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    • 专利摘要:
    COMPOUND OF M-DIAMIDE AND METHOD OF PREPARATION OF THE SAME AND USE OF THE SAME.The present invention relates to m-diamide compounds and a method of preparing and using them. The m-diamide compounds have a structure represented by the formula I. The m-diamide compounds of the present invention can have high insecticidal activity at a low dose and take effect quickly, they can exert insecticidal activity one day after application, they can reach high insecticidal activity within three days, and may have a satisfactory fast-acting property; in addition, due to the good effect at a low dose, m-diamide compounds can reduce damage to plants and humans caused by excessive concentrations of drugs, allowing the production of less medicinal residues during the application that is more conducive to protection of the environment, and have wide application possibilities.
    公开号:BR112020004919A2
    申请号:R112020004919-0
    申请日:2019-03-12
    公开日:2021-01-26
    发明作者:Liang Lv；Jiyong Liu；Juncheng XIANG；WenJing Ma；Liqi ZHOU；Shuang HOU；Jueping Ni；Zongcheng Li
    申请人:Cac Shanghai International Trading Co., Ltd.；
    IPC主号:
    专利说明:

    [001] [001] The present invention relates to the field of insecticides, it refers to certain benzamide meta-carboxamide derivatives, its production process and its utility as a pesticide, in particular it refers to derivatives of 3 -N-cyclopropyl methyl meta-carboxamido benzamide its production process and its utility as a pesticide. Background of the Invention
    [002] [002] The damage caused by pests is still very significant in agriculture and horticulture. The appearance of insects showing resistance to various insecticides and the environmental impact of existing pesticides represent serious problems, and new insecticides with better insecticidal activity at low concentration and environmentally friendly need to be constantly developed.
    [003] [003] The preparation and insecticidal activities of benzamide meta-carboxamido derivatives have already been disclosed. CN102119143A discloses the structures and insecticidal activities of KC1 and KC2 (compounds 7-1574 and 7-1595 in the patent, respectively). KC1 has been marketed as an insecticide and its common name is broflanilide. These compounds already disclosed have insecticidal activity, but their insecticidal activity is not satisfactory or is slow at low concentration.
    [004] [004] In order to satisfy the demands of the agricultural and forestry industry, new insecticides with high insecticidal activity and rapid efficacy at low concentration are still needed.
    [005] [005] In view of the deficiencies of the state of the art, the object of this invention is to present certain derivatives of benzamide meta-carboxamido, its production process and its utility as a pesticide, namely, derivatives of 3-N-cyclopropyl methyl meta-carboxamido benzamide and its production process and its usefulness as a pesticide. The 3-N-cyclopropyl methyl meta-carboxamido benzamide derivatives of this invention have satisfactory insecticidal activity at low concentration and satisfactory fast-acting property. The 3-N-cyclopropyl methyl meta-carboxamido benzamide derivatives of this invention are used at low concentration, and thus are more conducive to environmental protection.
    [006] [006] To achieve the above objectives, this invention is specified by the following technical modalities:
    [007] [007] This invention features benzamide meta-carboxamido derivatives (namely, 3-N-cyclopropyl methyl meta-carbamido benzamide derivatives), which are defined by formula I: Formula I where: Z is selected from the group that consists of H, F, Cl, Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1- C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl; Y1 is selected from the group consisting of F, Cl, Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl or C1-C6 haloalkoxy; Y2 is C1-C6 haloalkyl;
    [008] [008] The 3-N-cyclopropyl methyl meta-carboxamido benzamide derivatives defined in formula I have excellent insecticidal activity and fast-acting property. Its insecticidal activity could reach 80%, and even 90% -100% at low concentration. Its insecticidal activity can be exercised one day after application, and the excellent insecticidal activity can be achieved on the third day after application. The satisfactory insecticidal activity at the low concentration of the benzamide meta-carboxamido derivatives of this invention can reduce the dose and the pesticide residue, and thus are more conducive to protecting the environment.
    [009] [009] Preference is given to compounds of formula I, in which Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl; Y1 is selected from the group consisting of F, Cl, Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl or C1-C6 haloalkoxy; Y2 is C1-C6 haloalkyl; R1 is selected from the group consisting of F or OCH3; R2 is F. R3 is selected from the group consisting of H, F, Cl, Br, I, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl or C3-C8 halocycloalkyl; R4 is selected from the group consisting of H or halogen;
    [0010] [0010] Most preferred compounds of formula I, in which Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, difluoro-methoxy, trifluoromethoxy, methylsulfinyl, trifluoromethyl sulfinyl , methylsulfonyl or trifluoromethyl sulfonyl; Y1 is selected from the group consisting of F, Cl, Br, I, CN, NO2, methyl, i-propyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl or trifluoromethoxy; Y2 is selected from the group consisting of trifluoromethyl, pentafluoroethyl or heptafluoroisopropyl; R1 is selected from the group consisting of F or methoxy; R2 is F; R3 is selected from the group consisting of H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, t-butyl, n-pentyl, 1-methylbutyl, 2,2- dimethylpropyl, 2-methylbutyl, 1,3-dimethylbutyl, n-hexyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, cyclopropyl, cyclopropyl, cyclopropyl, cyclopropyl, cyclopentyl ; R4 is selected from the group consisting of H, F or Cl; W1 and W2 are independently of each other O.
    [0011] [0011] Most preferred compounds of formula I, in which the compound benzamide meta-carboxamide compound is any one selected from table 1. Table 1 Compound Z W1 Y1 Y2 R1 R2 R3 R4 Appearance (melting point ： ° C） N °
    [0012] [0012] Comments on the compounds in Table 1: W2 is O, "H" represents hydrogen, "F" represents fluorine, "Cl" represents chlorine, "Br" represents bromine, "I" represents iodine, "CN" represents cyan , "NO2" represents nitro, "OMe" represents methoxy, "CH2Cl" represents mo-
    [0013] [0013] Additional most preferred compounds of formula I, in which Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, trifluoromethyl, trifluoromethoxy, methylsulfonyl or trifluoromethyl sulfonyl; Y1 is selected from the group consisting of Br or I; Y2 is a trifluoromethyl group; R1 is selected from the group consisting of F or methoxy; R2 is F; R3 is selected from the group consisting of H, methyl or cyclopropyl; R4 is selected from the group consisting of H or Cl.
    [0014] [0014] Particular preferred compounds of formula I, in which the benzamide meta-carboxamido compound is selected from either one of the compounds below or a combination of at least two compounds below: N- (2-bromo-4- (perfluoropropan -2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (dicyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) - 6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluoro-robenzamide;
    [0015] [0015] The alkyl of the present invention represents a straight or branched alkyl group, for example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl , n-pentyl, i-pentyl, n-hexyl, among others. Haloalkyl represents alkyl substituted with one or more halogen atoms that can be the same or different from each other. Aloxoxy represents alkyl substituted with an oxygen atom, for example, methoxy, ethoxy, n-propoxy, i-propoxy, t-butoxy, among others. Haloalkoxy represents alkoxy substituted with one or more halogen atoms that can be the same or different from each other. Halogen means F, Cl, Br or I.
    [0016] [0016] As used in this application, the term "C1-C6 alkyl" represents a straight or branched alkyl group having 1 to 6 carbon atoms, including, but not limited to, methyl, ethyl, n-propyl , i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-pentyl, i-pentyl, n-hexyl among others. The term "C1-C6 alkoxy" represents a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propoxy, t-butoxy, among others. "C1-C6 haloalkyl" represents a straight or branched alkyl group having 1 to 6 carbon atoms, which is replaced with one or more halogen atoms which may be the same or different from each other, including, but not limited to, trifluoromethyl , pentafluoroethyl, heptafluoropropyl, heptafluoroisopropyl, among others. The term "C3-C8 cycloalkyl" represents a cycloalkyl group having 3 to 8 carbon atoms, including, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptanyl, cyclooctyl, among others . "C3-C8 halocycloalkyl" represents a cycloalkyl group having 3 to 8 carbon atoms, which is replaced with one or more halogen atoms that can be the same or different from each other, including, but not limited to, 1- chlorocyclopropyl, 1-fluorocyclopropyl, perfluorocyclopropyl, 1-chlorocyclopentyl, 1-chlorocyclobutyl, among others.
    [0017] [0017] C1-C6, C3-C8 and the like in front of a specific group means the number of carbon atoms contained in the group, for example, C1-C6 represents that the group contains 1, 2, 3, 4, 5 or 6 carbon atoms, C3-C8 represents that the group contains 3, 4, 5, 6, 7 or 8 carbon atoms, C2-C4 represents that the group contains 2, 3 or 4 carbon atoms, among others.
    [0018] [0018] Furthermore, "i-" means iso, "s-" means secondary and "t-" means tertiary, "Me" represents methyl, "Et" represents ethyl, "i-Pr" represents iso-propyl, " c-Pr "represents cyclopropyl," c-Bu "represents cyclobutyl," c-Pent "represents cyclopentyl," c-Hex "represents cyclohexyl," CF3 "represents trifluoromethyl," OCF3 "represents trifluoromethoxy," OCF2H " represents difluoromethoxy, "H" represents hydrogen, "F" represents fluorine, "Cl" represents chlorine, "Br" represents bromine, "I" represents iodine, "O" represents oxygen, "S" represents a sulfur atom, "Ac" represents acetyl, "OMe" represents methoxy, "OEt" represents ethoxy, "O- (i-Pr)" represents i-propoxy, "MeS (O) 2" represents methylsulfonyl, "CF3S (O ) 2 "represents trifluoromethyl sulfonyl," CN "represents cyano," NO2 "represents nitro.
    [0019] [0019] The compounds of formula I can be prepared by the following methods. Each group of them is defined above, unless otherwise specified. Preparation method 1
    [0020] [0020] The structures of the compounds represented by general formula I according to this invention are as follows, which can be prepared by the following methods.
    [0021] [0021] Preferably, the compound represented by formula III can suitably be in the range of 0.5 to 2 molar equivalents based on the compound represented by formula IV, such as 0.5: 1, 0.8: 1, 1: 1, 1.2: 1, 1.4: 1, 1.5: 1, 1.8: 1 or 2: 1.
    [0022] [0022] In the process of reaction 1- (i), it is possible to use a base, including organic bases and / or inorganic bases.
    [0023] [0023] Preferably, examples of organic bases include any of triethylamine, N, N-diisopropylethylamine, N, N-dimethylaniline, pyridine, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide or a combination of at least two of them.
    [0024] [0024] Preferably, examples of inorganic bases include any of sodium hydroxide, potassium hydroxide or sodium hydride or a combination of at least two of them.
    [0025] [0025] Preferably, the solvents of reaction 1- (i) include any one of dichloromethane, chloroform, toluene, ethyl acetate, acetone, acetonitrile, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphatidyl triamide or a combination of at least two of them.
    [0026] [0026] Preferably, the reaction temperature of reaction 1- (i) can be appropriately selected within the ambient temperature range up to the boiling point of the solvent used, such as 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C or the boiling point, that is, the reflux temperature preferably used solvent.
    [0027] [0027] Preferably, the reaction time of 1- (i) can be appropriately selected within the range of half an hour to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours , 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours. 1- (ii) ： Formula V + Formula VI → Formula VII
    [0028] [0028] By reacting a compound represented by the general formula V with a compound represented by the general formula VI, it is possible to prepare a compound represented by the general formula VII.
    [0029] [0029] Preferably, the compound represented by formula V can be suitably selected in the range of 0.5 to 2 molar equivalents based on the compound represented by formula VI, such as 0.5: 1, 0.8: 1, 1 : 1, 1.2: 1, 1.4: 1, 1.6: 1, 1.8: 1 or 2: 1.
    [0030] [0030] In the process of reaction 1- (ii), it is possible to use a base, including organic bases and / or inorganic bases.
    [0031] [0031] Preferably, examples of the organic bases include any of triethylamine, N, N-diisopropylethylamine, N, N-dimethylaniline, pyridine, sodium carbonate, potassium carbonate, sodium methoxide, sodium ethoxide, sodium tert-butoxide, potassium tert-butoxide or a combination of at least two of them.
    [0032] [0032] Preferably, examples of the inorganic bases include any of sodium hydroxide, potassium hydroxide or sodium hydride or a combination of at least two of them.
    [0033] [0033] Preferably, solvents from reaction 1- (ii) include any of dichloromethane, chloroform, toluene, ethyl acetate, acetonitrile, tetrahydrofuran, dioxane, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphatidyl triamide or a combination of at least two of them.
    [0034] [0034] Preferably, the reaction temperature of t 1- (ii) can be appropriately selected within the range of -10 ° C to the boiling point of the solvent used, such as -10 ° C, -5 ° C, 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C or boiling point, that is, the reflux temperature of the solvent used.
    [0035] [0035] Preferably, the reaction time of 1- (ii) can be appropriately selected within the range of half an hour to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours , 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours. 1- (iii) ： Formula VII → Formula VIII
    [0036] [0036] By hydrolysis of a compound represented by the general formula VII, it is possible to obtain a compound represented by the general formula VIII.
    [0037] [0037] The hydrolysis reaction of 1- (iii) is carried out in any one of water, methanol, ethanol, tetrahydrofuran, dioxane or a mixture of at least two of them.
    [0038] [0038] Preferably, in the reaction process 1- (iii), it is also possible to use a base, preferably including lithium hydroxide, sodium hydroxide or potassium hydroxide.
    [0039] [0039] Preferably, the base may be suitably selected in the range 1 to 1 to molar equivalents based on the compound represented by formula VII, such as 1.0: 1, 1.3: 1, 1.5: 1, 1.8: 1, 2.0: 1, 2.5: 1, 3.0: 1, 3.5: 1, 4.0: 1, 4.5: 1, or 5.0: 1 . 1- (iv) ： Formula VIII → Formula II
    [0040] [0040] A compound represented by general formula II having a displaceable group can be prepared by a well known method by reacting a compound represented by general formula VIII with thionyl chloride, oxalyl chloride, carbonyl chloride, phosphoryl chloride , phosphorus pentachloride, phosphorus trichloride, triphosgene thionyl bromide, isopropyl trichloroformate or similar. 1- (v) ： Formula II + Formula IX → Formula I
    [0041] [0041] By reacting a compound represented by general formula II with a compound represented by general formula IX, it is possible to prepare a compound represented by general formula I.
    [0042] [0042] Preferably, the compound represented by formula II can be appropriately selected in the range of 0.5 to 2 molar equivalents based on the compound represented by formula IX, such as 0.5: 1, 0.8: 1, 1 : 1, 1.2: 1, 1.4: 1, 1.6: 1, 1.8: 1 or 2: 1.
    [0043] [0043] In the process of reaction 1- (v), it is possible to use a base, including organic bases and / or inorganic bases.
    [0044] [0044] Preferably, examples of the organic bases include any of trimethylamine, triethylamine, N, N-diisopropylethylamine, tributylamine, pyridine, piperidine, 3-methylpyridine, 2,6-dimethylpyridine, N-methylmorpholine, 3-methylimidazole, 4-N, N-dimethylaminopyridine, alkaline alcohol, lithium amino or a combination of at least two of them.
    [0045] [0045] Preferably, the alkaline alcoholate is sodium methoxide and / or sodium ethoxide. And the amino lithium is lithium diisopropylamide.
    [0046] [0046] Preferably, the inorganic bases include any of hydroxides, carbonates, alkali metal phosphates, or a combination of at least two of them.
    [0047] [0047] Preferably, the alkali metal hydroxides contain any of lithium hydroxide, sodium hydroxide, potassium hydroxide or a combination of at least two of them. Preferably, the alkali metal carbonates include any one of sodium bicarbonate, sodium carbonate, potassium carbonate or a combination of at least two of them. Preferably, alkali metal phosphates include hydrogen dipotassium phosphate and / or trisodium phosphate.
    [0048] [0048] Preferably, the solvents of 1- (v) can be any of those that do not significantly inhibit the present reaction. The solvent can include any one of halogenated hydrocarbons, aromatic hydrocarbons, chain or cyclic ethers, ketones, nitriles, aprotic polar inert solvents or a combination of at least two of them.
    [0049] [0049] Preferably, halogenated hydrocarbons include any one of methylene chloride, chloroform or carbon tetrachloride or a combination of at least two of them. Preferably, aromatic hydrocarbons include any of benzene, toluene, xylene, chlorobenzene or dichlorobenzene or a combination of at least two of them. Preferably, the chain or cyclic ethers include any of ether, tetrahydrofuran, dioxane or 1,2-dimethoxyethane or a combination of at least two of them. Preferably, the esters include ethyl acetate and / or butyl acetate. Preferably, ketones include any of acetone, methyl isobutyl ketone, cyclohexanone or a combination of at least two of them. Preferably, the nitriles include acetonitrile and / or acrylonitrile. Preferably, the inert polar aprotic solvents include any one of 1,3-dimethyl-2-imidazolinone, sulfolane, dimethyl sulfoxide, N, N-dimethylformamide, N-methylpyrrolidone, N, N-dimethylacetamide or hexamethylphosphamide or a combination of at least two of them.
    [0050] [0050] Preferably, the reaction temperature of reaction 1- (v) can be appropriately selected within the range of -70 ° C to the boiling point of the solvent used, such as -70 ° C, -50 ° C, -30 ° C, - 10 ° C, -5 ° C, 0 ° C, 5 ° C, 15 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C , 60 ° C, 70 ° C, 75 ° C, 80 ° C, 85 ° C, 90 ° C or the boiling point, that is, the reflux temperature of the solvent used.
    [0051] [0051] Preferably, the reaction time of reaction 1- (v) can be appropriately selected within the range of half an hour to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours. Preparation method 2
    [0052] [0052] The compounds of general formula I of this invention can be prepared by an alternative method, shown below, in which R1, R2, R3, R4, Z, Y1, Y2 ,, W1, W2, Hal and LG are as defined above , unless otherwise specified. Y2 F H 2N F R2 R1 Y2
    [0053] [0053] A compound represented by the general formula XI having a displaceable group can be prepared by a method well known
    [0054] [0054] By reacting a compound represented by the general formula XI with a compound represented by the general formula IX according to the conditions described in 1- (v), it is possible to prepare a compound represented by the general formula XII. 2- (iii) ： Formula XII → Formula XIII
    [0055] [0055] An aromatic carboxamide derivative having an amino group represented by the formula XIII can be derived from the aromatic carboxamide derivative having a nitro group represented by the formula XII by means of a reduction reaction. Such a reduction is illustrated by a process that uses hydrogenation, a process that uses a metallic compound (for example, stannous chloride) or a metal such as iron powder, zinc powder, among others.
    [0056] [0056] The hydrogenation reaction can be carried out in a suitable solvent in the presence of a catalyst at atmospheric pressure or at a higher pressure in a hydrogen atmosphere. Examples of the catalyst may include palladium-based catalysts such as palladium-carbon, cobalt-based catalysts, ruthenium-based catalysts, platinum-based catalysts, among others. Examples of the solvent may include alcohols such as methanol and ethanol; aromatic hydrocarbons such as benzene and toluene; chain or cyclic ethers such as ether and tetrahydrofuran; esters such as ethyl acetate.
    [0057] [0057] Preferably, the hydrogenation reaction pressure can be appropriately selected within the range of 0.1 MPa to 10 MPa, such as 0.1 MPa, 0.5 MPa, 0.8 MPa, 1 MPa, 1.5 MPa, 2 MPa, 3
    [0058] [0058] Preferably, the temperature of the hydrogenation reaction can be appropriately selected within the range of -20 ° C to the boiling point of the solvent used, such as -20 ° C, -10 ° C, -5 ° C, 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C, 70 ° C, 75 ° C, 80 ° C or the boiling point, that is, the reflux temperature of the solvent used.
    [0059] [0059] Preferably, the hydrogenation reaction time can be appropriately selected within the range of half an hour to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours , 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours.
    [0060] [0060] Preferably, the process that uses a metallic compound or a metal is carried out in any one of methanol, ethanol, ethyl acetate or a mixture of at least two of them.
    [0061] [0061] Preferably, the metallic compound is stannous chloride and the metal is any one of iron powder, zinc powder or a combination of at least two of them.
    [0062] [0062] Preferably, the reaction temperature using a metallic compound or a metal can be appropriately selected within the range of -10 ° C to the boiling point of the solvent used, such as -10 ° C, -5 ° C, 0 ° C, 5 ° C, 10 ° C, 15 ° C, 20 ° C, 25 ° C, 30 ° C, 35 ° C, 40 ° C, 45 ° C, 50 ° C, 60 ° C , 70 ° C, 75 ° C, 80 ° C or the boiling point, that is, the reflux temperature of the solvent used.
    [0063] [0063] Preferably, the reaction time using a metallic compound or a metal can be appropriately selected within the range of half an hour to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours , 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours or 48 hours.
    [0057] [0057] By reacting a compound represented by general formula XIII with a compound represented by general formula IV according to the conditions described in 1- (i), it is possible to prepare a compound represented by general formula XIV. 2- (v) ： Formula XIV + Formula VI → Formula I
    [0058] [0058] By reacting a compound represented by the general formula XIV with a compound represented by the general formula VI according to the conditions described in 1- (ii), it is possible to prepare a compound represented by the general formula I.
    [0059] [0059] On the other hand, this invention presents an intermediate represented by formula VIII for the preparation of benzamide meta-carboxamido compounds of formula I.
    [0060] [0060] Table 2 lists the representative compounds of the intermediate
    [0061] [0061] In addition, the invention features tautomers, enantiomers, non-enantiomers or salts of benzamide meta-carboxamide derivatives.
    [0062] [0062] Tautomers, enantiomers, non-enantiomers or salts of benzamide meta-carboxamido derivatives have the same insecticidal activity as benzamide meta-carboxamido derivatives, that is, they have insecticidal activity at low concentration and fast-acting property satisfactory.
    [0063] [0063] In addition, the invention presents the use of benzamide meta-carboxamide derivatives for the control of insects and plants and nematodes in agriculture, forestry and horticulture.
    [0064] [0064] The benzamide meta-carboxamide derivatives of this invention can effectively control pests in agriculture, forestry and horticulture, public health and nematodes, which are harmful to rice, corn, wheat, potato, fruit trees , vegetables, other crops and ornamentals, etc.
    [0065] [0065] The pests according to this invention are lepidoptera, coleoptera, hemiptera, tisanoptera, diptera, orthoptera, homoptera, isoptera, hymenoptera, tetraniquidae and nematodes, mosquitoes, flies, ants, etc.
    [0066] [0066] Preferably, the pests according to this invention include the following, but this invention is not limited to the same: Helicoverpa armigera (Hübner), Plutella xylostella (Linnaeus), Spodoptera exigua (Hübner), Spodoptera litura (Fabricius ), Pieris rapae (Linne), Chilo suppressalis (Walker), Tryporyza incertulas (Walker), Semaia inferens (Walker), Spodoptera frugiperda (JESmmith), Cnapha-locrocis medinalis (Guenee), Chloethrips oryzae (Wila.), Frankliniella occidentalis (Pergande), Thrips fevas (Schrank), Thrips alliorum (Priest), Myzus persicae (Sulzer), Aphis gossypii (Glover), Aphis craccivo- ra (Koch), Aphis citricolavander Goot, Rhopalosiphum padi, flea beetle , stink bug, Laodelphax striatellus, Nilaparvata lugens (Stal), Somatella furcifera, termites, flies and mosquitoes, Tetranychus cinnabarius, red citrus mite.
    [0067] [0067] The compounds of this invention can be widely applied to the following categories: vegetables such as cucumber, loofah, watermelon, melon, pumpkin, melon, spinach, celery, cabbage, cabbage, gourd, pepper, eggplant, tomato, chives, ginger , garlic, leeks, lettuce, purple beans, string beans, broad beans, radish, carrots, potatoes, yams; cereals such as wheat, barley, corn, rice, sorghum; fruits such as apple, pear, banana, citrus, grape, lychee, mango; ornamental plants such as peony, rose, flamingo flower; oil crops such as peanuts, soybeans, rapeseed, sunflower, sesame; sugar-producing crops such as sugar beet, sugar cane; other crops such as strawberry, potato, sweet potato, tobacco and tea; horticulture, forestry, residences and public areas, etc. The scope of utility of the benzamide meta-carboxamido derivatives according to the invention is not limited to the categories listed above.
    [0068] [0068] In another aspect, this invention features an insecticidal composition comprising active ingredients and vehicles acceptable in agriculture, where the active ingredients are the benzamide meta-carboxamido compounds described above, or the tautomers, enantiomers, diastereomers or salts thereof.
    [0069] [0069] The composition of this invention can be used in the form of a formulation, in which the compounds represented by the general formula I are dissolved or dispersed in the vehicle as active ingredients or they can be formulated so as to make them easier to disperse when they are used as pesticides.
    [0070] [0070] The present invention relates to insecticidal compositions, which are placed in a variety of formulation ways, such as a wetting powder, a suspension concentrate, an aqueous emulsion or an emulsifiable concentrate, etc.
    [0071] [0071] The present invention was created to solve the problems of related areas such as agriculture, forestry, public health, etc.
    [0072] [0072] Preferably, in the insecticidal composition, the weight percentage of the active component is 1-99%, such as 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99%.
    [0073] [0073] Preferably, the acceptable vehicle in pesticide science includes surfactants.
    [0074] [0074] The surfactants researched in the present invention include ionic surfactants or non-ionic surfactants.
    [0075] [0075] Surfactants include emulsifiers, dispersants, or emulsifying agents. Emulsifiers researched in the present invention include fatty acid ester with polyoxyethylene, aliphatic alcohol ether with polyoxyethylene, polyoxyethylene ether with grease amine and commercially available emulsifiers such as pesticidal emulsifiers 2201B, 0203B, 100 #, 500 #, 600 #, 600-2 #, 1601, 2201, NP-10, NP-15, 507 #, OX-635, OX-622, OX-653, OX-667, 36 # among others. The dispersants researched in the present invention include sodium lignosulfonate, nekal, calcium lignosulfonate, methylnaphthalene formaldehyde condensate, among others. The wetting agents investigated in the present invention include sodium lauryl sulfate, sodium dodecyl benzene sulfonate, sodium alkyl naphthalene sulfonate, among others.
    [0076] [0076] Preferably, vehicles acceptable in pestilence science include solid vehicles and / or liquid vehicles.
    [0077] [0077] Preferably, the solid vehicles investigated in the present invention include natural or synthetic clays and silicates (for example, natural silica, diatomite); magnesium silicate, for example, talc); mixed magnesium and aluminum silicate (for example, kaolin, kaolin, montmorillonite and mica); precipitated silica, calcium carbonate, light calcium carbonate, calcium sulfate, limestone, sodium sulfate; amine salt (eg, ammonium sulfate, hexamethylenediamine). The liquid vehicles researched in the present invention include water and organic solvents. When water is used as a solvent or diluent
    [0078] [0078] During the preparation of the pesticidal composition, the active ingredients can be mixed with the liquid and / or solid vehicles. Surfactants (such as emulsifiers, dispersants, stabilizers, wetting agents) and other auxiliaries (such as adhesives, antifoaming agents, oxidizers, etc.) can also be added.
    [0079] [0079] In another aspect, the present invention presents a method for the control of insects, in which an effective concentration of the benzamide meta-carboxamido compounds, or the tautomers, enantiomers, diastereomers or salts thereof, or the composition described above it will be used in the insects to be controlled or in their habitats.
    [0080] [0080] Preferably, the effective concentration ranges from 10 g / ha to 1000 g / ha, such as 10 g / ha, 20 g / ha, 50 g / ha, 80 g / ha, 100 g / ha, 120 g / ha, 150 g / ha, 180 g / ha, 200 g / ha, 250 g / ha, 300 g / ha, 350 g / ha, 400 g / ha, 450 g / ha, 500 g / ha, 600 g / ha, 700 g / ha, 800 g / ha, 900 g / haor1000 g / ha. Most preferably, the effective concentration ranges from 25 g / ha to 500 g / ha.
    [0081] [0081] The composition of this invention can be used in insects and their habitat in the form of a formulation. The compounds represented by the general formula I are dissolved or dispersed in the vehicle as an active ingredient or they can be formulated so as to leave them
    [0082] [0082] For certain applications, for example, in agriculture, one or more additional agents, such as insecticides, fungicides, herbicides, plant growth regulators or fertilizers, can be added to the insecticidal composition of this invention, in order to obtain additional benefits and effects.
    [0083] [0083] Compared with the prior art, this invention has the following advantages:
    [0084] [0084] The benzamide meta-carboxamido derivatives of this invention are significantly effective in controlling pests and nematodes in agriculture, forestry and public health. They have excellent insecticidal activity at low concentration, which can be exercised one day after application, and excellent insecticidal activity can be achieved on the third day, with satisfactory fast-acting properties. The good insecticidal activity at the low concentration of the benzamide meta-carboxamide derivatives of this invention can reduce the damage of pesticide application to plants and humans and reduce the amount of residual pesticide, and thus are more conducive to the protection of the environment. environment. Production methods are also simple and efficient, and mass production can be carried out with ease. Therefore, the compounds and compositions of this invention have wide application possibilities. EXAMPLES
    [0085] [0085] Representative examples of this invention will be described in the Examples that follow. Those skilled in the art should understand that the examples presented here are illustrative only, and this invention is not limited to them. SGC represents chroma-
    [0086] [0086] To the solution of methyl 3-amino-2-fluorobenzoate (20 g ， 118.23 mmol) in anhydrous DMF (200 mL) were added potassium carbonate (21.24 g ， 153.70 mmol) and (bromomethyl ) cyclopropane (20.75 g ， 153.70 mmol). Then the mixture was heated and refluxed for 16 hours. TLC showed that the reaction was over. The reaction mixture was extracted with ethyl acetate (100 ml) and H2O (200 ml). The organic layer was washed with saturated brine, and then dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue obtained was purified by SGC (eluent: petroleum ether: ethyl acetate = 10: 1) to obtain 13 g (49.39% yield) of the target compound as a yellow liquid clear. Step 2: Preparation of methyl 3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzoate
    [0087] [0087] Thionyl chloride (31.99 g ， 268.9 mmol) was added to benzoic acid (6.67 g ， 53.78 mmol) in toluene (50 mL), and the mixture was heated and refluxed for 2 hours . After the solvent was distilled off, the crude product benzoyl chloride in THF (30 mL)
    [0088] [0088] Methyl 3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzoate (13.00 g ， 40.88 mmol) was dissolved in methanol (100 mL). A 10% aqueous sodium hydroxide solution (6.54 g ， 163.52 mmol ， 65.4 ml) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed that the reaction was complete. After the solvent was removed by distillation, the crude product was dissolved in H2O (100 ml) and extracted with ethyl acetate (50 ml). The pH of the aqueous phase was acidified to 7 by the addition of 2M hydrochloric acid and extracted with ethyl acetate (100 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain 12 g (yield 93.82%) of the target compound as a colorless liquid, which becomes a white solid after resting for a night.
    [0089] [0089] To the solution of 3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzoic acid (0.40 g ， 1.28 mmol) in toluene (6 mL) was added thionyl chloride (0.75 g ， 6 , 40 mmol). Then the mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the crude product 3- (N- (cyclopropylmethyl) benzamide) -2-fluorobenzoyl chloride in THF (3 ml) was used in the next step without further purification. 2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (0.52 g ， 1.28 mmol) was loaded into anhydrous THF (4 mL) and cooled to -70 ° C in a nitrogen atmosphere. A 2.0 M solution of lithium diisopropyl amide in hexane (0.77 mL ， 1.54 mmol) was added in drops. After 5 minutes, 3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzoyl chloride dissolved in THF (3 mL) was added in drops and the mixture was stirred at -70 ° C for 30 minutes and at room temperature room for another 30 minutes. TLC showed that the reaction was over. The reaction mixture was diluted with H2O (20 ml) and extracted with ethyl acetate (20 ml). The organic layer was washed with saturated brine and dried over anhydrous magnesium sulfate. The solvent was evaporated under reduced pressure and the residue obtained was purified by SGC (eluent: petroleum ether: ethyl acetate = 3: 1) to obtain 0.25 g (yield 27.84%) of target compound.
    [0090] [0090] For Compound No. 4: 1H NMR (CDCl3-d, 400 MHz), δ [pm] ： 8.15 (d, J = 2.1 Hz, 1H), 8.03 (br s, 2H ), 7.92 (d, J = 2.1 Hz, 1H), 7.55 (br s, 1H), 7.35-7.21 (m, 5H), 3.84 (d, J = 93 , 6 Hz, 2H), 1.14 (br s, 1H), 0.59 - 0.40 (m, 2H), 0.20 (d, J = 42.2 Hz, 2H).
    [0091] [0091] Thionyl chloride (3.2 g ， 26.9 mmol) was added to 4-cyanobenzoic acid (0.80 g ， 5.38 mmol) in toluene (6 mL). The mixture was heated and refluxed for 2 hours. After the solvent was distilled off, the crude 4-cyanobenzoyl chloride product was dissolved in THF (3 ml) and used in the next step. To the solution of 3- ((cyclopropylmethyl) amino) -2-fluorobenzoate (1.0 g ， 4.48 mmol) in anhydrous THF (6 mL) were added in triethylamine drops (0.74 g ， 5.38 mmol) and solution of 4-cyanobenzoyl chloride in THF. The mixture was stirred at room temperature for 4 hours. TLC showed that the reaction was complete. The mixture was diluted with H2O (20 ml) and extracted with ethyl acetate (20 ml) e. The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 3: 1) to obtain 1.40 g (yield 88.83%) of the target compound. Step 2: Preparation of 3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoic acid THE THE
    [0092] [0092] Methyl 3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzene
    [0093] [0093] To 3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoic acid (0.75 g ， 2.22 mmol) in toluene (6 mL) was added thionyl chloride (1.31 g ， 11.10 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was distilled off, the crude product of 3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoyl chloride was dissolved in THF (3 ml) and used in the next step. 2-Bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (0.90 g, 2.22 mmol) was loaded into anhydrous THF (4 mL) and cooled to -70oC in a nitrogen atmosphere . A 2.0 M solution of lithium diisopropyl amine in hexane (1.30 mL ， 2.66 mmol) was added in drops. After 5 minutes, a solution of 3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoyl in THF was added in drops. The mixture was stirred at -70 ° C for 30 minutes and at room temperature for another 30 minutes. TLC showed that the reaction was over. The reaction mixture was diluted with a saturated solution of NH4Cl (20 ml) and extracted with ethyl acetate (20 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 3: 1) to obtain 0.24 g (yield 14.91%) of the target compound.
    [0094] [0094] For Compound No. 23: 1H NMR (CDCl3-d, 400 MHz), δ [pm] ： 8.14 (d, J = 2.0 Hz, 1H), 8.12 - 7.94 ( m, 2H), 7.91 (t, J = 1.4 Hz, 1H), 7.58 - 7.39 (m, 4H), 7.32 (t, J = 7.9 Hz, 1H), 3.81 (dd, J = 76.0, 18.8 Hz, 2H), 1.11 (br s, 1H), 0.5 (br s, 2H), 0.20 (d, J = 36, 7 Hz, 2H). Example 3: Preparation of N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4- (trifluoromethyl) benzamido) -2 - fluorobenzamide (Compound No. 37)
    [0095] [0095] (1) To 3- (N- (cyclopropylmethyl) -4- (trifluoromethyl) benzamido) -2-fluorobenzoic acid (0.45 g ， 1.12 mmol) in toluene (6 mL) was added thionyl chloride (0.67 g ， 5.60 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the crude product 3- (N- (cyclopropylmethyl) -4- (trifluoromethyl) benzamido) -2-fluorobenzoyl chloride was dissolved in THF (3 ml) and used in the next step.
    [0096] [0096] (2) 2-Bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (0.46 g, 1.12 mmol) was loaded into anhydrous THF (4 mL) and cooled to - 70 ° C in a nitrogen atmosphere. A 2.0 M solution of lithium diisopropyl amide in hexane (0.70 mL ， 1.42 mmol) was added
    [0097] [0097] Example 4: Preparation of N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-chloro-N- (cyclopropylmethyl) benzamido) -2- fluorobenzamide (Compound No. 41)
    [0097] [0097] (1) To 3- (4-chloro-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoic acid (0.60 g ， 1.76 mmol) in toluene (6 mL) was added thionyl chloride (1 , 04 g ， 8.80 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was distilled off, the crude product of 3- (4-chloro-N- (cyclopropylmethyl) benzamido) -2-fluorobenzoyl chloride was dissolved in THF (3 mL) and used in the next step.
    [0098] [0098] (2) 2-Bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (0.72 g ， 1.76 mmol) was loaded into anhydrous THF (4 mL) and cooled to - 70 ° C in a nitrogen atmosphere. A 2.0 M solution of lithium diisopropyl amide in hexane (1.05 mL ， 2.11 mmol) was added
    [0098] [0098] For Compound No. 41: 1H NMR (CDCl3-d, 400 MHz), δ [pm] ： 8.18 - 7.84 (m, 4H), 7.53 (t, J = 7.7 Hz, 1H), 7.37 - 7.07 (m, 4H), 3.81 (d, J = 85.0 Hz, 2H), 1.11 (br s, 1H), 0.49 (br s , 2H), 0.17 (d, J = 32.1 Hz, 2H).
    [0099] [0099] Example 5: Preparation of N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4-fluorobenzamido) -2-fluorobenzamide (Compound No. 62)
    [0099] [0099] To 3- (N- (cyclopropylmethyl) -4-fluorobenzamido) -2-fluoro-benzoic acid (2.20 g ， 6.67 mmol) in toluene (20 mL) was added thionyl chloride (3 , 97 g ， 33.35 mmol l). The mixture was heated and refluxed for 2 hours. After the solvent was removed by distillation, the crude product 3- (N- (cyclopropylmethyl) -4-fluorobenzamido) -2-fluorobenzoyl chloride was used in the next step.
    [00100] [00100] 2-Bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (3.26 g ， 7.99 mmol), N, N-Di-isopropyl-ethylamine (1.72 g ， 13.30 mmol) and 4-N, N-dimethylaminopyridine (0.33 g ， 2.69 mmol) were added to 3- (N- (cyclopropylmethyl) -4-fluorobenzamido) -2-fluorobenzoyl chloride. The mixture was heated to 120 ° C for 2 hours. The reaction mixture was dissolved in H2O (20 ml) and extracted with ethyl acetate (20 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 3: 1) to obtain 1.80 g (yield 37.5%) of the target compound.
    [00101] [00101] For Compound No. 62: 1H NMR (CDCl3-d, 400 MHz), δ [pm] ： 10.56 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.70 - 7.56 (m, 2H), 7.38 - 7.32 (m, 3H), 7.09 (br s, 2H), 3.69 (br s, 2H), 1 , 03 - 1.01 (m, 1H), 0.41 - 0.39 (m, 2H), 0.08 - 0.06 (m, 2H).
    [00102] [00102] Example 6: Preparation of N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide ( Compound No. 8) Step 1: Preparation of methyl 3 - ((1-cyclopropylethyl) amino) -2-fluoro-benzoate
    [00102] [00102] To a solution of methyl 3-amino-2-fluorobenzoate (2.00 g ， 11.82 mmol) in anhydrous 1,2-dichloroethane (65 mL) were added 1- cyclopropylethan-1-one (2.98 g ， 35.47 mmol), trifluoroacetic acid (8.08 g ， 70.92 mmol) and sodium triacetoxyborohydride (7.51 g ， 35.47 mmol) at room temperature. The mixture was heated to 45 ° C for 1 hour. When TLC showed that the reaction was finished, the mixture was diluted with a saturated solution of NaHCO3 (50 ml) and extracted with dichloromethane (80 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 10: 1) to obtain 1.50 g (yield 53.5%) of the target compound as a colorless oil. Step 2: Preparation of methyl 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoate
    [00103] [00103] Thionyl chloride (6.27 g ， 52.68 mmol) was added to benzoic acid (1.54 g ， 12.64 mmol) in toluene (15 mL). The mixture was heated and refluxed for 2 hours. After the solvent was distilled off, the crude benzoyl chloride product was dissolved in THF (5 ml) and used in the next step.
    [00104] [00104] To a solution of methyl 3 - ((1-cyclopropylethyl) amino) -2-fluoro-benzoate (2.50 g ， 10.54 mmol) in anhydrous THF (15 mL) was added triethylamine (1, 60 g, 15.80 mmol) and a solution of benzoyl chloride in THF. The mixture was heated and stirred at 80 ° C for 6 hours. TLC showed that the reaction was complete. The mixture was diluted with H2O (50 ml) and extracted with ethyl acetate (60 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 10: 1) to obtain 1.03 g (yield 28.6%) of the target compound as a yellow solid. Step 3: Preparation of 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoic acid
    [00105] [00105] Methyl 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoate (1.00 g ， 2.93 mmol) was dissolved in methanol (10 mL). A 10% aqueous sodium hydroxide solution (0.46 g ， 11.72 mmol ， 4.6 mL) was added and the reaction mixture was stirred at room temperature for 2 hours. TLC showed that the reaction was complete. After the solvent was removed by distillation, the residue was dissolved in H2O (20 ml) and extracted with ethyl acetate (10 ml). The organic layer was discarded. The pH of the aqueous phase was acidified to 3 by the addition of 2M hydrochloride acid. Then, the mixture was extracted with ethyl acetate (10 ml). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure to obtain 0.60 g (yield 62.6%) of the target compound. Step 4: Preparation of
    [00106] [00106] To 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoic acid (0.60 g ， 1.83 mmol) in toluene (6 mL) was added thionyl chloride (1.09 g ， 9 , 16 mmol). The mixture was heated and refluxed for 2 hours. After the solvent was distilled off, the 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoyl chloride crude product was dissolved in THF (2 ml) and used in the next step.
    [00107] [00107] 2-Bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) aniline (0.75 g, 1.83 mmol) was loaded into anhydrous THF (6 mL) and cooled to -70 ° C in an atmosphere of nitrogen. A 2.0 M solution of diisopropyl amide lithium in hexane (1.10mL ， 2.20 mmol) was added in drops. After 5 minutes a solution of 3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzoyl chloride in THF was added. The mixture was stirred at -70 ° C for 30 minutes and at room temperature for another 30 minutes. When TLC showed that the reaction was finished, the reaction mixture was diluted with H2O (20 mL) and extracted with ethyl acetate (20 mL). The organic layer was washed with saturated brine, dried over anhydrous magnesium sulfate and evaporated under reduced pressure. The residue was purified by SGC (eluent: petroleum ether: ethyl acetate = 5: 1) to obtain 0.23 g (17.5% yield) of the target compound as a yellow solid.
    [00108] [00108] For Compound No. 8: 1H NMR (CDCl3-d, 400 MHz), δ [pm] ： 8.19 (s, 1H), 8.05 - 7.95 (m, 1H), 7, 89 (s, 1H), 7.77 - 7.73 (m, 1H), 7.56 - 7.52 (m, 1H), 7.28 - 7.11 (m, 6H), 4.26 - 4.23 (m, 1H), 1.63 (br s, 2H), 1.51 (br s, 1H), 0.89 - 0.40 (m, 5H).
    [00109] [00109] In addition to the compounds described in the examples, other compounds in Table 1 can be prepared according to similar methods as described in examples 1-6. next, Table 3 shows the NMR data of some compounds prepared according to examples 1-6 of this invention. The 1H NMR chemical shift values shown in this report are based on tetramethylsilane as an internal standard substance, unless otherwise specified. Table 3 Compound 1H NMR (CDCl3, ppm) No. 22 400 MHz, DMSO-d6, δ [pm] ： 10.44 (s, 1H), 8.40 (s, 1H), 7.96-7.93 (m, 2H), 7.64-7.58 (m, 1H), 7.34- 7.22 (m, 6H), 3.56 (br s, 1H), 1.06-1.03 ( m, 1H), 0.84-0.80 (m, 1H), 0.65-0.38 (m, 8H). 24 400 MHz, DMSO-d6, δ [pm] ： 10.50 (s, 1H), 8.19 (s, 1H), 7.82 - 7.35 (m, 8H), 3.75 (d, J = 86.5 Hz, 2H), 3.57 (s, 3H), 0.87 - 0.84 (m, 1H), 0.43 -0.13 (m, 4H). 26 400 MHz, DMSO-d6, δ [pm] ： 10.51 (d, J = 27.1 Hz, 1H), 8.54 - 8.35 (m, 1H), 7.95 (s, 1H) , 7.86 - 7.51 (m, 4H), 7.51 -7.20 (m, 3H), 4.03 (q, J = 7.1 Hz, 1H), 1.30 - 1.19 (m, 3H), 0.93 - 0.23 (m, 5H), 32 400 MHz, DMSO-d6, δ [pm] ： 10.45 (s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.84-7.80 (m, 1H), 7.71-7.61 (m, 3H), 7.45-7.35 (m, 3H), 3, 59-3.55 (m, 1H), 1.10 (br s, 1H), 0.85-0.80 (m, 1H), 0.67-0.40 (m, 8H). 38 1H NMR (400 MHz, DMSO-d6), δ [pm]: 10.46 (s, 1H), 8.19 (s, 1H), 7.78 (d, J = 25.9 Hz, 3H) , 7.56 (d, J = 40.0 Hz, 4H), 7.36 (s, 1H), 3.76 (d, J = 36.8 Hz, 2H), 3.57 (s, 3H) , 0.93 - 0.79 (m, 1H), 0.43 (s, 2H), 0.13 (d, J = 30.4 Hz, 2H). 39 400 MHz, DMSO-d6, δ [pm] ： 10.44 (d, J = 30.3 Hz, 1H), 8.41 (s, 1H), 7.94 (s, 1H), 7.80 - 7.73 (m, 1H), 7.70 - 7.27 (m, 6H), 4.09 - 4.07 (m, 1H), 1.50 - 1.15 (m, 3H), 0 , 95 - 0.19 (m, 5H). 43 400 MHz, DMSO-d6 δ [pm] ： 10.55 (s, 1H), 8.20 (s, 1H), 7.82 (s, 1H), 7.70-7.59 (m, 2H ), 7.32 (br s, 5H), 3.71 (br s, 2H), 3.57 (s, 3H), 1.03 (br s, 1H), 0.42 (br s, 2H) , 0.09 (br s, 2H). 44 400 MHz, DMSO-d6, δ [pm] ： 10.53 (d, J = 25.5 Hz, 1H), 8.46 - 8.37 (m, 1H), 7.98 - 7.91 ( m, 1H), 7.80 - 7.55 (m, 2H), 7.32 (d, J = 33.8 Hz, 5H), 4.03 (q, J = 7.1 Hz, 1H), 1.46 - 1.15 (m, 3H), 0.90 - 0.18 (m, 5H). 46 400 MHz, CDCl3-d ， δ [pm] ： 8.13 (d, J = 2.0 Hz, 1H), 8.05 (t, J = 7.6 Hz, 1H), 7.90 (s , 1H), 7.54 (t, J = 7.8 Hz, 1H), 7.32 (d, J = 9.7 Hz, 2H), 7.21 (t, J = 6.7 Hz, 3H ), 3.81 (d, J = 87.9 Hz, 2H), 1.10 (br s, 1H), 0.50 (br s, 2H), 0.18 (d, J = 35.8 Hz , 2H). 47 400 MHz, CDCl3-d ， δ [pm] ： 8.36 (d, J = 2.1 Hz, 1H), 8.26 - 7.91 (m, 3H), 7.59 (s, 1H) , 7.44 -7.29 (m, 3H), 7.23 (br s, 2H), 4.00 (br s, 1H), 3.69 (br s, 1H), 1.14 (br s , 1H), 0.52 (br s, 2H), 0.21 (d, J = 56.0 Hz, 2H). 49 400 MHz, DMSO-d6 δ [pm] ： 10.54 (s, 1H), 8.20 (s, 1H), 7.82 (s, 1H), 7.70-7.59 (m, 2H ), 7.51 - 7.18 (m, 5H), 3.70 (br s, 2H), 3.57 (s, 3H), 1.02-0.97 (m, 1H), 0.41 (d, J = 8.1 Hz, 2H), 0.17-0.02 (m, 2H). 50 400 MHz, DMSO-d6, δ [pm] ： 10.53 (d, J = 34.0 Hz, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.76 - 7.62 (m, 2H), 7.42 - 7.20 (s, 5H), 4.03 - 3.97 (m, 1H), 1.39 - 1.21 (m, 3H), 0 , 85 - 0.24 (m, 5H). 52 400 MHz, DMSO-d6 ， δ [pm] ： 10.43 (s, 1H), 7.95 (br s, 2H), 7.60 - 7.54 (m, 4H), 7.26 (br s, 2H), 7.01 (br s, 1H), 3.63 (br s, 2H), 0.93 (br s, 1H), 0.32 (d, J = 8.1 Hz, 2H) , 0.04 (br s, 2H). 53 400 MHz, DMSO-d6 ， δ [pm] ： 10.61 (s, 1H), 8.50 (d, J = 2.0 Hz, 1H), 7.94 (d, J = 2.1 Hz , 1H), 7.63 - 7.57 (m, 4H), 7.36 (br s, 2H), 7.09 (br s, 1H), 3.69 (br s, 2H), 1.01 (s, 1H), 0.41 (d, J = 8.2 Hz, 2H), 0.08 (br s, 2H). 57 400 MHz, DMSO-d6 ， δ [pm] ： 10.59 (s, 1H), 8.42 (d, J = 2.1 Hz, 1H), 7.95 (d, J = 2.1 Hz , 1H), 7.80 - 7.67 (m, 3H), 7.62-7.52 (m, 3H), 7.35 (s, 1H), 3.75 (s, 2H), 3, 16 (s, 3H), 1.03 (s, 1H), 0.53 - 0.30 (m, 2H), 0.13 (d, J = 16.2 Hz, 2H). 60 400 MHz, DMSO-d6, δ [pm] ： 10.46 (s, 1H), 8.34 (d, J = 2.1 Hz, 1H), 7.87 (d, J = 2.1 Hz , 1H), 7.65 (t, J = 7.4 Hz, 1H), 7.54 (br s, 1H), 7.36 (br s, 2H), 7.29 (br s, 1H), 7.16 (br s, 2H), 3.62 (br s, 2H), 0.95 (br s, 1H), 0.34 (br s, 2H), 0.07 (s, 2H). 63 400 MHz, DMSO-d6, δ [pm] ： 10.55 (br s, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.72 (d, J = 24 , 2 Hz, 1H), 7.61 (s, 1H), 7.39 - 7.26 (m, 3H), 7.05 (s, 2H), 4.02 (br s, 1H), 1, 39 (br s, 1H), 1.24 (s, 3H), 0.53 (d, J = 50.9 Hz, 2H), 0.32 (d, J = 44.6 Hz, 2H). 75 400 MHz, DMSO-d6, δ [pm] ： 8.04 (s, 1H), 7.95 (s, 1H), 7.94- 7.63 (m, 2H), 7.42 - 7, 35 (m, 3H), 7.12 - 6.99 (m, 2H), 5.08 - 4.78 (m, 1H), 1.48 - 1.43 (m, 1H), 1.34 - 1.08 (m, 6H). 77 400 MHz, DMSO-d6, δ [pm] ： 10.53 (d, J = 25.6 Hz, 1H), 8.41 (s, 1H), 7.95 (s, 1H), 7.77 (d, J = 7.6 Hz, 3H), 7.61 (s, 1H), 7.52 (s, 2H), 7.36 (t, J = 7.2 Hz, 1H), 4.06 (br s, 1H), 3.14 (s, 3H), 1.41 (br s, 1H), 1.25 (d, J = 8.5 Hz, 3H), 0.56 (d, J = 33.0 Hz, 2H), 0.35 (d, J = 43.5 Hz, 2H).
    [00110] [00110] Other compounds represented by the general formula I of this invention can also be prepared according to the methods described above.
    [00111] [00111] Preparation method: the quantity of each material in Table 4 was weighed. Trimethylbenzene was added to a 250 mL three-neck flask, followed by the addition of compound 4, calcium dodecylbenzene sulfonate and castor oil with polyoxyethylene. The mixture was stirred at 40 ~ 50 ° C for 1.5 hours and filtered. An emulsifiable concentrate of 4 to 5% compound was obtained. Example 2 ： Method of preparation of compostable powder sample of Compound 23 Table 5: Compoundable powder formulation of compound 23 Content 100% consistency Materials Remarks w / w ，%） compound 23 30 Active ingredient sodium dodecyl sulfate 1.5 Wetting agent sodium lignosulfonate 6 kaolin dispersant 62.5 vehicle
    [00112] [00112] Preparation method: the quantity of each material in Table 5 was weighed. Compound No. 23, sodium dodecyl sulfate, sodium lignosulfonate and kaolin were mixed uniformly and sprayed to an average particle size of 10 microns with a jet mill to obtain a wet powder of compound No. 23 to 30%. Examples of Bioactivity Tests
    [00113] [00113] Various types of pests have been tested with the representative compounds of this invention. Example 1 Indoor bioactivity test against Mythimna separata
    [00114] [00114] The leaf immersion method was used to evaluate the insecticidal activity of the compounds in strains of Mythimna sepatata. Fresh maize seedlings were cut above the land, about 10 cm. The corn seedlings were immersed in the solution prepared with the compound of this invention for 10 seconds and dried in a cold environment. Then, the dried corn seedlings were cut into 3 ~ 5 cm leaf sections and 3 leaf sections were placed in each petri dish. Ten larvae of Mythimna separates on the 4th instar were placed on each plate, and this was repeated 3 times. Then, the dishes were placed in a lighted incubator and incubated at 25 ° C in the dark. Symptoms were investigated on the 1st, 2nd and 3rd days after treatment, and mortality was calculated.
    [00115] [00115] The insecticidal activity of some compounds of this invention against Mythimna separate is ≥90% (mortality from Mythimna separata) at 1 ppm on the 3rd day after treatment. The compounds are 4, 8, 22, 23, 26, 37, 38, 39, 41, 44, 47, 52, 57, 60, 62 and 75. Example 2 Indoor bioactivity test against Spodoptera require Hiibner
    [00116] [00116] The leaf immersion method was used to evaluate the insecticidal activity of the compounds in strains of Spodoptera exigua Hiibner. Leaf discs were immersed in the solution prepared with the compound of this invention for 10 seconds, and dried in a cold environment. Then they were placed in a Petri dish with 4 discs per dish. Filter paper was placed on the Petri dish to humidify it. 10 Spodoptera exigua Hiibners were placed on each plate, and this was repeated 3 times. The dishes were placed in a lighted incubator and incubated at 25 ° C with 14 hL: 10 hD of illumination. The number of Spodoptera require dead Hiibners was investigated on the 1st, 2nd and 3rd days after treatment, and mortality was calculated
    [00117] [00117] The insecticidal activity of some compounds of this invention against Spodoptera exigua Hiibner is as follows:
    [00118] [00118] The insecticidal activity of compounds 53, 60, and 75 is ≥90% (mortality from Spodoptera exigue Hiibner) at 10 ppm on the 3rd day after treatment.
    [00119] [00119] The insecticidal activity of compounds 4, 23, 37, 41, 46, 47, 57 and 62 is ≥90% (mortality from Spodoptera exigue Hiibner) at 1 ppm on the 3rd day after treatment. Example 3 Indoor bioactivity test against Plutella xylostella
    [00120] [00120] The leaf immersion method was used to evaluate the insecticidal activity of the compounds in strains of Plutella xylostella. Leaf discs were immersed in the solution prepared with the compound of this invention for 10 seconds, and dried in a cold environment. Then they were placed in a Petri dish with 4 discs per dish. Filter paper was placed on the Petri dish to humidify it. 10 Plutella xylostella were placed on each plate, and this was repeated 3 times. The dishes were placed in a lighted incubator and incubated at 25 ° C with 14 hL: 10 hD of illumination. The number of Plutella xylostella dead was investigated on the 1st, 2nd and 3rd days after treatment, and mortality was calculated.
    [00121] [00121] The insecticidal activity of some compounds of this invention against Plutella xylostella is as follows:
    [00122] [00122] The insecticidal activity of compounds 37, 39, 57, 60, 63 and 75 is ≥90% (mortality from Plutella xylostella) at 1 ppm on the 3rd day after treatment.
    [00123] [00123] The insecticidal activity of compounds 4, 8, 23, 26, 41 and 62 is ≥90% (mortality from Plutella xylostella) at 0.4 ppm on the 3rd day after treatment.
    [00124] [00124] According to the method above, compound 4 and KCl were selected and tested in parallel against Plutella xylostella to compare their insecticidal activity. The results are shown in Table 6. Table 6 Mortality of compounds 4 and KC1 against Plutella xylostella Name of Mortality （%） Structure dose compound 1d 2d 3d Compound 4 0.04 ppm 30 80 100 KC1 0.04 ppm 0 56, 67 90 （broflanilide）
    [00124] [00124] Table 6 shows that compound 4 of this invention has a fast-acting effect better than KC1 at a low dose. The mortality of Plutella xylostella is 30% on the first day and 80% on the second day after treatment. It has efficient insecticidal activity. Example 4 Indoor bioactivity test against Spodoptera litura
    [00125] [00125] The leaf immersion method was used to evaluate the insecticidal activity of the compounds in strains of Spodoptera litura. Leaf discs were immersed in the solution prepared with the compound of this invention for 10 seconds, and dried in a cold environment. Then they were placed in a Petri dish with 4 discs per dish. Filter paper was placed on the Petri dish to humidify it. 10 Spodoptera litura were placed on each plate, and this was repeated 3 times. The dishes were placed in a lighted incubator and incubated at 25 ° C with 14 hL: 10 hD of illumination. The number of dead Spodoptera litura was investigated on the 1st, 2nd and 3rd days after treatment, and mortality was calculated.
    [00126] [00126] The insecticidal activity of some compounds of this invention against Spodoptera litura is as follows:
    [00127] [00127] The insecticidal activity of compounds 4, 52, 53, 57, 75 is
    [00128] [00128] The insecticidal activity of compounds 23, 37, 41, 47, 60, 62 is ≥90% (mortality from Spodoptera litura) at 0.4 ppm on the 3rd day after treatment.
    [00129] [00129] According to the method above, compounds 4, 23 and KCl were selected and tested in parallel against Spodoptera litura for comparison of insecticidal activity. The results are shown in Table 7. Table 7: Mortality of compounds 4, 23 and KC1 in Spodoptera litura Name of Structure Dose Mortality （%） compound 1d 2d 3d Compound 4 1ppm 73.33 73.33 73.33 0.4 ppm 20.00 26.67 26.67 Compound 23 1 ppm 93.33 100.00 100.00 0.4 ppm 40.00 46.67 60.00 KCl 1 ppm 26.67 33.33 33, 33 (broflanilide） 0.4 ppm 0.00 0.00 0.00
    [00130] [00130] The results in Table 7 show that the compounds of this invention have better fast-acting properties and higher insecticide activity than KC1 at a low dose. Example 5 Indoor bioactivity test against Chilo suppressalis
    [00131] [00131] The leaf immersion method was used to evaluate the insecticidal activity of the compounds in strains of Chilo suppressalis. Rice was grown in a plastic pot with a diameter of 9 cm and a height of 10 cm. When the rice was about 25 cm, the aerial part of robust and consistent rice seedlings was selectively cut. Its leaves were removed and its 8 cm stems were kept for use. The solution prepared with the compound of this invention was poured into a Petri dish (about 40 mL) and the rice dishes were immersed in the solution for 10 seconds. The rice stalks were removed and dried in a cold environment. A wet cotton pad was placed at the bottom of the finger-shaped glass tube and 5 rice stalks were placed in each tube. 10 chilo larvae suppressed in the 3rd instar were placed in a tube, and this was repeated 3 times. The tubes were wrapped in black cotton fabric, which was sealed with rubber tape. The tubes were placed in an incubator lit at 28 ° C and incubated in the dark. The number of Chilo suppressalis vivas and the total number were investigated 3 days after treatment. Mortality was calculated.
    [00132] [00132] The insecticidal activity of some compounds of this invention against Chilo suppressalis is as follows:
    [00133] [00133] Compounds 39, 47, 50, 52 and 53 have a satisfactory insecticidal effect at 10 ppm on the 3rd after treatment, and t mortality is ≥90% (Chilo suppressalis mortality).
    [00134] [00134] Compounds 4, 23, 26, 37, 41, 46 and 62 have a satisfactory insecticidal effect at 5 ppm on the 3rd after treatment, and the mortality is ≥90% (mortality from Chilo suppressalis).
    [00135] [00135] According to the method above, compounds 23 and KC2 were selected and tested in parallel against Chilo suppressalia. The results are shown in Table 8. Table 8: Mortality of compounds 23 and KC2 in Chilo suppressalis Structure Name Mortality （% ， 3d） compound 5 ppm 2 ppm 1 ppm 0.4 ppm Compound 23 100 100 93.33 53.33 KC2 93.33 86.67 53.33 0
    [00136] [00136] The results of Table 8 show that the compound of this invention has a better insecticidal effect than KC2 at a lower dose. Example 6 Biological activity of compounds in soybean plants (in the greenhouse)
    [00137] [00137] Date of the Experiment: 06.08.2018 ~ 12.08.2018
    [00138] [00138] Test system: population of naturally occurring thrips in soybean plants planted in greenhouses. The basic number of active thrips was greater than 100 thrips per trifoliate leaf. Under the same conditions, the sensitivity of the thrips population to Spinetoram (dope: 50mg / L) is 96.55% mortality from the 6th after treatment.
    [00139] [00139] Lot size: 10 m2, without repetition.
    [00140] [00140] Test formulation: each compound was transformed into 5% SL (5% compound + 5% emulsifier + solvent to complete 100%).
    [00141] [00141] Method: foliar spraying. ① Spray time; both adult thrips and larvae were in the active period. Number of sprays: 1 time. ② Standard for water use: when the dose was in mg / kg, the top leaves became wet and water started dripping from them. ③ Inspection standard: count three individual sheets as a single sheet. Three leaves were randomly selected and investigated for the number of adult thrips and larvae in them. ④ Time and number of inspections: inspections were carried out 2 days and 6 days after spraying, independently. Two inspections were carried out.
    [00142] [00142] Results and Analysis: the results of the field activity of compound 4 against soybean trypses are shown in Table 9.
    [00143] [00143] The applicant claims that the benzamide meta-carboxamide compounds of this invention, the methods of preparation and applications thereof can be illustrated by the examples mentioned above, but this invention is not limited to them, that is , does not mean that the practice of this invention depends on the examples above. Those skilled in the art should understand that any improvement of this invention, equivalent replacement of raw materials to prepare the compounds of this invention, addition of auxiliary ingredients, selection of specific methods, etc., fall within the scope of protection and disclosing this invention.
    权利要求:
    Claims (10)
    [1]
    1. Benzamide meta-carboxamido compounds, characterized by the fact that it has formula I ： Formula I in which: Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, C1 -C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1-C6 haloalkylsulfonyl; Y1 is selected from the group consisting of F, Cl, Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl or C1-C6 haloalkoxy; Y2 is C1-C6 haloalkyl; R1 is selected from the group consisting of H, F or OCH3; R2 is selected from the group consisting of F or CF3; R3 is selected from the group consisting of H, F, Cl, Br, I, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl or C3-C8 halocycloalkyl; R4 is selected from the group consisting of H or halogen; W1 and W2 are independently of each other O or S.
    [2]
    2. Benzamide meta-carboxamido type compounds according to claim 1, characterized by the fact that: R1 is selected from the group consisting of F or OCH3; R2 is F.
    [3]
    3. Benzamide meta-carboxamido compounds according to claim 1, characterized by the fact that:
    Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl, difluo-rometoxyl, trifluoromethoxy, methylsulfinyl, trifluoromethyl sulfinyl, methylsulfonyl or trifluoromethyl sulfonyl; Y1 is selected from the group consisting of F, Cl, Br, I, CN, NO2, methyl, i-propyl, trifluoromethyl, pentafluoroethyl, heptafluoroisopropyl or trifluoromethoxy; Y2 is selected from the group consisting of trifluoromethyl, pentafluoroethyl or heptafluoroisopropyl; R1 is selected from the group consisting of F or methoxy; R2 is F; R3 is selected from the group consisting of H, F, methyl, ethyl, n-propyl, i-propyl, n-butyl, iso-butyl, t-butyl, n-pentyl, 1-methyl-butyl, 2, 2-dimethylpropyl, 2-methylbutyl, 1,3-dimethylbutyl, n-hexyl, monofluoromethyl, difluoromethyl, trifluoromethyl, monochloromethyl, dichloromethyl, trichloromethyl, pentafluoroethyl, heptafluoroisopropyl, cyclopropyl, perfopropyl, cyclobutyl, cyclobutyl, cyclobutyl, ; R4 is selected from the group consisting of H, F or Cl; W1 and W2 are independently of each other O; preferably, Z is selected from the group consisting of H, F, Cl, Br, I, CN, NO2, trifluoromethyl, trifluoromethoxy, methylsulfonyl or trifluoromethyl sulfonyl; Y1 is selected from the group consisting of Br or I; Y2 is a trifluoromethyl group; R1 is selected from the group consisting of F or methoxy; R2 is F; R3 is selected from the group consisting of H, methyl or cyclopropyl; R4 is selected from the group consisting of H or Cl.
    [4]
    4. Benzamide meta-carboxamido compounds according to any one of claims 1 to 3, characterized by the fact that meta-bisamide derivatives are selected from any of the compounds below, or a combination of at least two of the same: N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (dicyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) - 6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (cyclopropylmethyl) benzamido) -2-fluoro-robenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-cyano-N- (dicyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4- (trifluoromethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) - 6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) - 4- (trifluoromethyl) benzamide) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) -4- (trifluoromethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-chloro-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) - 6- (trifluoromethyl) phenyl) -3- (4-chloro-N- (cyclopropylmethyl) benzamido) -2-fluoro-benzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3-
    (4-chloro-N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-bromo-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-iodo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-bromo-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (1,1,1,3,3,3-hexafluoro-2-methoxypropan-2-yl) - 6- (trifluoromethyl) phenyl) -3- (4-bromo-N- (cyclopropylmethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (4-bromo-N- (1-cyclopropylethyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4-iodobenzamido) -2-fluorobenzamide; N- (2-iodo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4-iodobenzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4- (methylsulfonyl) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4- (trifluoromethoxy) benzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (cyclopropylmethyl) -4-fluorobenzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) -4-fluorobenzamido) -2-fluorobenzamide; N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1- (1-chlorocyclopropyl) ethyl) -4-cyanobenzamido) -2-fluorobenzamide; or N- (2-bromo-4- (perfluoropropan-2-yl) -6- (trifluoromethyl) phenyl) -3- (N- (1-cyclopropylethyl) -4- (methylsulfonyl) benzamido) -2-fluorobenzamide.
    [5]
    5. Tautomers, enantiomers, diastereomers or salts, characterized by the fact that they are of the compounds as defined in any one of claims 1 to 4.
    [6]
    6. Intermediate to prepare the compounds as defined in any of claims 1 to 4, characterized by the fact that it has a structure like that shown in formula VIII Formula VIII in which: Z is selected from the group consisting of H, F, Cl , Br, I, CN, NO2, C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl, C1- C6 haloalkylsulfonyl; R3 is selected from the group consisting of H, F, Cl, Br, I, C1-C6 alkyl, C1-C6 haloalkyl, C3-C8 cycloalkyl or C3-C8 halocycloalkyl; R4 is selected from the group consisting of H or halogen. W1 and W2 are independently of each other O or S.
    [7]
    7. Use of the compounds as defined in any one of claims 1 to 4 or of the tautomers, enantiomers, diastereomers or salts thereof as defined in claim 5, characterized by the fact that it is for the control of plant insects.
    [8]
    8. Insecticidal composition, characterized by the fact that it comprises active ingredients and an acceptable agricultural vehicle, in which the active ingredients are the benzamide meta-carboxamido compounds as defined in any one of claims 1 to 4 or the tautomers, enantiomers, diastereomers or salts thereof as defined in claim 5.
    [9]
    9. Insecticidal composition according to claim 8, characterized by the fact that the weight percentage of the active ingredients is 1% -99%.
    [10]
    10. Insect control method, characterized by the fact that an effective concentration of the compounds as defined in any of claims 1 to 4, or of the tautomers, enantiomers, diastereomers or salts thereof as defined in claim 5, or composition as defined in claim 8 or 9, in insects or their habitat; the preferred effective concentration varying within a range of 10 g / ha to 1000 g / ha, the most preferred effective concentration varies within a range of 25 g / ha to 500 g / ha.
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    CA3074759A1|2020-01-02|
    PH12020500515A1|2021-05-10|
    JP2020535109A|2020-12-03|
    CN110028423A|2019-07-19|
    IL272620D0|2020-03-31|
    KR20200031684A|2020-03-24|
    EP3816150A4|2021-10-06|
    CN109497062B|2019-11-26|
    CN109497062A|2019-03-22|
    WO2020001067A1|2020-01-02|
    CN108586279A|2018-09-28|
    AU2019296636B2|2020-10-15|
    US20200178525A1|2020-06-11|
    JP6771116B1|2020-10-21|
    AU2019296636A1|2020-03-05|
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    法律状态:
    2021-12-14| B350| Update of information on the portal [chapter 15.35 patent gazette]|
    优先权:
    申请号 | 申请日 | 专利标题
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    CN201810669847.7A|CN108586279A|2018-06-26|2018-06-26|One inter-species diamide compound and its preparation method and application|
    CN201811555432.3A|CN109497062B|2018-06-26|2018-12-18|One inter-species diamide compound and its preparation method and application|
    CN201811555432.3|2018-12-18|
    PCT/CN2019/077756|WO2020001067A1|2018-06-26|2019-03-12|M-diamide compound and preparation method therefor and use thereof|
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