP- 10、 农乳 NP- 15、 农乳 507*、 农乳 0X- 635、 农 乳 0X-622、 农乳 0X-653、 农乳 0X-667、 宁乳 36s。 分散剂包括木质素磺酸钠、 拉开粉、 木质 素磺酸钙、 甲基萘磺酸甲醛缩合物等。 湿润剂为： 月桂醇硫酸钠、 十二垸基苯磺酸钠、 垸基 萘磺酸钠等。
上述农药化学杀虫剂可由通用的方法制备。例如，将活性物质与液体溶剂和 /或固体载体 混合， 同时加入表面活性剂如乳化剂、 分散剂、 稳定剂、 湿润剂， 还可以加入其它助剂如： 粘合剂、 消泡剂、 氧化剂等。
本发明所述的的含氰基的邻苯二甲酰胺类化合物还可以与除草剂、 杀菌剂、 杀线虫剂、 植物生长调节剂、 肥料， 以及其它杀虫剂或其他农用化学品混配使用。
在防治有害生物时， 当将本发明所述的农药制剂施于需要控制的有害生物或其生长的介 质上， 其中活性组分即式 （I ) 表示的含氰基的邻苯二甲酰胺类化合物的有效量为每公顷 10 克到 1000克。
本发明所述的式（I )表示的含氰基的邻苯二甲酰胺类化合物或其农业上适用的盐及其制 剂， 相比现有技术具有以下优点：
( 1 )本发明首次在邻苯二甲酰胺结构中引入 α -氨基腈官能团，化合物结构具有新颖性;
( 2 )本发明的化合物及其制剂具有超高的杀虫活性： 在 0. 16mg/L剂量下对鳞翅目害虫 表现出很好的效果；
( 3 )本发明的化合物及其制剂具有很好的安全性， 对部分作物如小麦、 大豆、 棉花、 玉 米、 水稻等安全性好， 并且对环境具有性。
(4)本发明的化合物及其制剂具有合理的毒性、生态毒性和环境相容性， 属低毒环境友 好型农药。 具体实施方式
以下具体实施例用来进一步说明本发明， 但是本发明不限定于此。
合成实施例 实施例 1
3—碘一 N1— （2 甲基一 4一七氟异丙基苯基） N2— （1 甲基一 1一氰基乙基） 邻苯二 甲酰胺的制备 （化合物 24)
歩骤 1 : 合成 3—碘一 N— （1 甲基一 1一氰基乙基）邻酰胺基苯甲酸
2-氨基 -2-二甲基丙腈（0. 8½， lOmmol)和三乙胺（0. 20g, 2mmol)的混合物溶于 Ν, Ν-二甲 基乙酰胺 (DMA, 3mL)中，在室温下缓慢加入到 3-碘代邻苯二甲酸酐（2. 74g， lOmmol)的 DMA (8mL) 溶液中。 反应混合物搅拌 lh， 倒入水中， 用稀盐酸酸化。 水相用乙酸乙酯萃取， 用无水硫酸 镁干燥。 在减压下除去溶剂得到橙色油状产物， 物在数小时内析出固体， 用乙醚和正己垸的 混合物洗涤。得白色固体产物 1. 80g (50%)， 熔点 141〜143° C, 核磁数据为： 1誦 R (400丽 z， DMSO-c ,)： δ =13. 23 (1Η, brs) , 8. 77 (1H, s) , 8· 09- 8. 07 (1H， d)， 7. 93- 7· 91 (1H， d)，
7. 28-7. 24 (1H, t) , 1. 64 (6H，s)。
歩骤 2: 合成 3—碘一 N— （1 甲基一 1一氰基乙基）邻苯异酰亚胺
将三氟乙酸酐 (0. 76g， 3. 6mmol)加入到 3—碘一 N— （1 甲基一 1一氰基乙基） 邻酰胺基 苯甲酸（1. 07g， 3mmol)在 10ml甲苯的悬浮液中， 反应混合物在室温下搅拌 30min。减压下除去 溶剂得到 1. 02^且品， 该粗品可不经过纯化直接进入下一步反应。 化合物熔点 148〜150° C, 核磁数据为： ¾ NMR (400MHz, CDC13)： δ =8. 30-8. 28 (1Η, d) , 7. 98-7· 96 (1H， d) ,
7. 45-7. 41 (1H, t) , 1. 85 (6H，s)。
步骤 3: 合成 3—碘一 N1— （2 甲基一 4一七氟异丙基苯基） N2— （1 甲基一 1一氰基乙基) 邻苯二甲酰胺
在 3—碘一 N—（1 甲基一 1一氰基乙基）邻苯异酰亚胺（1. 02g， 3mmol)的乙腈溶液（lOmL) 中， 加入 2-甲基 -4-七氟异丙基苯胺（0. 80g， 2. 90mmol)和三氟乙酸 (O. Olg) , 反应混合物搅拌 3h。 过滤， 收集沉淀物， 用少量低温乙腈洗涤， 得到第一批产物； 滤液蒸除溶剂后， 将所得 残余物通过硅胶柱色谱纯化 （洗脱剂： 正己烷 /乙酸乙酯 = 2/1-1/1 ) , 得第二批产物， 将两 批产物合并， 得到 3—碘一 N1— （2 甲基一 4一七氟异丙基苯基） N2— （1 甲基一 1一氰基 乙基）邻苯二甲酰胺 1. 04g (60%) ,熔点 243〜245° C,核磁数据为： 1誦 R (400MHz, DMS0- 4)： δ = 9. 85 (1H, s) , 8. 99 (1H, s) , 8. 05-8. 03 (1H, d) , 7. 79-7. 77 (2H, d) , 7. 53-7. 49 (2H, t) , 7. 33-7. 29 (1H, t) , 2. 36 (3H, s) , 1. 61 (6H，s)。 实施例 2
4一氯一 N1— （2， 4一二氯苯基） N2— （1 甲基一 1一氰基乙基） 邻苯二甲酰胺的制备 (化合物 48) 步骤 1 : 合成 4一氯一 N （1 甲基一 1一氰基乙基）邻酰胺基苯甲酸
2-氨基 -2-二甲基丙腈（0. 84g, lOmmol)和三乙胺（0. 20g, 2mmol)的混合物溶于 Ν, Ν-二甲 基乙酰胺 (DMA, 3mL)中， 在室温下缓慢加入到 4-氯邻苯二甲酸酐（2. 74g, lOmmol)的 DMA (8mL) 溶液中。 反应混合物搅拌 lh， 倒入水中， 用稀盐酸酸化。 水相用乙酸乙酯萃取， 用无水硫酸 镁干燥。 在减压下除去溶剂得到透明油状产物， 物在数小时内析出固体， 用乙醚和正己垸的 混合物洗涤。 得产物 1. 73g (65 %)， 熔点 127〜130° C。
步骤 2 : 合成 4一氯一 N （1 甲基一 1一氰基乙基）邻苯异酰亚胺
将三氟乙酸酐（l. Olg, 4. 8mmol)加入到 4一氯一 N ( 1 甲基一 1一氰基乙基) 邻酰胺基 苯甲酸（1. 06g, 4mmol)在 12ml甲苯的悬浮液中， 反应混合物在室温下搅拌 30min。减压下除去 溶剂得到 0. 99g粗品， 该粗品可不经过纯化直接进入下一步反应。
步骤 3: 合成 4一氯一 N1— ( 2, 4一二氯苯基） N2 （1 甲基一 1一氰基乙基） 邻苯二甲酰 胺
在 4一氯一 N （1 甲基一 1一氰基乙基）邻苯异酰亚胺 (0. 99g， ½mol)的乙腈溶液（12mL) 中， 加入 2， 4-二氯苯胺 (0. 63g， 3. 9mmol)和三氟乙酸 (0. 01g)， 反应混合物搅拌 3h。 过滤， 收集沉淀物， 用少量低温乙腈洗涤， 得到第一批产物； 滤液蒸除溶剂后， 将所得残余物通过 硅胶柱色谱纯化（洗脱剂： 正己烷 /乙酸乙酯 = 2/1-1/1 )，得第二批产物， 将两批产物合并， 得到 4一氯一 N1 （2， 4一二氯苯基） N2 （1 甲基一 1一氰基乙基）邻苯二甲酰胺 1. 13g (71 %)，熔点 176〜178° C,核磁数据为： 1誦 R (400MHz, DMS0- )： δ =9. 96 ( 1H, s)， 9. 08 (1H, s)， 7. 85-7. 70 (4H, m) , 7. 67-7. 55 ( 1Η, m) , 7. 49- 7. 41 (1H， m)， 1. 61 (6H，s)。 索引表 1、 索引表 2和表 3中列举的本发明化合物 （I ) 均可根据上述合成实施例 1 -2 所述的制备方法进行合成。 以下实施例 3 至实施例 5给出以本发明的化合物 （I ) 作为活性物质组份， 加工配制几 种杀虫剂剂型的实际例子， 需要指出的是本发明并不仅仅局限在下述实例的范围内。 在这些 配方例子中， 所有的 "％"均指重量百分比。 实施例 3 可湿性粉剂配方
将 15%的化合物（24 ) (表 1 )、 5%的木质素磺酸盐（MQ)、 1%的月桂醇聚氧乙烯醚（JFC)、 40%的硅藻土和 44%的轻质碳酸钙均匀地混合， 粉碎， 即得可湿性粉剂。 实施例 4乳油配方
将 10%的化合物（24) (表 1、 5%的农乳 500号（钙盐）、 5%的农乳 602号、 5%的 N-甲基 -2- 吡咯垸酮和 75%的二甲苯加热搅拌均匀， 即得乳油。 实施例 5 粒剂配方
将 5%的化合物（24) (表 1 )、 1%的聚乙烯醇（PVA)、 4%的萘磺酸钠甲醛缩合物（NM0)和 90%粘土均匀地混合， 粉碎， 然后向此 100份混合物加入 20份水， 捏合， 用挤压成粒机， 制 成 14 32目的颗粒， 干燥， 即得颗粒剂。 下面给出使用本发明的化合物进行生物活性测定的实例， 需要指出的是本发明并不仅仅 局限在下述实例的范围内。
杀虫活性评价试验根据下列方法进行：
称取一定质量制剂， 加蒸馏水稀释配制成测定所需浓度药液。 筛选浓度为从 500、 100、 20, 4.0. 8、0. 16, 0. 032mg/L,药剂处理药液量 lOmL。试验靶标为东方粘虫（ i 'mg separa ta), 棉铃虫 ( Helico this armigera)、首猜 ¾ϊ ( Aphis medicagini),小菜娥 ( PI u tell a xylostella)、 斜纹夜蛾（ oofe ^'s litura) 草地贪夜蛾 Spodoptem frugiperda)等。
( 1 ) 东方粘虫筛选一浸苗词喂法
将玉米叶在药液中充分浸润后自然阴干， 放入培养皿中， 接 3龄中期幼虫， 加盖标记后置 于观察室内。 试验重复 4次。 72h后检査结果。 以毛笔轻触虫体， 无反应视为死虫。
( 2) 棉铃虫筛选——喷雾法
将盆栽棉花 （2-3张叶龄）进行药剂喷雾处理， 晾干。 放入培养室继续正常培养。 在 5、 12、 19d后用剪刀将叶片剪下， 放于 Φ 9cm塑料培养皿内， 接草地贪夜蛾或棉铃虫幼虫， 放 一张滤纸， 加盖。 置于观察室内， 6d后检查结果。
( 3 ) 小菜蛾筛选——浸渍法
将甘蓝片剪下， 打孔成圆片， 然后浸于药液中 20s， 放于 Φ9™塑料培养皿内 （5片 /皿）， 接小菜蛾 2龄幼虫 15头 /皿， 放一张滤纸， 加盖。 置于 26°C室内培养。 试验重复 4次。 72h 后检查结果。 以尖头镊子轻触虫体， 无反应视为死虫。
(4) 苜蓿蚜筛选——浸渍法
将蚕豆叶片剪去两端， 背面朝上放在小块棉花上， 置于塑料培养皿内， 加少量水， 接苜蓿 蚜成蚜以产若蚜。 24h后去除成蚜， 继续培养 2d后将叶片在药液中充分浸润 5s后， 重新置 于棉花上， 自然凉干。 24h后检查结果。 ( 5 )斜纹夜蛾筛选一浸渍法
将甘蓝片剪下， 用打孔器打取甘蓝圆叶， 于药液中浸 20s， 晾干。 放入带有圆孔 （ 2cm) 的六孔塑料盒内， 每孔 3片。 接入斜纹夜蛾 3龄中期幼虫 1头 /孔， 放入观察室内。试验重复
4次。 72h后检查结果。 以尖头镊子轻触虫体， 无反应视为死虫。
( 6) 草地贪夜蛾筛选——喷雾法
将盆栽棉花 （2-3张叶龄）进行药剂喷雾处理， 晾干。 放入培养室继续正常培养。 在 5、 12、 19d后用剪刀将叶片剪下， 放于 Φ 9cm塑料培养皿内， 接草地贪夜蛾或棉铃虫幼虫， 放 一张滤纸， 加盖。 置于观察室内， 6d后检査结果。 注：生物活性测定实施例所述的编号与索引表 1、索引表 2和表 3所述的化合物编号相对应。 试验统计： 统计各个处理的死虫数和活虫数， 计算死亡率。
cr 试虫数 -药后活虫数 i m
死 IT率 (%) = , x lOO
试虫数
CK对照死亡率〈20 %，试验结果可信，试验结果进行校正， CK对照死亡率〈5%时可不校正。 生测试验结果表明： 本发明化合物具有良好的杀虫活性， 特别是对鳞翅目害虫， 如东方 粘虫、 棉铃虫、 小菜蛾、 斜纹夜蛾、 草地贪夜蛾等具有广谱的杀虫活性， 对同翅目害虫也有 一定的杀虫活性。 "mg/L" 均指每毫克活性物 /升。
500mg/L浓度下， 化合物 23、 24和 137对东方粘虫的死亡率为 100 %。
500mg/L浓度下， 化合物 32、 33对苜蓿蚜的死亡率为 100 %。
500mg/L浓度下， 化合物 23、 24、 32、 33、 34、 40、 46、 47、 48、 137对小菜蛾的死亡 率大于 80 %， 100mg/L浓度下， 化合物 23、 24、 33、 34、 46、 47、 48、 137对小菜蛾的死亡 率大于 80 %， 20mg/L浓度下， 化合物 23、 24、 34、 46、 47、 48对小菜蛾的死亡率大于 80 %， 4mg/L浓度下， 化合物 23、 24、 34、 47、 48对小菜蛾的死亡率大于 80 % , 0. 8mg/L浓度下， 化合物 23、 24、 47对小菜蛾的死亡率大于 80%， 0. 16mg/L浓度下， 化合物 24、 47对小菜蛾 的死亡率为 100%。
0. 8mg/L浓度下， 化合物 23、 24对棉铃虫的死亡率为 100 %， 0. 16mg/L浓度下， 化合物 24对棉铃虫的死亡率为 100%。
0. 8mg/L浓度下， 化合物 23、 24对草地贪夜蛾的死亡率大于 80 %， 0. 16mg/L浓度下， 化合物 24对草地贪夜蛾的死亡率为 100%。
0. 16mg/L浓度下， 化合物 24对斜纹夜蛾的死亡率为 100 %。
将本发明化合物与对照化合物氟虫酰胺（flubendiamide)的杀虫活性进行比较， 结果列 于表 4。
杀虫活性比较
Figure imgf000024_0001
表 4显示， 与现有化合物氟虫酰胺相比， 当浓度大于 0. 16 mg/L时， 本发明化合物对小 菜蛾的杀虫活性基本相当， 对斜纹夜蛾发挥了较高的杀虫作用， 特别是在低施用率下 (0. 032Mg/L), 本发明化合物要比现有化合物优异， 远远高于毒死蜱和氯氰菊酯的活性。 基 于这些化合物结构上的相似性， 这种提高的结果是出人意料的。
对化合物 24进行了温室残留活性试验， 结果列于表 5。 试验结果表明： 在 0. 8mg/L时， 对化合物 24在药后 19 天处理试虫， 小菜蛾、 草地贪夜蛾和棉铃虫死亡率仍达 100 % ; 在 0. 16mg/L时， 随着处理时间的延长， 药效降低， 药后 12天， 仍能达 100%， 药后 19天， 小 菜蛾、 草地贪夜蛾和棉铃虫死亡率分别降为 60%、 55 %和 80 % ; 0. 032 mg/L时， 对 3种试 虫的药效均较低。 对化合物 24具有很高的残留活性。 表 5化合物 24残留活性试验结果
死亡率 （％)
浓度
化合物 小菜蛾 草地贪夜蛾 棉铃虫
(mg/L)
5 12 19 5 12 19 5 12 19
0. 8 100 100 100 100 100 100 100 100 100
24 0. 16 80 100 60 100 100 55 100 100 80
0. 032 60 70 0 0 20 20 0 50 30

Claims

权利要求书
1、 一种式 （I )表示的含氰 二甲酰胺类化合物或其农业上适用的盐，
Figure imgf000025_0001
R R2独立地选自氢、 Cf 院基、 C3- ( 环垸基、 C2-C6链烯基或(：2-(：6炔基， 所述基团上的 氢还可以被卤素、 氰基、 硝基、 d-C6垸氧基、 苯基、 取代的苯基、 苯氧基、 取代的苯氧基、 垸硫基、 垸基亚磺酰基或烷基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环垸基；
R3选自氢、 卤素、 氰基、 硝基、 芳基、 酯基、 d-C6垸基、 卤代 d-C6垸基、 d-C6垸氧基或 卤代 氧基；
R4选自氢或(^-( 6垸基；
X选自亚甲基、 d-C6垸基、 氰基取代的亚甲基或直接键；
或者 X和 R4同所连接的 N组成三元环、四元环、五元环、六元环、五元杂环或六元杂环； Y选自氢、 卤素、氰基、硝基、羟基、 d-C6垸基、 卤代 d-C6垸基、 d- C3垸氧基、 卤代 d-C3 垸氧基、 苯基、 取代的苯基、 杂环芳基或取代的杂环芳基；
A为 CH或 N;
m为 0〜4的整数。
2、 按照权利要求 1所述的含氰基的邻苯二甲酰胺类化合物， 其特征在于：
R R2独立地选自氢、 d-C3院基、 （3_( 6环垸基或 (：2_( 3链烯基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 烷硫基、 烷基亚磺酰基或垸基磺酰基进一歩取代；
或者 R1和 R2同所连接的碳一起形成环己基；
R3选自氢或卤素；
R4选自氢或^-(：3垸基；
或者 X和 R4同所连接的 N组成五元杂环或六元杂环；
Y选自氢、 卤素原子、 硝基、羟基、 垸基、 氟代 d-C3垸基、 d-C3垸氧基或氟代 d-C3 院氧基；
m为 1〜3的整数。
3、 按照权利要求 2所述的含氰基的邻苯二甲酰胺类化合物， 其特征在于：
R R2独立地选自氢、 甲基、 乙基、异丙基、 环丙基或烯丙基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 甲硫基、 甲基亚磺酰基、 甲基磺酰基等基团进一步取代；
R3选自氟、 氯、 溴或碘， R3位于苯环的 3位或 4位；
R4为氢或甲基；
X为亚甲基、 甲基、 氰基取代的亚甲基或直接键；
或者 X和 R4同所连接的 N组成含氧六元杂环；
Y选自氢、 氟、 氯、 硝基、 羟基、 甲基、 甲氧基、 三氟甲基、 三氟甲氧基或七氟异丙基。
4、按照权利要求 3所述的含氰基的邻苯二甲酰胺类化合物，其特征在于所述的邻苯二甲酰胺 类化合
Figure imgf000026_0001
5、按照权利要求 1所述的含氰基的邻苯二甲酰胺类化合物，其特征在于包括任意比例的 R和 /或 S旋光异构体。
6、 一种用于制备按照权利要求 1 所述的含氰基的邻苯二甲酰胺类化合物的中间体， 其特征 在于具有如下式 （Π ) 或 （
Figure imgf000026_0002
( I I ) ( III )
其中：
R R2独立地选自氢、 C「C6烧基、（3-(：6环垸基、 C2-C6链烯基或 C2-C5炔基， 所述基团上的 氢还可以被卤素、 氰基、 硝基、 （^-[：6垸氧基、 苯基、 取代的苯基、 苯氧基、 取代的苯氧基、 院硫基、 垸基亚磺酰基或垸基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环烷基； R3选自氢、 卤素、 氰基、 硝基、 芳基、 酯基、 d-C6垸基、 卤代 d-C6烷基、 d-C6垸氧基或 卤代 垸氧基。
7、 按照权利要求 6所述的用于制备按照权利要求 1所述的邻苯二甲酰胺类化合物的中间体， 其特征在于：
R R2独立地选自氢、 d-C3烧基、 C3-C6环垸基或 C2-C3链烯基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 垸硫基、 垸基亚磺酰基或垸基磺酰基进一步取代；
或者 R1和 R2同所连接的碳一起形成环己基；
R3选自氢或卤素。
8、 按照权利要求 7所述的用于制备按照权利要求 1所述的邻苯二甲酰胺类化合物的中间体， 其特征在于：
R R2独立地选自氢、 甲基、 乙基、异丙基、 环丙基或烯丙基， 所述基团上的氢还可以被 取代的苯基、 取代的苯氧基、 甲硫基、 甲基亚磺酰基、 甲基磺酰基等基团进一歩取代； R3选自氟、 氯、 溴或碘， R3位于苯环的 3位或 4位。
9、一种权利要求 1所述的含氰基的邻苯二甲酰胺类化合物的制备方法，其特征在于包括以下 步骤：
( 1 )在惰性溶剂， 在存在或不存在碱的情况下， 结构式 (VI)表示的取代的邻苯二甲 酸酐与结构式（V)表示的取代的氨基乙腈进 N-酰化反应得到结构式（I I I)表示的取代邻酰 胺基苯甲酸；
Figure imgf000027_0001
( 2 ) 在惰性溶剂， 结构式（I I I)表示的取代邻酰胺基苯甲酸与酰化试剂反应得到结 构式（I I)表示的取代的邻苯二甲酰异
Figure imgf000027_0002
( 3 )在惰性溶剂中， 在存在或不存在酸的情况下， 结构式（Π)表示的取代的邻苯二 甲酰异酰亚胺与结构式（IV)表示的取代的胺反应得到结构式 α)表示的含氰基的邻苯二甲 酰胺类化合物；
Figure imgf000028_0001
其中： R R2、 R R\ A、 X、 Y和 m定义如权利要求 1所述。
10、 按照权利要求 9所述的含氰基的邻苯二甲酰胺类化合物的制备方法， 其特征在于：
歩骤（1 )中所述惰性溶剂选自四氢呋喃、 乙腈、 1， 4-二氧六环、 N，N-二甲基甲酰胺、
N，N-二甲基乙酰胺、 甲苯或二氯甲垸中的一种或两种以上组合， 所述碱包括有机碱和无 机碱， 所述有机碱选自三乙胺、 吡啶或 3-甲基吡啶， 所述无机碱选自碳酸钾、 碳酸氢钠、 氢氧化钠或无水乙酸钠；
步骤 （2 ) 中所述惰性溶剂选自甲苯、 1， 2-二氯乙垸、 乙酸乙酯、 四氢呋喃、 乙腈、 1， 4-二氧六环或二氯甲垸中的一种或两种以上组合， 所述酰化试剂为氯甲酸甲酯、 乙酸 酐或三氟乙酸酐；
步骤 （3 ) 中所述惰性溶剂选自四氢呋喃、 二氯甲垸、 1， 2-二氯乙垸、 乙醚、 1， 4- 二氧六环、 乙腈或甲苯中的一种或两种以上组合， 所述酸包括有机酸和无机酸， 所述有 机酸选自乙酸、 三氟乙酸或对甲基苯磺酸， 所述无机酸为盐酸或硫酸；
反应温度为在 0° C到所用惰性溶剂的沸点之间。
11、 一种按照权利要求 1至 10之一所述的结构式 （I )表示的含氰基的邻苯二甲酰胺类化合 物或其农业上适用的盐的用途， 其特征在于用于农用化学杀虫剂。
12、 一种农药制剂， 其特征在于， 含有 0. 001%-99. 99% (重量） 的权利要求 1所述的结构式 ( I )表示的含氰基的邻苯二甲酰胺类化合物或其农业上适用的盐，以及农业上可接受的载体。
13、一种防治有害生物的方法， 其特征在于： 将权利要求 12所述的农药制剂施于需要控制的 有害生物或其生长的介质上， 其中活性组分含氰基的邻苯二甲酰胺类化合物的有效量为每公 顷 10克到 1000克。
PCT/CN2011/078711 2010-09-13 2011-08-22 一种含氰基的邻苯二甲酰胺类化合物、制备方法和作为农用化学品杀虫剂的用途 WO2012034472A1 (zh)

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