WO2013064079A1 - Use of compound of pyrazole amides as agricultural fungicide - Google Patents

Use of compound of pyrazole amides as agricultural fungicide Download PDF

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WO2013064079A1
WO2013064079A1 PCT/CN2012/083868 CN2012083868W WO2013064079A1 WO 2013064079 A1 WO2013064079 A1 WO 2013064079A1 CN 2012083868 W CN2012083868 W CN 2012083868W WO 2013064079 A1 WO2013064079 A1 WO 2013064079A1
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group
alkyl
alkoxy
hydrogen
halogenated
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PCT/CN2012/083868
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French (fr)
Chinese (zh)
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刘长令
王立增
兰杰
孙旭峰
孙芹
张金波
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中国中化股份有限公司
沈阳化工研究院有限公司
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Priority to CN201280043368.5A priority Critical patent/CN103781357B/en
Publication of WO2013064079A1 publication Critical patent/WO2013064079A1/en

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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
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles

Definitions

  • the invention belongs to the field of agricultural fungicides, and in particular relates to the use of a pyrazole amide compound as an agricultural fungicide. Background technique
  • Patent US 4,950,668 A discloses that N-benzylpyrazole amide derivatives such as tebufenpyrad have insecticidal and acaricidal activity.
  • Patent US 5,091,693 A discloses that a phenoxy-substituted N-benzylpyrazole amide derivative such as tolfenpyrad has insecticidal and acaricidal activity.
  • Patent CN1927860A discloses that a pyrazole amide derivative of a phenylbiaryl group has insecticidal and acaricidal activity. No bactericidal activity was reported.
  • Patent WO02083647A1 discloses pyridylamide derivatives containing biphenyl having bactericidal, insecticidal and acaricidal activity.
  • Patent US 5,091,693 discloses a compound of the formula having insecticidal and acaricidal activity, but the patent does not disclose its bactericidal activity.
  • Patent EP0394043A1, US5264448A discloses a compound of the formula having insecticidal and acaricidal activity
  • Patent EP 0 365 925 A1 discloses a compound of the formula having insecticidal and acaricidal activity. Although the compound of the patent is partially identical to the compound of the formula (I), the patent does not report any bactericidal activity.
  • Patent WO2009024342A2 discloses a compound of the following formula and a specific compound CK1 (patent number 1.581), and some compounds have a minimum of 50% for wheat powdery mildew, barley net blotch, wheat brown rust, wheat black carp at 0.02% active ingredient content. %.
  • Patent WO02089583A1 discloses a compound of the general formula and a specific compound azole amide (patent number No. 4), CK2 (patent number No. 5), CK3 (patent number No. 2), CK4 (patent No. l), With sterilization
  • Patent WO02083647A1 discloses a compound of the following formula and a specific compound CK5 (patent number No. 18) having bactericidal, insecticidal and acaricidal activity.
  • the present invention has intensively studied the bactericidal activity of pyrazole amide compounds represented by the following formula, and found that the compounds have a broad spectrum of sterilization.
  • Activity - can be used to control diseases caused by various pathogens such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes on various crops, and because of the high biological activity of these compounds, at very low doses You can get good results.
  • R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 8 alkyl, halogenated C r C 8 alkyl, 8 -alkoxy, halo- -3 ⁇ 4 alkoxy, cyano dC 8 alkyl, cyano dC 8 alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, dC 8 alkyl, halo dC 8 An alkyl group, a dC 8 alkoxy group or a halogenated CrC 8 alkoxy group;
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 8 alkyl, halo dC 8 alkyl, dC 8 alkoxy, halogenated dC 8 alkoxy, 8 -alkylthio or dC 8 alkyl sulfonate Acyl group
  • A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CN)(CH 3 ) - or -CH(CN)-;
  • R 5 may be the same or different and are respectively selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, dC 8 alkyl, halogenated Ci-C 8 3 ⁇ 43 ⁇ 4 ⁇ 4 Ci-Cg ⁇ ⁇ Ci-Cg C 3 -C 8 ring; ⁇ group, C 2 -C 8 ⁇ 3 ⁇ 4 C 2 -C 8 block group, C 2 -C 8 alkenyloxy group, ⁇ 3 ⁇ 4-3 ⁇ 4 alkenyloxy group, 3 ⁇ 4-3 ⁇ 4 Blockoxy, ⁇ 3 ⁇ 4 8 oxy, 8 alkylthio, ⁇ -3 ⁇ 4 alkane, Ci-C8 3 ⁇ 43 ⁇ 43, 3
  • Q is selected from hydrogen, halo, cyano, nitro, hydroxy, amino, dC 8 alkyl, haloalkyl dC 8 alkyl, dC 8 alkoxy, substituting ⁇ dC 8 alkoxy, C 3 -C 8 cycloalkyl a group, a C 2 -C 8 alkenyl group, a C 2 -C 8 block group, a C 2 -C 8 alkenyloxy group, a C 2 -C 8 alkenyloxy group, an 8-oxyl group, a halogenated 8- oxyl group, dC 8 thiol, halogenated dC 8 alkylthio, dC 8 alkoxy dC 8 alkyl, 13 ⁇ 4 generation Ci-Cs, alkoxy-Ci-Cs, Ci-Cs, thio-Ci-Cs, 13 ⁇ 4 generation Ci-Cs Institute thio-Ci-Cs, dC 8 alkyls
  • the pyrazole amide compound as an agricultural bactericide is a compound selected from the group consisting of pyridyloxy groups in the formula I, and has a structure such as
  • Ci-C 6 alkyl Selected from hydrogen, Ci-C 6 alkyl, ⁇ dC 6 alkyl, Ci-C 6 alkoxy C r C 3 alkyl, cyano dC 6 alkyl or C 3 -C 6 cycloalkyl;
  • R 2 is selected from the group consisting of hydrogen, halogen, cyano, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, halo C r C 6 alkoxy, cyano dC 6 alkyl, cyano dC 6 Alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, dC 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy or halo CC 6 alkoxy;
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 Alkoxy, 6 alkylthio or c r c 6 alkylsulfonyl;
  • R 5 may be the same or different and are respectively selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, ⁇ Generation C r C 6 alkoxy, C 2 -C 6 alkenyloxy, ⁇ C 2 -C 6 alkenyloxy, C 2 -C 6 -oxyl, halo C 2 -C 6 -oxyl, C r C 6 alkylsulfinyl, halogenated C r C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, halogenated C r C 6 alkylsulfonyl, C r C 6 alkylamino, halogen Generation C r C 6 alkylamino or C 2 -C 6 dialkylamino; is selected from hydrogen, halo, cyano, nitro, hydroxy
  • A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
  • a further preferred embodiment of the present invention is a pyrazole amide compound represented by the formula (I-A) as an agricultural bactericide:
  • R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, cyano 6 alkyl , cyano 6 alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, C r C 6 alkyl, Halogenated C r C 6 alkyl, C r C 6 alkoxy or halo 6 alkoxy;
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, 6 alkane Thio or c r c 6 alkylsulfonyl;
  • R 5 is selected from hydrogen
  • n is selected from an integer from 0 to 4; when n is greater than 1, it may be the same or different;
  • A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
  • a still further preferred embodiment of the present invention is a pyrazole amide compound represented by the formula (I-A) as an agricultural bactericide:
  • R 2 is selected from hydrogen, halo, cyano, C r C 4 alkyl, C r C 4 halogenated alkyl, alkoxy, halo ⁇ 4 alkoxy, cyano dC 3 alkyl, cyano - 3 ⁇ 4 alkoxy, unsubstituted or substituted by 1 to 3 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halo 4 alkoxy;
  • R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkane Oxy or halogenated C r C 4 alkoxy;
  • R 5 is selected from hydrogen
  • n selected from An integer from 0 to 4; when n is greater than 1, it may be the same or different;
  • A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
  • a still further preferred embodiment is the pyrazole amide compound represented by the general formula (IA) as an agricultural bactericide: Selected from hydrogen, methyl, ethyl, cyclopropyl or cyclohexyl;
  • R 2 is selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, chloromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, monofluoromethoxy, Trifluoromethoxy, trifluoroethoxy, cyanomethyl, cyanomethoxy, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, P-methoxyphenyl, p-trifluoromethoxyphenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl;
  • R 3 is selected from the group consisting of hydrogen, chlorine, bromine or methyl
  • R 5 is selected from hydrogen
  • n is selected from an integer of 0 to 4; when n is greater than 1, it may be the same or different;
  • A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
  • R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-trifluoromethoxy Phenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl;
  • R 3 is selected from the group consisting of hydrogen, chlorine or methyl
  • R 5 is selected from hydrogen
  • n is selected from an integer from 0 to 4; When n is greater than 1, it may be the same or different;
  • A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
  • R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl or p-fluorophenyl;
  • R 3 is selected from the group consisting of hydrogen, chlorine or methyl
  • R 5 is selected from hydrogen
  • n is selected from the integers from 1 to 3;
  • A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl or t-butyl.
  • Cycloalkyl a substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen and the like.
  • Haloalkyl a straight or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Fluoromethyl, trifluoromethyl, and the like.
  • Alkoxy A linear or branched alkyl group bonded to a structure via an oxygen atom.
  • Alkoxyalkyl Alkoxy is attached to the structure via an alkyl group. For example, CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -.
  • Haloalkoxyalkyl group The hydrogen atom on the alkyl group of the alkoxyalkyl group may be partially or completely substituted by a halogen atom. Such as ClCH 2 CH 2 OCH 2 -.
  • Haloalkoxy a linear or branched alkoxy group, and a hydrogen atom on these alkoxy groups may be partially or completely substituted by a halogen atom.
  • Alkylthio a linear or branched alkyl group bonded to a structure via a sulfur atom bond.
  • Alkylthioalkyl An alkylthio group is attached to the structure via an alkyl group. Such as CH 3 SCH 2 -.
  • Haloalkylthio a linear or branched alkylthio group in which a hydrogen atom may be partially or completely substituted by a halogen atom. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.
  • Haloalkylthioalkyl A haloalkylthio group is attached to the structure via an alkyl group, such as ClCH 2 SCH 2 -.
  • Alkylamino a linear or branched alkyl group bonded to the structure via a nitrogen atom.
  • Haloalkylamino group a linear or branched alkylamino group in which a hydrogen atom may be partially or completely substituted by a halogen atom.
  • Alkenyl a linear or branched olefin such as a vinyl group, a 1-propenyl group, a 2-propenyl group and a different butenyl, pentenyl group and hexenyl isomer.
  • Alkenyl groups also include polyenes such as 1,2-propadienyl and 2,4-hexyl Dienyl.
  • Haloalkenyl group a linear or branched olefin in which a hydrogen atom on these alkenyl groups may be partially or completely substituted by a halogen atom.
  • Block base A linear or branched block type, such as an ethyl group, a 1-propyl block, a 2-propyl block, and different butyr, pentyl and hexyl isomers.
  • the block group also includes a group consisting of a plurality of triple bonds, such as a 2,5-hexane block.
  • Halogenated block A linear or branched block, in which a hydrogen atom may be partially or completely replaced by a halogen atom.
  • Alkenyloxy A linear or branched olefin that is bonded to the structure via an oxygen atom.
  • Haloalkenyloxy a linear or branched alkenyloxy group, and a hydrogen atom on these alkenyloxy groups may be partially or completely substituted by a halogen atom.
  • Block Oxygen A linear or branched block that is attached to a structure via an oxygen atom.
  • Halo blockoxy a linear or branched blockoxy group, and a hydrogen atom on these blockoxy groups may be partially or completely substituted by a halogen atom.
  • Alkylsulfinyl A straight or branched alkyl group is attached to the structure via a sulfinyl group (-SO-), such as a methylsulfinyl group.
  • Haloalkylsulfinyl a linear or branched alkylsulfinyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom.
  • Alkylsulfonyl A straight or branched alkyl group is attached to the structure via a sulfonyl group (-so 2 -), such as a methylsulfonyl group.
  • Haloalkylsulfonyl a linear or branched alkylsulfonyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom.
  • Alkylcarbonyl An alkyl group is attached to the structure via a carbonyl group, such as CH 3 CO-, CH 3 CH 2 CO-.
  • Haloalkylcarbonyl The hydrogen atom on the alkyl group of the alkylcarbonyl group may be partially or completely substituted by a halogen atom such as CF 3 CO-.
  • Alkylaminocarbonyl such as CH 3 NHCO-, CH 3 CH 2 NHCO-.
  • Alkoxycarbonyl alkoxy is attached to the structure via a carbonyl group.
  • CH 3 OCO-, CH 3 CH 2 OCO alkylcarbonyloxy such as CH 3 COO-, CH 3 CH 2 NHCOO-.
  • Alkylcarbonylamino such as CH 3 CONH-, CH 3 CH 2 NHCONH -.
  • Heteroaryl The heteroaryl group referred to in the present invention is a five-membered or six-membered ring aryl group containing one or more N, O, s hetero atoms.
  • Heteroaryloxy A heteroaryl ring is attached to the structure via an oxygen group, such as a pyridyloxy group, a pyrimidinyloxy group or the like.
  • L is a leaving group and is a halogen, a methanesulfonate or a p-toluenesulfonate.
  • the other groups are defined as before.
  • the compound of the formula (VI-1) and (V) are reacted in a suitable solvent in the presence of a suitable base to give (IV-1).
  • the specific preparation can be carried out by referring to the method described in Fine Chemicals, 2005, 22(12): 944-960.
  • the reaction is usually carried out at a temperature ranging from room temperature to the boiling point of the solvent, and a suitable reaction temperature is 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • Suitable solvents may be selected from, for example, acetone, butanone, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, methanol or ethanol, and the like.
  • Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine or sodium hydride, and the like.
  • (IV-1) is hydroreduced in the presence of a suitable catalyst and aqueous ammonia in a suitable solvent to give (11-1).
  • a suitable catalyst and aqueous ammonia in a suitable solvent to give (11-1).
  • Specific preparation Reference may be made to the literature J. Am. Chem. Soc, 70, 3788 (1948); 82, 681 (1960); 82, 2386 (1960); Can. J. Chem, 49, 2990 (1971); J. Org. Chem, 37, 335 (1972); Organic Syntheses, Coll. Vol. 3, p. 229, p. 720 (1955), Vol. 23, p. 71 (1943) or Vol. 27, p. 18 (1947).
  • the reaction is usually carried out at a temperature ranging from room temperature to the boiling point of the solvent, and a suitable reaction temperature is 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • Suitable solvents may be selected from the group consisting of methanol, ethanol, isopropanol, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, dichloromethane, methyl acetate, ethyl acetate, tetrahydrofuran, dioxane. , N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide.
  • Suitable catalysts may be selected from the group consisting of Raney nickel, palladium carbon or platinum oxide.
  • the compound represented by the formula (IA-1) may be an amine represented by the formula (II-1) and a pyrazolecarbonyl chloride represented by the formula (III) in a suitable solvent in the presence of a suitable base (also Can be obtained without condensation.
  • a suitable solvent may be selected from the group consisting of benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylene.
  • Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine or sodium hydride, and the like.
  • the reaction temperature may be between room temperature and the boiling point of the solvent, and is usually from 20 to 100 °C.
  • the reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
  • A is a corresponding structure having one carbon atom less than A.
  • the other groups are defined as before.
  • reaction conditions obtained by the reaction of (VI-2) and (V), the intermediate (IV-2) and (II-2) (IA-2) and the choice of solvent, base and metal catalyst are the same as the first In the case of (VI-1) and (V), the corresponding steps of (IA-1) are obtained via intermediates (IV-1) and (II-1).
  • Boc 2 0 refers to di-tert-butyl dicarbonate.
  • the other groups are defined as before.
  • the di-tert-butyl dicarbonate is reacted with the corresponding aminophenol at 0 to 100 ° C in a suitable solvent in the presence of a suitable base to first obtain a Boc-protected aminophenol (VII).
  • the reaction temperature is preferably 0 to 50 ° C; the reaction time is 30 minutes to 20 hours, preferably 0.5 to 10 hours.
  • Suitable solvents are selected from the group consisting of benzene, toluene, xylene, chloroform, dichloromethane, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide;
  • the base is selected from alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate or potassium hydrogencarbonate.
  • (VII) and (V) are condensed in a suitable solvent in the presence of a suitable base at 0 to 100 ° C to obtain a (VII1) o reaction time of 30 minutes to 20 hours, preferably 0.5 to 10 hours.
  • suitable solvents are selected from the group consisting of benzene, toluene, xylene, chloroform, dichloromethane, acetone, butanone, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethylene.
  • a suitable base is selected from metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, and organic amines such as pyridine or triethylamine.
  • Suitable solvents are selected from the group consisting of ethyl acetate, methyl acetate, methyl formate, benzene, toluene, xylene, chloroform, dichloromethane, water, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; etc.; suitable acids are selected from the group consisting of hydrochloric acid, trifluoroacetic acid, sulfuric acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, and stearic acid.
  • the base is selected from the group consisting of metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonate
  • metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide
  • alkali metal carbonate For a specific preparation method of a salt such as sodium carbonate or potassium carbonate, uuuuu is described in WO2004093800A.
  • the compound represented by the formula (IA-3) may be an amine represented by the formula ( ⁇ -3) and a pyrazolecarbonyl chloride represented by the formula (III) in a suitable solvent in the presence of a suitable base (also Can be obtained without condensation.
  • a suitable solvent also Can be obtained without condensation.
  • the reaction conditions and the choice of solvent and base are the same as those obtained by the reaction of ( ⁇ -1) and (III) in the first case (I-A-l) o
  • the raw materials involved in the preparation method of the above compound of the general formula (I) are as follows:
  • the compounds represented by the general formulae (VI-1), (VI-2) and (V) are commercially available, (VI-3)
  • the compounds shown are either commercially available or prepared according to known methods such as those reported in JP61024550, US4843160, US4746754, US2396580, JP02017164, Afmidad, 42(397), 270-2; 1985, and the like.
  • the compound of the formula (III) is commercially available or can be reported according to known literature such as Annalen der Chemie Justus Liebig's, 536, 97 (1938) Bull. Soc. Chim. France, 293 (1966) US 4950668 JP 2292263 JP 2053776 JP4069361 or JP 4069379. Method preparation.
  • the present invention can be illustrated by the compounds listed in Tables 1 to 3 below, but does not limit the present invention.
  • the present invention Since the present invention has found for the first time that a pyrazole amide compound represented by the general formula (I) has excellent bactericidal activity, the compound can be applied to various crops in agricultural fields such as agriculture, horticulture and flower cultivation.
  • the disease is especially suitable for controlling the following plant diseases: cucumber downy mildew, corn rust, etc.
  • the plant pathogen which can be controlled by the compound of the present invention is not limited to the above. Accordingly, the technical solution of the present invention includes the use of a pyrazole amide compound represented by the formula (I), particularly a pyrazole amide compound represented by the formula (I-A), as an agricultural bactericide.
  • the use of the pyrazole amide compound (preferably the compound of the formula (IA)) represented by the formula (I) proposed by the present invention as an agricultural bactericide further comprises providing a bactericidal composition containing bactericidal activity in the composition
  • the compound of the formula (I) (preferably the compound of the formula (IA)) as an active ingredient, the active ingredient in the composition is present in an amount of from 0.1 to 99% by weight.
  • the composition also contains an agriculturally acceptable carrier and surfactant.
  • the above compositions can be prepared into a desired dosage form according to known methods, such as wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols.
  • carrier and surfactant in the formulation is well known to those skilled in the art.
  • bactericides By incorporating other one or more bactericides into the composition, it has a broader spectrum of activity than the compound of formula (I) alone. Further, other bactericides have a synergistic effect on the bactericidal activity of the compound of the formula (I).
  • the compound of the formula (I) can also be used in combination with other insecticides or at the same time with another fungicide and other insecticides. detailed description
  • the organic layer was poured into 20 mL of water, and the organic layer was washed successively with 5% diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and then evaporated and evaporated. Pure product 0.38 g was obtained, the yield was 88.0%, and the melting point was 97-98 °C.
  • Compound 170 melting point 145-146 ° C o 5 ppm 1.23 (3H, t), 2.60-2.63 (2H, m), 2.96 (2H, t), 3.74-3.76 (2H, (m), 4.12 (3H, s) ).
  • Compound 176 mp 157-158°C o 5ppm 1.22 (3H, t), 2.57-2.64 (2H, m), 2.96 (2H, t), 3.74-3.79 (2H, m), 4.13 (3H, s), 7.12(2H, d), 7.30(2H, d), 7.85(1H, s).
  • Compound 972 Melting point 100-lOr. Sppm 1.23(3H, t), 1.42(3H, t), 2.59-2.67(2H, m), 4.00-4.07(2H, m), 4.15(3H, s), 4.56(2H, d), 6.88(2H , d), 7.27 (2H, d).
  • Example 8 60% wettable powder
  • Kaolin is made up to 100%
  • the components (both solids) are mixed and comminuted in a pulverizer until the granules reach the standard.
  • Example 9 30% aqueous suspension
  • Compound 53 was pulverized together with 80% of the water to be added and sodium dodecylnaphthalene sulfonate in a ball mill (1 mm beads). The other components were dissolved in the remaining water, and then the other components were stirred.
  • the compound 54 and the other components are thoroughly mixed, and the thus obtained suspension concentrate is diluted with water to obtain a diluent of any desired concentration.
  • test method is as follows:
  • the test was carried out using a potted seedling assay.
  • the two-leaf stage potted cucumber seedlings with uniform growth were selected as test materials for cucumber downy mildew; the two-leaf potted corn seedlings with uniform growth were selected as test materials for corn rust; the two-leaf potted wheat seedlings with uniform growth were selected as wheat white powder.
  • Disease test material The compound of the present invention was subjected to foliar spray treatment at a designed concentration, and a blank control of sprayed water was additionally provided, three times of repetition, and the disease was inoculated the next day after the treatment. After inoculation, the plants are placed in an artificial climate chamber (temperature: ⁇ 25 °C, night 20 °C, relative humidity: 95 ⁇ 99%).
  • the control effect of the compounds 53, 54, 115, 169, 170, 972, 973, 1024, 1025, 1027, 1028, etc. is 100%; the control effect of the compound 189, 591, etc. is 98%; The control effect of 519 is 95%; the control effect of compound 157 is 85%;
  • the control effects of the compounds 53, 54, 115, 169, 170, 972, 973, 1024, 1027, etc. are 100%; the control effect of the compound 1025 is 80%;
  • the control effects of the compounds 53, 54, 169, 1024, etc. are 100%; the control effects of the compounds 115, 972 are 98% and 95%, respectively;
  • the concentration of the chemical solution is 12.5 ppm, the control effect of the compound 53, 54 and the like is 100%; the control effect of the compound 1024 is 85%; and when the concentration of the chemical liquid is 3.125 ppm, the control effect of the compound 53 is 95%.
  • the control effects of the compounds 115, 169, 519, 972, 973, 1024, 1025, 1026, 1027, 1028, etc. are 100%, and the control effect of the compound 189 or the like is 95%;
  • the control effect of the compounds 972, 973, 1024, 1026, 1027, etc. is 100%; the control effect of the compound 1025 is 95%;
  • the concentration of the chemical solution is 25 ppm
  • the control effect of the compounds 973, 1024, 1027, etc. is 100%
  • the control effect of the compound 1026 is 90%
  • the compound 973 and 1024 have a control effect of 90% or more.
  • the determination method is as follows:
  • the high-throughput screening method is adopted, that is, the sample of the test compound is dissolved in a suitable solvent (such as acetone, methanol, DMF, etc., and selected according to the solvency of the sample) to prepare a desired concentration.
  • a suitable solvent such as acetone, methanol, DMF, etc., and selected according to the solvency of the sample
  • the liquid to be tested In the ultra-clean working environment, the test solution is added to the micropores of the 96-well culture plate, and the pathogen propagule suspension is added thereto, and the treated plate is placed in a constant temperature incubator for cultivation, and then investigated after 24 hours. .
  • the germination or growth of the pathogen of the pathogen was visually observed at the time of the investigation, and the bacteriostatic activity of the compound was evaluated based on the germination or growth of the control treatment.
  • the control effects of the compounds 115, 181, 499, 519, 973, 1024, 1028, etc. are 100%; the control effects of the compounds 155, 972, 1025, 1027 are all 80%;
  • the concentration of the chemical solution is 0.9 ppm
  • the control effect of the compound 115 and 519 is 100%
  • the control effect of the compound 973 is 80%
  • the control effect of the compound 115, 519, etc. is 100%; the control effect of the compound 499 is 80%; when the concentration of the chemical solution is 8.3 ppm, the control effect of the compound 519 is 100%; 80%;
  • the compound 519 had an effect of 80%.
  • the test was carried out in July 2011 in Yitian District, Yuhong District, Shenyang City, Liaoning Republic. The test was carried out in accordance with the relevant standards of the National Standard for Pesticide Field Efficacy Test of the People's Republic of China.
  • the concentration of the compound of the present invention 54 (10% concentrated suspension of Example 10, the same hereinafter) was 400, 100 ppm, and the concentration of the control agent 50% dimethomorph wettable powder (commercially available) was 200 ppm.
  • the area of the plot is 20m 2 , randomly arranged, and repeated twice. The amount of liquid spray is about 600 L/hm 2 , and fresh water is used as a blank control.
  • Table 5 The results of the test of compound 54 against cucumber downy mildew field plot are shown in Table 5.

Abstract

Disclosed is the use of a compound of pyrazole amides as shown in general formula (I) as an agricultural fungicide. The definitions of each substituent in formula (I) are given in the description. The compound of the present invention has a broad spectrum of fungicidal activity, and an excellent activity against diseases such as cucumber downy mildew, rice blast, corn rust, wheat powdery mildew, cucumber gray mould etc.. In particular, the compound has a higher activity against diseases such as cucumber downy mildew, rice blast etc., and can achieve an excellent effect at a very low concentration.

Description

吡唑酰胺类化合物作为农用杀菌剂的用途 技术领域  Use of pyrazole amides as agricultural fungicides
本发明属农用杀菌剂领域， 具体地涉及一种吡唑酰胺类化合物作为农用杀菌剂的用途。 背景技术  The invention belongs to the field of agricultural fungicides, and in particular relates to the use of a pyrazole amide compound as an agricultural fungicide. Background technique
专利 US4950668A公开了吡螨胺（tebufenpyrad)等 N-苄基吡唑酰胺类衍生物具有杀虫杀 螨活性。 专利 US5039693A公开了唑虫酰胺 （tolfenpyrad) 等苯氧基取代的 N-苄基吡唑酰胺 类衍生物具有杀虫杀螨活性。 专利 CN1927860A公开了苯联芳基的吡唑酰胺类衍生物具有杀 虫杀螨活性。均无杀菌活性报道。专利 WO02083647A1公开了含联苯基的吡唑酰胺类衍生物 具有杀菌、 杀虫和杀螨活性。  Patent US 4,950,668 A discloses that N-benzylpyrazole amide derivatives such as tebufenpyrad have insecticidal and acaricidal activity. Patent US 5,091,693 A discloses that a phenoxy-substituted N-benzylpyrazole amide derivative such as tolfenpyrad has insecticidal and acaricidal activity. Patent CN1927860A discloses that a pyrazole amide derivative of a phenylbiaryl group has insecticidal and acaricidal activity. No bactericidal activity was reported. Patent WO02083647A1 discloses pyridylamide derivatives containing biphenyl having bactericidal, insecticidal and acaricidal activity.
专利 US5039693公开了如下通式的化合物， 具有杀虫杀螨活性， 但该专利没有公开其具 有杀菌活性。  Patent US 5,091,693 discloses a compound of the formula having insecticidal and acaricidal activity, but the patent does not disclose its bactericidal activity.
Figure imgf000003_0001
Figure imgf000003_0001
专利 EP0394043A1、 US5264448A 公开了如下通式的化合物， 具有杀虫杀螨活性； Patent EP0394043A1, US5264448A discloses a compound of the formula having insecticidal and acaricidal activity;
JP2001064176也公开了如下通式的化合物仅作为减肥药剂使用。 其中 =吡唑环， B为吡啶 环， 与本通式 (I)化合物部分相同 尽管如此， 该三件专利并没有任何杀菌活性报道; JP2001064176 also discloses that a compound of the following formula is used only as a slimming agent. Wherein = pyrazole ring, B is a pyridine ring, which is partially identical to the compound of the formula (I). Nevertheless, the three patents do not have any bactericidal activity reports ;
Figure imgf000003_0002
Figure imgf000003_0002
专利 EP0365925A1公开了如下通式的化合物， 具有杀虫杀螨活性， 尽管专利中化合物与 本通式 (I)化合物部分相同， 但该专利也没有任何杀菌活性报道。  Patent EP 0 365 925 A1 discloses a compound of the formula having insecticidal and acaricidal activity. Although the compound of the patent is partially identical to the compound of the formula (I), the patent does not report any bactericidal activity.
Figure imgf000003_0003
Figure imgf000003_0003
专利 WO2009024342A2 公开了如下通式的化合物及具体化合物 CK1 (专利中编号为 1.581 )， 部分化合物在 0.02%有效成分含量下对小麦白粉病、 大麦网斑病、 小麦褐锈病、 小麦 黑胫 最低为 50%。  Patent WO2009024342A2 discloses a compound of the following formula and a specific compound CK1 (patent number 1.581), and some compounds have a minimum of 50% for wheat powdery mildew, barley net blotch, wheat brown rust, wheat black carp at 0.02% active ingredient content. %.
Figure imgf000003_0004
Figure imgf000003_0004
专利 WO02089583A1 公开了如下通式的化合物及具体化合物唑虫酰胺 （专利中编号为 No.4)， CK2 (专利中编号为 No.5)， CK3 (专利中编号为 No.2)， CK4 (专利中编号为 No. l )， 具有杀菌 Patent WO02089583A1 discloses a compound of the general formula and a specific compound azole amide (patent number No. 4), CK2 (patent number No. 5), CK3 (patent number No. 2), CK4 (patent No. l), With sterilization
Figure imgf000004_0001
Figure imgf000004_0001
专利 WO02083647A1 公开了如下通式的化合物及具体化合物 CK5 (专利中编号为 No.18), 具有杀菌、 杀虫杀螨活性。  Patent WO02083647A1 discloses a compound of the following formula and a specific compound CK5 (patent number No. 18) having bactericidal, insecticidal and acaricidal activity.
Figure imgf000004_0002
Figure imgf000004_0002
CK5  CK5
尽管本发明的化合物大多是已知的， 但对于已经报道的上述结构中含吡啶环的 5-吡唑酰 胺类化合物未见杀菌活性报道。 发明内容  Although the compounds of the present invention are mostly known, no bactericidal activity has been reported for the 5-pyrazolamide compound containing a pyridine ring in the above structure which has been reported. Summary of the invention
为了获得新的作用机理独特的防治各种作物病害的新杀菌剂， 本发明对如下通式所示的 吡唑酰胺类化合物杀菌活性进行了深入地研究， 结果发现该类化合物具有广谱的杀菌活性 —可用于防治在各种作物上由卵菌纲、 担子菌纲、 子囊菌和半知菌类等多种病菌引起的病 害， 而且由于这些化合物具有很高的生物活性使得在很低的剂量下就可以获得很好的效果。 该类化合物对各种霜霉病如黄瓜霜霉病， 众多疫病如马铃薯晚疫病、 辣椒疫病， 众多灰霉病 如黄瓜灰霉病， 水稻稻瘟病、 水稻稻曲病、 水稻纹枯病， 玉米锈病， 各种白粉病如小麦白粉 病、 小麦锈病、 小麦纹枯病， 大豆锈病等病害具有很好的防效， 对黄瓜霜霉病、 水稻稻瘟病 防效更好， 从而完成了本发明。  In order to obtain a new fungicide having a unique mechanism of action for controlling various crop diseases, the present invention has intensively studied the bactericidal activity of pyrazole amide compounds represented by the following formula, and found that the compounds have a broad spectrum of sterilization. Activity - can be used to control diseases caused by various pathogens such as Oomycetes, Basidiomycetes, Ascomycetes and Deuteromycetes on various crops, and because of the high biological activity of these compounds, at very low doses You can get good results. This kind of compound against various downy mildew diseases such as cucumber downy mildew, many diseases such as potato late blight, pepper blight, many gray mold diseases such as cucumber gray mold, rice blast, rice blast disease, rice sheath blight, corn Rust, various powdery mildew diseases such as wheat powdery mildew, wheat rust, wheat sheath blight, soybean rust and other diseases have good control effect, and are more effective against cucumber downy mildew and rice blast, thereby completing the present invention.
本发明技术方案如下：  The technical scheme of the present invention is as follows:
一种吡唑酰胺类化合物作为农用杀菌剂的用途， 所述化合物结构如通式 （I ) 所示：  A use of a pyrazole amide compound as an agricultural bactericide, the compound having the structure shown in the formula (I):
Figure imgf000004_0003
Figure imgf000004_0003
式中：  In the formula:
选自氢、 C C8烷基、 ^代 CrC8烷基、 d-C8烷氧基 CrC8烷基、氰基 CrC8烷基或 C3-C, 环烷基； R2选自氢、 卤素、氰基、 CrC8烷基、 卤代 CrC8烷基、 8烷氧基、 卤代 ^-¾烷氧基、 氰基 d-C8烷基、 氰基 d-C8烷氧基、 未取代的或被 1-5个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 羟基、 氨基、 巯基、 d-C8烷基、 卤代 d-C8烷基、 d-C8烷氧基或 卤代 CrC8烷氧基； Is selected from hydrogen, CC 8 alkyl, C r C 8 substituting ^ alkyl, dC 8 alkoxy, C r C 8 alkyl, cyano C r C 8 alkyl or C 3 -C, cycloalkyl; R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 8 alkyl, halogenated C r C 8 alkyl, 8 -alkoxy, halo- -3⁄4 alkoxy, cyano dC 8 alkyl, cyano dC 8 alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, dC 8 alkyl, halo dC 8 An alkyl group, a dC 8 alkoxy group or a halogenated CrC 8 alkoxy group;
R3选自氢、 卤素、 氰基、 硝基、 d-C8烷基、 卤代 d-C8烷基、 d-C8烷氧基、 卤代 d-C8 烷氧基、 8烷硫基或 d-C8烷基磺酰基； R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 8 alkyl, halo dC 8 alkyl, dC 8 alkoxy, halogenated dC 8 alkoxy, 8 -alkylthio or dC 8 alkyl sulfonate Acyl group
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-、 -C(CH3)2-、 -C(CN)(CH3)-或 -CH(CN)-; 、 R5可相同或不同， 分别选自氢、 卤素、 氰基、 硝基、 羟基、 氨基、 d-C8烷基、 卤代 Ci-C8 ¾¾¾ Ci-Cg \ ί Ci-Cg C3-C8环; ^基、 C2-C8 ^ ¾ C2-C8块基、 C2-C8 烯氧基、 ^代 ¾-¾烯氧基、 ¾-¾块氧基、 ^代 ¾ 8块氧基、 8烷硫基、 ^代 -¾烷 ¾ 、 Ci-C8 ¾¾¾,¾ Ci-Cg ¾¾¾ \ ί Ci-C8 ¾¾¾,¾ Ci-Cg ¾¾¾ Ci-Cg ¾¾¾¾¾ Ci-Cg ¾¾¾ \ 代 d-C8烷硫基 d-C8烷基、 d-C8烷基亚磺酰基、 卤代 d-C8烷基亚磺酰基、 d-C8烷基磺酰 基、 卤代 d-C8烷基磺酰基、 d-C8烷基氨基、 卤代 d-C8烷基氨基或 C2-C8二烷基氨基；A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CN)(CH 3 ) - or -CH(CN)-; , R 5 may be the same or different and are respectively selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, dC 8 alkyl, halogenated Ci-C 8 3⁄43⁄4⁄4 Ci-Cg \ ί Ci-Cg C 3 -C 8 ring; ^ group, C 2 -C 8 ^ 3⁄4 C 2 -C 8 block group, C 2 -C 8 alkenyloxy group, ^3⁄4-3⁄4 alkenyloxy group, 3⁄4-3⁄4 Blockoxy, ^3⁄4 8 oxy, 8 alkylthio, ^-3⁄4 alkane, Ci-C8 3⁄43⁄43, 3⁄4 Ci-Cg 3⁄43⁄43⁄4 \ ί Ci-C8 3⁄43⁄43⁄4,3⁄4 Ci-Cg 3⁄43⁄43⁄4 Ci-Cg 3⁄43⁄43⁄43⁄43⁄4 Ci-Cg 3⁄43⁄43⁄4 代 dC 8 alkylthio dC 8 alkyl, dC 8 alkylsulfinyl, halogenated dC 8 alkylsulfinyl, dC 8 alkylsulfonyl, halogenated dC 8 alkylsulfonyl, a dC 8 alkylamino group, a halogenated dC 8 alkylamino group or a C 2 -C 8 dialkylamino group;
Q选自氢、 卤素、 氰基、 硝基、 羟基、 氨基、 d-C8烷基、 卤代 d-C8烷基、 d-C8烷氧基、 ^代 d-C8烷氧基、 C3-C8环烷基、 C2-C8烯基、 C2-C8块基、 C2-C8烯氧基、 ^代 C2-C8烯氧基、 8块氧基、 卤代 8块氧基、 d-C8浣硫基、 卤代 d-C8烷硫基、 d-C8烷氧基 d-C8烷 基、 1¾代 Ci-Cs院氧基 Ci-Cs院基、 Ci-Cs院硫基 Ci-Cs院基、 1¾代 Ci-Cs院硫基 Ci-Cs院基、 d-C8烷基亚磺酰基、 卤代 d-C8烷基亚磺酰基、 d-C8烷基磺酰基、 卤代 d-C8烷基磺酰基、Q is selected from hydrogen, halo, cyano, nitro, hydroxy, amino, dC 8 alkyl, haloalkyl dC 8 alkyl, dC 8 alkoxy, substituting ^ dC 8 alkoxy, C 3 -C 8 cycloalkyl a group, a C 2 -C 8 alkenyl group, a C 2 -C 8 block group, a C 2 -C 8 alkenyloxy group, a C 2 -C 8 alkenyloxy group, an 8-oxyl group, a halogenated 8- oxyl group, dC 8 thiol, halogenated dC 8 alkylthio, dC 8 alkoxy dC 8 alkyl, 13⁄4 generation Ci-Cs, alkoxy-Ci-Cs, Ci-Cs, thio-Ci-Cs, 13⁄4 generation Ci-Cs Institute thio-Ci-Cs, dC 8 alkylsulfinyl, halogenated dC 8 alkylsulfinyl, dC 8 alkylsulfonyl, halogenated dC 8 alkylsulfonyl,
Ci-Cg ¾¾¾ ¾ \ ί Ci-Cg ¾¾¾ ¾ c2-C8― Ci-Cg \ ί Ci-Cg ¾¾¾ 羰基、 8烷基羰基氧基、 8烷基羰基氨基、 d-c8烷氧基羰基、 8烷基氨基羰基或 选自未取代的或被 1-5个独立选自以下基团进一步取代的苯基、 萘基、 杂芳基、 苯氧 基、 萘氧基、 杂芳氧基： 卤素、 氰基、 硝基、 羟基、 氨基、 巯基、 d-C8烷基、 卤代 8烷 基、 d-C8烷氧基、 ^代 d-C8烷氧基、 C3-C8环烷基、 C2-C8烯基、 ^代 C2-C8烯基、 C2-C8 块基、 ^代 C2-C8块基、 C2-C8烯氧基、 ^代 C2-C8烯氧基、 C2-C8块氧基、 ^代 C2-C8块氧基、 CrC8烷硫基、 卤代 d-C8烷硫基、 d-C8烷氧基 d-C8烷基、 卤代 d-C8烷氧基 d-C8烷基、 d-C8烷硫基 d-C8烷基、 卤代 d-C8烷硫基 d-C8烷基、 d-C8烷基亚磺酰基、 卤代 d-C8烷 基亚磺酰基、 d-C8烷基磺酰基、 ^代 d-C8烷基磺酰基、 d-C8烷基氨基、 ^代 d-C8烷基氨 基或 C2-C8二烷基氨基。 Ci-Cg ¾¾¾ ¾ \ ί Ci -Cg ¾¾¾ ¾ c 2 -C8- Ci-Cg \ ί Ci-Cg ¾¾¾ carbonyl group, alkylcarbonyl group, 8 alkylcarbonylamino, DC 8 alkoxycarbonyl group, an alkoxy 8 a phenylaminocarbonyl group or a phenyl group, a naphthyl group, a heteroaryl group, a phenoxy group, a naphthyloxy group, a heteroaryloxy group selected from the group consisting of unsubstituted or further substituted with 1 to 5 independently selected from the group consisting of halogen, cyanogen group, a nitro group, a hydroxyl group, an amino group, a mercapto group, an alkyl group dC 8, 8 haloalkyl group, an alkoxy group 8 dC, dC ^ substituting 8 alkoxy, C 3 -C 8 cycloalkyl, C 2 -C 8 Alkenyl, ^C 2 -C 8 alkenyl, C 2 -C 8 block, ^C 2 -C 8 block, C 2 -C 8 alkenyl, ^ C 2 -C 8 alkenyloxy , C 2 -C 8 blockoxy, ^ C 2 -C 8 blockoxy, CrC 8 alkylthio, halogenated dC 8 alkylthio, dC 8 alkoxy dC 8 alkyl, halogenated dC 8 alkane Oxy dC 8 alkyl, dC 8 alkylthio dC 8 alkyl, halogenated dC 8 alkylthio dC 8 alkyl, dC 8 alkylsulfinyl, halogenated dC 8 alkylsulfinyl, dC 8 alkane A sulfamoyl group, a dC 8 alkylsulfonyl group, a dC 8 alkylamino group, a dC 8 alkylamino group or a C 2 -C 8 dialkylamino group.
本发明较为优选的技术方案为： 作为农用杀菌剂的吡唑酰胺类化合物为通式 I中 选自 吡啶氧基的化合物， 结构如  A preferred technical solution of the present invention is as follows: The pyrazole amide compound as an agricultural bactericide is a compound selected from the group consisting of pyridyloxy groups in the formula I, and has a structure such as
Figure imgf000005_0001
Figure imgf000005_0001
( I-A )  ( I-A )
式中:  In the formula:
选自氢、 Ci-C6烷基、 ^代 d-C6烷基、 Ci-C6烷氧基 CrC3烷基、氰基 d-C6烷基或 C3-C6 环烷基； Selected from hydrogen, Ci-C 6 alkyl, ^dC 6 alkyl, Ci-C 6 alkoxy C r C 3 alkyl, cyano dC 6 alkyl or C 3 -C 6 cycloalkyl;
R2选自氢、 卤素、氰基、 d-C6烷基、 卤代 d-C6烷基、 d-C6烷氧基、 卤代 CrC6烷氧基、 氰基 d-C6烷基、 氰基 d-C6烷氧基、 未取代的或被 1-5个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 羟基、 氨基、 巯基、 d-C6烷基、 卤代 CrC6烷基、 CrC6烷氧基或 卤代 C C6烷氧基； R 2 is selected from the group consisting of hydrogen, halogen, cyano, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, halo C r C 6 alkoxy, cyano dC 6 alkyl, cyano dC 6 Alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, dC 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy or halo CC 6 alkoxy;
R3选自氢、 卤素、 氰基、 硝基、 d-C6烷基、 卤代 d-C6烷基、 d-C6烷氧基、 卤代 d-C6 烷氧基、 6烷硫基或 crc6烷基磺酰基； R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, dC 6 alkyl, halo dC 6 alkyl, dC 6 alkoxy, halogenated dC 6 Alkoxy, 6 alkylthio or c r c 6 alkylsulfonyl;
、 R5可相同或不同， 分别选自氢、 卤素、 氰基、 硝基、 羟基、 氨基、 CrC6烷基、 卤 代 CrC6烷基、 CrC6烷氧基、 ^代 CrC6烷氧基、 C2-C6烯氧基、 ^代 C2-C6烯氧基、 C2-C6 块氧基、 卤代 C2-C6块氧基、 CrC6烷基亚磺酰基、 卤代 CrC6烷基亚磺酰基、 CrC6烷基磺酰 基、 卤代 CrC6烷基磺酰基、 CrC6烷基氨基、 卤代 CrC6烷基氨基或 C2-C6二烷基氨基； 选自氢、 卤素、氰基、硝基、羟基、氨基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 ¾ 6环烷基、 C2-C6烯基、 C2-C6块基、 ¾ 6烯氧基、 ^代 ¾ 6烯氧基、 C2-C6块氧基、 卤代 C2-C6块氧基、 CrC6浣硫基、 卤代 CrC6烷硫基、 CrC6烷氧基 CrC6烷 、 Ci-C6 Ci-C6 Ci-C6 ¾¾¾¾¾ Ci-C6 \ ί Ci-C6 ¾¾¾¾¾ Ci-C6 CrC6烷基亚磺酰基、 卤代 CrC6烷基亚磺酰基、 CrC6烷基磺酰基、 卤代 CrC6烷基磺酰基、 CrC6烷基氨基、 卤代 CrC6烷基氨基或 C2-C6二烷基氨基； n选自 0至 4的整数； 当 n大于 1 时， 可相同或不同； And R 5 may be the same or different and are respectively selected from the group consisting of hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, ^ Generation C r C 6 alkoxy, C 2 -C 6 alkenyloxy, ^ C 2 -C 6 alkenyloxy, C 2 -C 6 -oxyl, halo C 2 -C 6 -oxyl, C r C 6 alkylsulfinyl, halogenated C r C 6 alkylsulfinyl, C r C 6 alkylsulfonyl, halogenated C r C 6 alkylsulfonyl, C r C 6 alkylamino, halogen Generation C r C 6 alkylamino or C 2 -C 6 dialkylamino; is selected from hydrogen, halo, cyano, nitro, hydroxy, amino, C r C 6 alkyl, halo C r C 6 alkyl , C r C 6 alkoxy, halo C r C 6 alkoxy, 3⁄4 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 block, 3⁄4 6 alkenyl, ^ 3⁄4 6 -alkenyloxy, C 2 -C 6 -blockoxy, halogenated C 2 -C 6 -oxyl, C r C 6 thiol, halogenated C r C 6 alkylthio, C r C 6 alkoxy C r C 6 alkane, Ci-C 6 Ci-C 6 Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6 \ ί Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6 C r C 6 alkylsulfinyl, halogenated C r C 6 alkylsulfinyl, C r C 6 alkylsulfonyl group, a halogen C r C 6 alkylsulfonyl, C r C 6 alkylamino, halo C r C 6 alkylamino or C 2 -C 6 dialkylamino group; n is selected from an integer from 0 to 4; when n is greater than 1 When they are the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
本发明进一步优选的技术方案为， 作为农用杀菌剂的通式 (I-A)所示的吡唑酰胺类化合物 中：  A further preferred embodiment of the present invention is a pyrazole amide compound represented by the formula (I-A) as an agricultural bactericide:
选自氢、 C C6烷基、 ^代 CrC6烷基、 d-C6烷氧基 CrC3烷基、氰基 CrC6烷基或 C3-C6 环烷基； Is selected from hydrogen, CC 6 alkyl, C r C 6 substituting ^ alkyl, dC 6 alkoxy C r C 3 alkyl, cyano C r C 6 alkyl or C 3 -C 6 cycloalkyl;
R2选自氢、 卤素、氰基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 氰基 6烷基、 氰基 6烷氧基、 未取代的或被 1-5个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 羟基、 氨基、 巯基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基或 卤代 6烷氧基； R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, cyano 6 alkyl , cyano 6 alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, C r C 6 alkyl, Halogenated C r C 6 alkyl, C r C 6 alkoxy or halo 6 alkoxy;
R3选自氢、 卤素、 氰基、 硝基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6 烷氧基、 6烷硫基或 crc6烷基磺酰基； R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, 6 alkane Thio or c r c 6 alkylsulfonyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 卤素、氰基、硝基、羟基、氨基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 ¾ 6环烷基、 C2-C6烯基、 C2-C6块基、 ¾ 6烯氧基、 ^代 ¾ 6烯氧基、 C2-C6块氧基、 卤代 C2-C6块氧基、 CrC6浣硫基、 卤代 CrC6烷硫基、 CrC6烷氧基 CrC6烷 、 Ci-C6 Ci-C6 Ci-C6 ¾¾¾¾¾ Ci-C6 \ ί Ci-C6 ¾¾¾¾¾ Ci-C6 Selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, 3⁄4 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 block, 3⁄6 6 alkenyloxy, ^ 3 6 unalkenyloxy, C 2 -C 6 -oxyl, halogenated C 2 - C 6 -oxyl group, C r C 6 thiol group, halogenated C r C 6 alkylthio group, C r C 6 alkoxy C r C 6 alkane, Ci-C 6 Ci-C 6 Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6 \ ί Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6
CrC6烷基亚磺酰基、 卤代 crc6烷基亚磺酰基、 crc6烷基磺酰基、 卤代 crc6烷基磺酰基、 d-C6烷基氨基、 卤代 CrC6烷基氨基或 C2-C6二烷基氨基； n选自 0至 4的整数； 当 n大于 1 时， 可相同或不同； C r C 6 alkylsulfinyl, halo c r c 6 alkylsulfinyl, c r c 6 alkylsulfonyl, halo c r c 6 alkylsulfonyl, dC 6 alkylamino, halogenated C r C 6 alkylamino or C 2 -C 6 dialkylamino; n is selected from an integer from 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
本发明更进一步优选的技术方案为， 作为农用杀菌剂的通式 (I-A)所示的吡唑酰胺类化合 物中：  A still further preferred embodiment of the present invention is a pyrazole amide compound represented by the formula (I-A) as an agricultural bactericide:
选自氢、 CrC4烷基或 C3-C6环烷基； Selected from hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl;
R2选自氢、 卤素、氰基、 CrC4烷基、 卤代 CrC4烷基、 4烷氧基、 卤代 ^ 4烷氧基、 氰基 d-C3烷基、 氰基 -¾烷氧基、 未取代的或被 1-3个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 4烷氧基； R3选自氢、 卤素、 氰基、 硝基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 CrC4 烷氧基； R 2 is selected from hydrogen, halo, cyano, C r C 4 alkyl, C r C 4 halogenated alkyl, alkoxy, halo ^ 4 alkoxy, cyano dC 3 alkyl, cyano - 3⁄4 alkoxy, unsubstituted or substituted by 1 to 3 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halo 4 alkoxy; R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkane Oxy or halogenated C r C 4 alkoxy;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 卤素、 氰基、 硝基、 羟基、 氨基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基 或卤代 4烷氧基； n选自 0至 4的整数； 当 n大于 1时， 可相同或不同； Selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halo 4 alkoxy; n selected from An integer from 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
再进一步优选的技术方案为， 作为农用杀菌剂的通式 (I-A)所示的吡唑酰胺类化合物中： 选自氢、 甲基、 乙基、 环丙基或环己基； A still further preferred embodiment is the pyrazole amide compound represented by the general formula (IA) as an agricultural bactericide: Selected from hydrogen, methyl, ethyl, cyclopropyl or cyclohexyl;
R2选自氢、 氯、 溴、 甲基、 乙基、 氯甲基、 二氟甲基、 三氟甲基、 甲氧基甲基、 甲氧基、 乙氧基、 一氟甲氧基、 三氟甲氧基、 三氟乙氧基、 氰基甲基、 氰基甲氧基、 苯基、 对氯苯基、 对氟苯基、 对甲基苯基、 对三氟甲基苯基、 对甲氧基苯基、 对三氟甲氧基苯基、 2，4-二氯苯基 或 2，4-二甲基苯基； R 2 is selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, chloromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, monofluoromethoxy, Trifluoromethoxy, trifluoroethoxy, cyanomethyl, cyanomethoxy, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, P-methoxyphenyl, p-trifluoromethoxyphenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl;
R3选自氢、 氯、 溴或甲基； R 3 is selected from the group consisting of hydrogen, chlorine, bromine or methyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 氟、 氯、 溴、 碘、 氰基、 硝基、 羟基、 氨基、 甲基、 乙基、 正丙基、 异丙基、 正丁基、 异丁基、 仲丁基、 叔丁基、 三氟甲基、 二氟一氯甲基、 甲氧基、 乙氧基或三氟甲氧 基； n选自 0至 4的整数； 当 n大于 1时， 可相同或不同；  Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl a group, a trifluoromethyl group, a difluoro-chloromethyl group, a methoxy group, an ethoxy group or a trifluoromethoxy group; n is selected from an integer of 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
上述吡唑酰胺类化合物中作为农用杀菌剂的用途时再进一步优选的化合物为： 通式 (I-A) 中  Further preferred compounds for use as an agricultural fungicide in the above pyrazole amide compounds are: in the formula (I-A)
选自甲基、 乙基或环丙基；  Selected from methyl, ethyl or cyclopropyl;
R2选自甲基、 乙基、 苯基、 对氯苯基、 对氟苯基、 对甲基苯基、 对三氟甲基苯基、 对甲 氧基苯基、 对三氟甲氧基苯基、 2，4-二氯苯基或 2，4-二甲基苯基； R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-trifluoromethoxy Phenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl;
R3选自氢、 氯或甲基； R 3 is selected from the group consisting of hydrogen, chlorine or methyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 氯、 溴、 甲基、 氰基、 三氟甲基、 二氟一氯甲基、 甲氧基、 乙氧基或三氟甲 氧基； n选自 0至 4的整数； 当 n大于 1时， 可相同或不同；  Selected from hydrogen, chlorine, bromine, methyl, cyano, trifluoromethyl, difluoromonochloromethyl, methoxy, ethoxy or trifluoromethoxy; n is selected from an integer from 0 to 4; When n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-或 -CH2CH2CH2-。 A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
本发明最优选的技术方案为， 通式 (I-A)中：  The most preferred technical solution of the present invention is, in the formula (I-A):
选自甲基；  Selected from methyl;
R2选自甲基、 乙基、 苯基、 对氯苯基或对氟苯基； R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl or p-fluorophenyl;
R3选自氢、 氯或甲基； R 3 is selected from the group consisting of hydrogen, chlorine or methyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氯、 三氟甲基或二氟一氯甲基； n选自 1至 3的整数；  Selected from chlorine, trifluoromethyl or difluoromonochloromethyl; n is selected from the integers from 1 to 3;
A选自 -CH2-、 -CH2CH2-或 -CH2CH2CH2-。 A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
上面给出的化合物 (I)的定义中， 汇集所用术语一般代表如下取代基：  In the definition of the compound (I) given above, the terms used in the collection generally represent the following substituents:
卤素： 指氟、 氯、 溴或碘。 烷基： 直链或支链烷基， 例如甲基、 乙基、 丙基、 异丙基、 正丁基或叔丁基。 环烷基： 取代或未取代的环状烷基， 例如环丙基、 环戊基或环己基。 取代 基如甲基、 卤素等。 卤代烷基： 直链或支链烷基， 在这些烷基上的氢原子可部分或全部被卤 原子所取代， 例如， 氯甲基、 二氯甲基、 三氯甲基、 氟甲基、 二氟甲基、 三氟甲基等。 烷氧 基： 直链或支链烷基， 经氧原子键连接到结构上。 烷氧基烷基： 烷氧基经烷基连接到结构上。 如 CH3OCH2-， CH3CH2OCH2-。 卤代烷氧基烷基： 烷氧基烷基的烷基上的氢原子可部分或全 部被卤原子所取代。 如 ClCH2CH2OCH2-。 卤代烷氧基： 直链或支链烷氧基， 在这些烷氧基上 的氢原子可部分或全部被卤原子所取代。 例如， 氯甲氧基、 二氯甲氧基、 三氯甲氧基、 氟甲 氧基、 二氟甲氧基、 三氟甲氧基、 氯氟甲氧基、 三氟乙氧基等。 烷硫基： 直链或支链烷基， 经硫原子键连接到结构上。 烷硫基烷基： 烷硫基经烷基连接到结构上。 如 CH3SCH2-。 卤代烷 硫基： 直链或支链烷硫基， 在这些烷基上的氢原子可部分或全部被卤原子所取代。 例如， 氯 甲硫基、 二氯甲硫基、 三氯甲硫基、 氟甲硫基、 二氟甲硫基、 三氟甲硫基、 氯氟甲硫基等。 卤代烷硫基烷基： 卤代烷硫基经烷基连接到结构上， 如 ClCH2SCH2-。 烷基氨基： 直链或支链 烷基， 经氮原子键连接到结构上。 卤代烷基氨基： 直链或支链烷基氨基， 在这些烷基上的氢 原子可部分或全部被卤原子所取代。 烯基： 直链或支链烯类， 例如乙烯基、 1-丙烯基、 2-丙 烯基和不同的丁烯基、 戊烯基和己烯基异构体。 烯基还包括多烯类， 如 1，2-丙二烯基和 2，4-己 二烯基。 卤代烯基： 直链或支链烯类， 在这些烯基上的氢原子可部分或全部被卤原子所取代。 块基： 直链或支链块类， 例如乙块基、 1-丙块基、 2-丙块基和不同的丁块基、 戊块基和己块 基异构体。块基还包括由多个三键组成的基团，如 2，5-己二块基。卤代块基： 直链或支链块类， 在这些块基上的氢原子可部分或全部被卤原子所取代。 烯氧基： 直链或支链烯类， 经氧原子 键连接到结构上。 卤代烯氧基： 直链或支链烯氧基， 在这些烯氧基上的氢原子可部分或全部 被卤原子所取代。 块氧基： 直链或支链块类， 经氧原子键连接到结构上。 卤代块氧基： 直链 或支链块氧基， 在这些块氧基上的氢原子可部分或全部被卤原子所取代。 烷基亚磺酰基： 直 链或支链烷基经亚磺酰基 （-SO-) 连接到结构上， 如甲基亚磺酰基。 卤代烷基亚磺酰基： 直 链或支链烷基亚磺酰基， 其烷基上的氢原子可部分或全部被卤原子所取代。 烷基磺酰基： 直 链或支链烷基经磺酰基 （-so2-) 连接到结构上， 如甲基磺酰基。 卤代烷基磺酰基： 直链或支 链烷基磺酰基， 其烷基上的氢原子可部分或全部被卤原子所取代。 烷基羰基： 烷基经羰基连 接到结构上， 如 CH3CO-， CH3CH2CO-。 卤代烷基羰基： 烷基羰基的烷基上的氢原子可部分或 全部被卤原子所取代， 如 CF3CO-。 烷基氨基羰基： 如 CH3NHCO-， CH3CH2NHCO-。 烷氧基 羰基：烷氧基经羰基连接到结构上。如 CH3OCO-， CH3CH2OCO 烷基羰基氧基：如 CH3COO-， CH3CH2NHCOO-。 烷基羰基氨基： 如 CH3CONH-， CH3CH2NHCONH -。 杂芳基： 本发明中所 指杂芳基是含 1个或多 N、 O、 s杂原子的五元环或六元环芳基。 例如吡啶基、 嘧啶基、 吡嗪基、 哒嗪基、 三嗪基、 呋喃基、 噻唑基、 喹啉基、 异噻唑基、 恶唑基、 异恶唑基、 恶二唑基、 噻 二唑基、 吡唑基、 吡喃基、 三唑基、 四唑基、 苯并噻唑基、 苯并呋喃基等。 杂芳氧基： 将杂 芳环经氧连接到结构上， 如吡啶氧基、 嘧啶氧基等。 Halogen: Refers to fluorine, chlorine, bromine or iodine. Alkyl: a linear or branched alkyl group such as methyl, ethyl, propyl, isopropyl, n-butyl or t-butyl. Cycloalkyl: a substituted or unsubstituted cyclic alkyl group such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen and the like. Haloalkyl: a straight or branched alkyl group in which a hydrogen atom may be partially or completely substituted by a halogen atom, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, Fluoromethyl, trifluoromethyl, and the like. Alkoxy: A linear or branched alkyl group bonded to a structure via an oxygen atom. Alkoxyalkyl: Alkoxy is attached to the structure via an alkyl group. For example, CH 3 OCH 2 -, CH 3 CH 2 OCH 2 -. Haloalkoxyalkyl group: The hydrogen atom on the alkyl group of the alkoxyalkyl group may be partially or completely substituted by a halogen atom. Such as ClCH 2 CH 2 OCH 2 -. Haloalkoxy: a linear or branched alkoxy group, and a hydrogen atom on these alkoxy groups may be partially or completely substituted by a halogen atom. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, and the like. Alkylthio: a linear or branched alkyl group bonded to a structure via a sulfur atom bond. Alkylthioalkyl: An alkylthio group is attached to the structure via an alkyl group. Such as CH 3 SCH 2 -. Haloalkylthio: a linear or branched alkylthio group in which a hydrogen atom may be partially or completely substituted by a halogen atom. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like. Haloalkylthioalkyl: A haloalkylthio group is attached to the structure via an alkyl group, such as ClCH 2 SCH 2 -. Alkylamino: a linear or branched alkyl group bonded to the structure via a nitrogen atom. Haloalkylamino group: a linear or branched alkylamino group in which a hydrogen atom may be partially or completely substituted by a halogen atom. Alkenyl: a linear or branched olefin such as a vinyl group, a 1-propenyl group, a 2-propenyl group and a different butenyl, pentenyl group and hexenyl isomer. Alkenyl groups also include polyenes such as 1,2-propadienyl and 2,4-hexyl Dienyl. Haloalkenyl group: a linear or branched olefin in which a hydrogen atom on these alkenyl groups may be partially or completely substituted by a halogen atom. Block base: A linear or branched block type, such as an ethyl group, a 1-propyl block, a 2-propyl block, and different butyr, pentyl and hexyl isomers. The block group also includes a group consisting of a plurality of triple bonds, such as a 2,5-hexane block. Halogenated block: A linear or branched block, in which a hydrogen atom may be partially or completely replaced by a halogen atom. Alkenyloxy: A linear or branched olefin that is bonded to the structure via an oxygen atom. Haloalkenyloxy: a linear or branched alkenyloxy group, and a hydrogen atom on these alkenyloxy groups may be partially or completely substituted by a halogen atom. Block Oxygen: A linear or branched block that is attached to a structure via an oxygen atom. Halo blockoxy: a linear or branched blockoxy group, and a hydrogen atom on these blockoxy groups may be partially or completely substituted by a halogen atom. Alkylsulfinyl: A straight or branched alkyl group is attached to the structure via a sulfinyl group (-SO-), such as a methylsulfinyl group. Haloalkylsulfinyl: a linear or branched alkylsulfinyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom. Alkylsulfonyl: A straight or branched alkyl group is attached to the structure via a sulfonyl group (-so 2 -), such as a methylsulfonyl group. Haloalkylsulfonyl: a linear or branched alkylsulfonyl group in which a hydrogen atom on the alkyl group may be partially or completely substituted by a halogen atom. Alkylcarbonyl: An alkyl group is attached to the structure via a carbonyl group, such as CH 3 CO-, CH 3 CH 2 CO-. Haloalkylcarbonyl: The hydrogen atom on the alkyl group of the alkylcarbonyl group may be partially or completely substituted by a halogen atom such as CF 3 CO-. Alkylaminocarbonyl: such as CH 3 NHCO-, CH 3 CH 2 NHCO-. Alkoxycarbonyl: alkoxy is attached to the structure via a carbonyl group. For example, CH 3 OCO-, CH 3 CH 2 OCO alkylcarbonyloxy: such as CH 3 COO-, CH 3 CH 2 NHCOO-. Alkylcarbonylamino: such as CH 3 CONH-, CH 3 CH 2 NHCONH -. Heteroaryl: The heteroaryl group referred to in the present invention is a five-membered or six-membered ring aryl group containing one or more N, O, s hetero atoms. For example, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, furyl, thiazolyl, quinolinyl, isothiazolyl, oxazolyl, isoxazolyl, oxadiazolyl, thiadiazole Base, pyrazolyl, pyranyl, triazolyl, tetrazolyl, benzothiazolyl, benzofuranyl and the like. Heteroaryloxy: A heteroaryl ring is attached to the structure via an oxygen group, such as a pyridyloxy group, a pyrimidinyloxy group or the like.
通式 (I)化合物大多是已知的， 可以按照已知制备方法获得所需要的目的产物。 对于首次 公开的化合物， 本发明通式 (I)所示的化合物的制备方法如下：  Most of the compounds of the formula (I) are known, and the desired product of the desired product can be obtained according to known methods. For the first disclosed compound, the preparation of the compound of the formula (I) of the present invention is as follows:
当 Q不为未取代或取代的苯氧基、萘氧基或杂芳氧基时，制备方法可参照文献 Synthesis Communications (合成通讯)， 11卷， 第 513页 （1981 ) 制备。  When Q is not an unsubstituted or substituted phenoxy, naphthyloxy or heteroaryloxy group, the preparation can be carried out by referring to the literature Synthesis Communications, Vol. 11, p. 513 (1981).
当 Q为未取代或取代的苯氧基、 萘氧基或杂芳氧基时， 制备方法分为以下三种情况（以 Q为吡啶氧基为例， 即本发明优选的通式 (I-A)所示的化合物的制备）：  When Q is an unsubstituted or substituted phenoxy, naphthyloxy or heteroaryloxy group, the preparation method is divided into the following three cases (taking Q as a pyridyloxy group, that is, a preferred formula (IA) of the present invention Preparation of the compounds shown):
第一 -CH2 -时， 制备方法如下面反应路线所示： When the first -CH 2 -, the preparation method is as shown in the following reaction scheme:
Figure imgf000008_0001
式中， L是离去基团， 为卤素、 甲基磺酸酯或对甲苯磺酸酯。 其他各基团定义同前。 在适当的溶剂中、 适当的碱存在下， 通式 (VI-1)与 (V)反应， 处理即得 (IV-1)。 具体制备可 以参照精细化工， 2005,22(12): 944-960中描述的方法进行。 反应通常在室温至溶剂沸点温度 范围内进行， 较适宜的反应温度为 20〜100°C。 反应时间为 30分钟至 20小时， 通常 1〜10小 时。 适当的溶剂可选自如丙酮、 丁酮、 四氢呋喃、 乙腈、 甲苯、 二甲苯、 苯、 N，N-二甲基甲 酰胺、 二甲亚砜、 甲醇或乙醇等。 适当的碱可选自如氢氧化钾、 氢氧化钠、 碳酸钠、 碳酸钾、 碳酸氢钠、 三乙胺、 吡啶或氢化钠等。
Figure imgf000008_0001
Wherein L is a leaving group and is a halogen, a methanesulfonate or a p-toluenesulfonate. The other groups are defined as before. The compound of the formula (VI-1) and (V) are reacted in a suitable solvent in the presence of a suitable base to give (IV-1). The specific preparation can be carried out by referring to the method described in Fine Chemicals, 2005, 22(12): 944-960. The reaction is usually carried out at a temperature ranging from room temperature to the boiling point of the solvent, and a suitable reaction temperature is 20 to 100 °C. The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours. Suitable solvents may be selected from, for example, acetone, butanone, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide, dimethyl sulfoxide, methanol or ethanol, and the like. Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine or sodium hydride, and the like.
在适当的溶剂中， （IV-1)在适当的催化剂和氨水存在下经加氢还原得到 (11-1)。 具体制备 可以参照文献 J.Am.Chem.Soc，70，3788(1948); 82,681(1960); 82,2386(1960)； Can.J.Chem , 49,2990 ( 1971 ); J.Org. Chem, 37,335(1972)； Organic Syntheses, Coll. Vol. 3, p.229 p.720 (1955)， Vol. 23, p.71 (1943)或 Vol. 27， p.18 (1947)中描述的方法进行。反应通常在室温至溶剂沸点温度 范围内进行， 较适宜的反应温度为 20〜100°C。 反应时间为 30分钟至 20小时， 通常 1〜10小 时。 适宜的溶剂可选自甲醇、 乙醇、 异丙醇、 苯、 甲苯、 二甲苯、 丙酮、 甲乙酮、 甲基异丁 酮、 氯仿、 二氯甲烷、 乙酸甲酯、 乙酸乙酯、 四氢呋喃、 二噁烷、 N，N-二甲基甲酰胺、 N-甲 基吡咯烷酮或二甲亚砜等。 适宜的催化剂可选自雷尼镍、 钯碳或氧化铂等。 (IV-1) is hydroreduced in the presence of a suitable catalyst and aqueous ammonia in a suitable solvent to give (11-1). Specific preparation Reference may be made to the literature J. Am. Chem. Soc, 70, 3788 (1948); 82, 681 (1960); 82, 2386 (1960); Can. J. Chem, 49, 2990 (1971); J. Org. Chem, 37, 335 (1972); Organic Syntheses, Coll. Vol. 3, p. 229, p. 720 (1955), Vol. 23, p. 71 (1943) or Vol. 27, p. 18 (1947). The reaction is usually carried out at a temperature ranging from room temperature to the boiling point of the solvent, and a suitable reaction temperature is 20 to 100 °C. The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours. Suitable solvents may be selected from the group consisting of methanol, ethanol, isopropanol, benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, chloroform, dichloromethane, methyl acetate, ethyl acetate, tetrahydrofuran, dioxane. , N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide. Suitable catalysts may be selected from the group consisting of Raney nickel, palladium carbon or platinum oxide.
通式 (I-A-1)所代表的化合物可以由通式 (II-1)所示的胺与通式 (III)所示的吡唑甲酰氯在适 宜的溶剂中， 适当的碱存在下 （也可不用碱） 縮合制得。 具体制备方法参照 EP0365925A1、 US5264448A。适宜的溶剂可选自苯、 甲苯、 二甲苯、 丙酮、 甲乙酮、 甲基异丁酮、 四氢呋喃、 乙腈、 二噁烷、 N，N-二甲基甲酰胺、 N-甲基吡咯烷酮、 二甲亚砜、 吡啶、 二氯甲烷、 氯仿、 二氯乙烷、 乙酸甲酯或乙酸乙酯等。 适当的碱可选自如氢氧化钾、 氢氧化钠、 碳酸钠、 碳酸 钾、 碳酸氢钠、 三乙胺、 吡啶或氢化钠等。 反应温度可在室温至溶剂沸点温度之间， 通常为 20〜100°C。 反应时间为 30分钟至 20小时， 通常 1〜10小时。  The compound represented by the formula (IA-1) may be an amine represented by the formula (II-1) and a pyrazolecarbonyl chloride represented by the formula (III) in a suitable solvent in the presence of a suitable base (also Can be obtained without condensation. For specific preparation methods, refer to EP0365925A1, US5264448A. Suitable solvents may be selected from the group consisting of benzene, toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone, dimethylene. Sulfone, pyridine, dichloromethane, chloroform, dichloroethane, methyl acetate or ethyl acetate. Suitable bases may be selected from, for example, potassium hydroxide, sodium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogencarbonate, triethylamine, pyridine or sodium hydride, and the like. The reaction temperature may be between room temperature and the boiling point of the solvent, and is usually from 20 to 100 °C. The reaction time is from 30 minutes to 20 hours, usually from 1 to 10 hours.
第二种情况， 当 A-CH2CH2-或 -CH2CH2CH2-时， 制备方法如下面反应路线所示： In the second case, when A-CH 2 CH 2 - or -CH 2 CH 2 CH 2 -, the preparation method is as shown in the following reaction scheme:
Figure imgf000009_0001
Figure imgf000009_0001
式中， A为比 A少一个碳原子的对应结构。 其他各基团定义同前。  In the formula, A is a corresponding structure having one carbon atom less than A. The other groups are defined as before.
由 （VI-2) 和 （V) 反应， 经中间体 （IV-2)、 (II-2) 制得 （I-A-2) 的反应条件及溶剂、 碱和金属催化剂的选择均同于第一种情况中由（VI-1 )和（V)反应，经中间体（IV-1 )、 (II-1 ) 制得 (I-A-1 ) 的相应步骤。  The reaction conditions obtained by the reaction of (VI-2) and (V), the intermediate (IV-2) and (II-2) (IA-2) and the choice of solvent, base and metal catalyst are the same as the first In the case of (VI-1) and (V), the corresponding steps of (IA-1) are obtained via intermediates (IV-1) and (II-1).
第三种情况， 当 A为 -CH(CH3)-、 -C(CH3)2-、 -C(CN)(CH3)-、 -CH(CN)-或 -C(CH2CH3)(CH3)- 时， ： In the third case, when A is -CH(CH 3 )-, -C(CH 3 ) 2 -, -C(CN)(CH 3 )-, -CH(CN)- or -C(CH 2 CH 3 )(CH 3 )-, :
Figure imgf000009_0002
Figure imgf000009_0002
式中， Boc20指二碳酸二叔丁酯。 其他各基团定义同前。 In the formula, Boc 2 0 refers to di-tert-butyl dicarbonate. The other groups are defined as before.
首先，在适宜的溶剂中、适宜碱的存在下，二碳酸二叔丁酯与相应的氨基苯酚于 0〜100°C 反应， 首先制得 Boc保护的氨基苯酚 （VII )。 反应温度优选 0〜50°C ; 反应时间为 30分钟至 20小时， 优选 0.5〜10小时。适宜的溶剂选自苯、 甲苯、 二甲苯、氯仿、 二氯甲烷、 四氢呋喃、 乙腈、 二噁烷、 N，N-二甲基甲酰胺、 N-甲基吡咯烷酮或二甲亚砜等； 适宜的碱选自碱金属碳 酸盐例如碳酸钠、 碳酸氢钠、 碳酸钾或碳酸氢钾。 First, the di-tert-butyl dicarbonate is reacted with the corresponding aminophenol at 0 to 100 ° C in a suitable solvent in the presence of a suitable base to first obtain a Boc-protected aminophenol (VII). The reaction temperature is preferably 0 to 50 ° C; the reaction time is 30 minutes to 20 hours, preferably 0.5 to 10 hours. Suitable solvents are selected from the group consisting of benzene, toluene, xylene, chloroform, dichloromethane, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; The base is selected from alkali metal carbonates such as sodium carbonate, sodium hydrogencarbonate, potassium carbonate or potassium hydrogencarbonate.
然后， 将 （VII ) 与 （V) 在适宜的溶剂中、 适宜碱的存在下， 于 0〜100°C縮合反应得到 ( VIIl ) o反应时间 30分钟至 20小时， 优选 0.5〜10小时。适宜的溶剂选自苯、 甲苯、二甲苯、 氯仿、 二氯甲烷、 丙酮、 丁酮、 四氢呋喃、 乙腈、 二噁烷、 N，N-二甲基甲酰胺、 N-甲基吡咯 烷酮或二甲亚砜等； 适宜的碱选自金属氢化物例如氢化钠， 碱金属氢氧化物例如氢氧化钠或 氢氧化钾， 碱金属碳酸盐例如碳酸钠或碳酸钾， 有机胺类例如吡啶或三乙胺。  Then, (VII) and (V) are condensed in a suitable solvent in the presence of a suitable base at 0 to 100 ° C to obtain a (VII1) o reaction time of 30 minutes to 20 hours, preferably 0.5 to 10 hours. Suitable solvents are selected from the group consisting of benzene, toluene, xylene, chloroform, dichloromethane, acetone, butanone, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethylene. Sulfone or the like; a suitable base is selected from metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide, alkali metal carbonates such as sodium carbonate or potassium carbonate, and organic amines such as pyridine or triethylamine. .
( VIII ) 在适宜的溶剂中， 经适宜的酸脱保护得相应的盐， 再碱化得 （11-3)。 反应温度 优选 0〜50°C ; 反应时间为 30分钟至 20小时， 优选 0.5〜10小时。 适宜的溶剂选自乙酸乙酯、 乙酸甲酯、 甲酸甲酯、 苯、 甲苯、 二甲苯、 氯仿、 二氯甲烷、 水、 四氢呋喃、 乙腈、 二噁烷、 N，N-二甲基甲酰胺、 N-甲基吡咯烷酮或二甲亚砜等； 适宜的酸选自盐酸、 三氟乙酸、 硫酸、 乙酸、 丙酸、 丁酸、 草酸、 己二酸、 十二烷二酸、 月桂酸、 硬脂酸、 富马酸、 马来酸、 苯甲 酸或苯二甲酸等； 所述的碱选自金属氢化物例如氢化钠， 碱金属氢氧化物例如氢氧化钠或氢 氧化钾，； 碱金属碳酸盐例如碳酸钠或碳酸钾， u u u u u u 具体制备方法参 见 WO2004093800A。  (VIII) The corresponding salt is deprotected by a suitable acid in a suitable solvent and then basified to give (11-3). The reaction temperature is preferably 0 to 50 ° C; and the reaction time is 30 minutes to 20 hours, preferably 0.5 to 10 hours. Suitable solvents are selected from the group consisting of ethyl acetate, methyl acetate, methyl formate, benzene, toluene, xylene, chloroform, dichloromethane, water, tetrahydrofuran, acetonitrile, dioxane, N,N-dimethylformamide, N-methylpyrrolidone or dimethyl sulfoxide; etc.; suitable acids are selected from the group consisting of hydrochloric acid, trifluoroacetic acid, sulfuric acid, acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, and stearic acid. Acid, fumaric acid, maleic acid, benzoic acid or phthalic acid, etc.; the base is selected from the group consisting of metal hydrides such as sodium hydride, alkali metal hydroxides such as sodium hydroxide or potassium hydroxide; alkali metal carbonate For a specific preparation method of a salt such as sodium carbonate or potassium carbonate, uuuuuu is described in WO2004093800A.
通式 (I-A-3)所代表的化合物可以由通式 (Π-3)所示的胺与通式 (III)所示的吡唑甲酰氯在 适宜的溶剂中， 适当的碱存在下 （也可不用碱） 縮合制得。 反应条件及溶剂、 碱的选择均同 于第一种情况中由 (Π-1 ) 和 (III ) 反应制得 (I-A-l ) o  The compound represented by the formula (IA-3) may be an amine represented by the formula (Π-3) and a pyrazolecarbonyl chloride represented by the formula (III) in a suitable solvent in the presence of a suitable base (also Can be obtained without condensation. The reaction conditions and the choice of solvent and base are the same as those obtained by the reaction of (Π-1) and (III) in the first case (I-A-l) o
上述通式 （I ) 化合物的制备方法中所涉及的原料来源如下： 通式 (VI-1)、 (VI-2) 和 (V) 所示的化合物均有市售， （VI-3)所示的化合物或有市售或按照已知文献如 JP61024550、 US4843160、 US4746754、 US2396580、 JP02017164、 Afmidad, 42(397)， 270-2; 1985等报道的 方法制备。通式 (III)化合物可市购，也可以按照已知文献如 Annalen der Chemie Justus Liebig's, 536,97 ( 1938 ) Bull.Soc.Chim.France,293(1966) US4950668 JP2292263 JP2053776 JP4069361 或 JP4069379等报道的方法制备。  The raw materials involved in the preparation method of the above compound of the general formula (I) are as follows: The compounds represented by the general formulae (VI-1), (VI-2) and (V) are commercially available, (VI-3) The compounds shown are either commercially available or prepared according to known methods such as those reported in JP61024550, US4843160, US4746754, US2396580, JP02017164, Afmidad, 42(397), 270-2; 1985, and the like. The compound of the formula (III) is commercially available or can be reported according to known literature such as Annalen der Chemie Justus Liebig's, 536, 97 (1938) Bull. Soc. Chim. France, 293 (1966) US 4950668 JP 2292263 JP 2053776 JP4069361 or JP 4069379. Method preparation.
可以用下面表 1至表 3中列出的化合物来说明本发明， 但并不限定本发明。  The present invention can be illustrated by the compounds listed in Tables 1 to 3 below, but does not limit the present invention.
Figure imgf000010_0001
Figure imgf000010_0001
Figure imgf000010_0002
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Figure imgf000011_0001
Figure imgf000011_0001
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Figure imgf000012_0001
Figure imgf000012_0001
Π Π
Figure imgf000013_0001
Figure imgf000013_0001
Figure imgf000014_0001
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Figure imgf000014_0001
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Figure imgf000015_0001
Figure imgf000015_0001
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Figure imgf000016_0001
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Figure imgf000017_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000018_0001
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Figure imgf000019_0001
Figure imgf000019_0001
U u U U U u U U
U U U U U U U U
U U U U U U U UU U U U U U U U
U U U UU U U U
U U U UU U U U
U U U U U U U U U U U U U U U U U U U U U U U U
o o o o U U U U U U o o o o U U U U U U
o o ( ( u u ( ( u u  o o ( ( u u ( u u u
( ( u u ( ( u u u  ( ( u u ( u u u u
u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u w u ω u w u w u w u w u w u w u w u w u w u w u w u w u w u w u w u w u w u w u w  u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u
ω w w ω u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u o o o o o o < o o ω w w ω u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u u o o o o o o < o
O O o o o o o o o o o o < < ( OO oooooooooo << (
Figure imgf000021_0001
Figure imgf000021_0001
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Figure imgf000022_0001
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Figure imgf000023_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000024_0001
Figure imgf000024_0002
Figure imgf000025_0001
Figure imgf000025_0001
898C80/ZT0ZN3/X3d 6.0l790/Cl0Z OAV
Figure imgf000026_0001
1021 CH3 Et CI H H 、„N 898C80/ZT0ZN3/X3d 6.0l790/Cl0Z OAV
Figure imgf000026_0001
1021 CH 3 Et CI HH, „N
\=J  \=J
1022 CH3 Et CI H H 1022 CH 3 Et CI HH
1023 CH3 CH3 H H H 1023 CH 3 CH 3 HHH
1024 CH3 Et CI -CH2- OCH3 H 0CH31024 CH 3 Et CI -CH 2 - OCH 3 H 0CH3
1025 CH3 CH3 CI -CH2- H H 0CF31025 CH 3 CH 3 CI -CH 2 - HH 0CF3
1026 CH3 CH3 CI -CH2- H H 0(CH2)4CH3 1026 CH 3 CH 3 CI -CH 2 - HH 0(CH 2 ) 4 CH 3
1027 CH3 Et CI H H 0(CH2)4CH3 1027 CH 3 Et CI HH 0(CH 2 ) 4 CH 3
1028 CH3 CH3 CI H H OEt1028 CH 3 CH 3 CI HH OEt
1029 CH3 Et CI -CH(CH3) - H H 0(CH2)7CH3 表 3 通式 （I-A u) 另一部分化合物 u u u u u u u u u u u u u u
Figure imgf000027_0001
1029 CH 3 Et CI -CH(CH 3 ) - HH 0(CH 2 ) 7 CH 3 Table 3 General formula (IA u) Another part of the compound uuuuuuuuuuuuuu
Figure imgf000027_0001
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Figure imgf000029_0001
Figure imgf000029_0001
由于本发明首次发现了如通式（I )所示的吡唑酰胺类化合物具有优异的杀菌活性， 因此 可以将该类化合物应用于防治农业、 园艺和花卉栽培等农用领域中各种作物上的病害， 特别 适合于防治下列植物病害： 黄瓜霜霉病、 玉米锈病等。 本发明的化合物可防治的植物病菌不 限于上述内容。 因此， 本发明的技术方案包括了通式 （I )所示的吡唑酰胺类化合物、 特别是 通式 （I-A) 所示的吡唑酰胺类化合物作为农用杀菌剂的用途。 Since the present invention has found for the first time that a pyrazole amide compound represented by the general formula (I) has excellent bactericidal activity, the compound can be applied to various crops in agricultural fields such as agriculture, horticulture and flower cultivation. The disease is especially suitable for controlling the following plant diseases: cucumber downy mildew, corn rust, etc. The plant pathogen which can be controlled by the compound of the present invention is not limited to the above. Accordingly, the technical solution of the present invention includes the use of a pyrazole amide compound represented by the formula (I), particularly a pyrazole amide compound represented by the formula (I-A), as an agricultural bactericide.
本发明提出的通式 （I )所示的吡唑酰胺类化合物 （优选通式 （I-A)化合物）作为农用杀 菌剂的用途还包括提供了一种杀菌组合物，组合物中含有具有杀菌活性的通式（I)化合物（优 选通式 （I-A) 化合物） 作为活性组分， 组合物中活性组分的重量百分含量为 0.1-99%。 组合 物中还含有农业上可接受的载体和表面活性剂。 上述组合物可以按照已知方法制备成所需剂 型， 例如可湿性粉剂、 粉剂、 颗粒剂和溶液、 可乳化的浓縮剂、 乳剂、 悬浮浓縮剂、 气雾剂 和烟雾剂。 制剂中载体及表面活性剂的选择是本领域的技术人员所熟悉的。  The use of the pyrazole amide compound (preferably the compound of the formula (IA)) represented by the formula (I) proposed by the present invention as an agricultural bactericide further comprises providing a bactericidal composition containing bactericidal activity in the composition The compound of the formula (I) (preferably the compound of the formula (IA)) as an active ingredient, the active ingredient in the composition is present in an amount of from 0.1 to 99% by weight. The composition also contains an agriculturally acceptable carrier and surfactant. The above compositions can be prepared into a desired dosage form according to known methods, such as wettable powders, powders, granules and solutions, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. The choice of carrier and surfactant in the formulation is well known to those skilled in the art.
通过在组合物中加入其他的一种或多种杀菌剂， 使其能比单独的通式 （I)化合物具有更 广谱的活性。此外， 其他杀菌剂可对通式 (I)化合物的杀菌活性具有增效作用。也可将通式（I) 化合物与其他杀虫剂混用， 或同时与另一种杀菌剂以及其他杀虫剂混用。 具体实施方式  By incorporating other one or more bactericides into the composition, it has a broader spectrum of activity than the compound of formula (I) alone. Further, other bactericides have a synergistic effect on the bactericidal activity of the compound of the formula (I). The compound of the formula (I) can also be used in combination with other insecticides or at the same time with another fungicide and other insecticides. detailed description
以下具体的实例可以进一步说明本发明， 但本发明绝非仅限于这些例子 （除特殊说明外 的所有原料均有市售）。  The invention is further illustrated by the following specific examples, but the invention is by no means limited to these examples (all materials except the specific ones are commercially available).
合成实施例  Synthesis example
实施例 1 : 中间体 (4-(5- (三氟甲基)吡啶 -2-氧基)苯基)甲胺的制备方法  Example 1 : Preparation of intermediate (4-(5-(trifluoromethyl)pyridine -2-oxy)phenyl)methylamine
1 ) 4- (5- (三 -2-氧基)苯腈的制备
Figure imgf000030_0001
1) Preparation of 4-(5-(tri-2-oxyl)benzonitrile
Figure imgf000030_0001
18.15g ( O.lmol) 2-氯 -5-三氟甲基吡啶与 14.28g ( 0.12mol) 对羟基苯腈加入 200ml丁酮 中， 加入 27.60g ( 0.2mol) 碳酸钾， 搅拌下加热至回流， 反应 4-5小时， TLC监测反应完毕 后， 减压蒸除溶剂， 加入 300ml 乙酸乙酯萃取， 依次用 5%氢氧化钠水溶液、 饱和食盐水各 50ml洗涤， 脱溶后残余物通过柱层析分离得到白色固体 21.90g， 收率 83.0%， 熔点 84-85 °C。 核磁数据 1H NMR (300 MHz, CDC13): 5ppm 7.13(1H, d)， 7.29(2H, d)， 7.47(2H, d)， 7.99(1H, d)， 8.44(lH，d)。 18.15 g (O.lmol) of 2-chloro-5-trifluoromethylpyridine and 14.28 g (0.12 mol) of p-hydroxybenzonitrile were added to 200 ml of methyl ethyl ketone, and 27.60 g (0.2 mol) of potassium carbonate was added, and the mixture was heated to reflux with stirring. After reacting for 4-5 hours, after TLC monitoring, the solvent was evaporated under reduced pressure, extracted with ethyl acetate (300 ml), and then washed with 5% sodium hydroxide aqueous solution and saturated brine, respectively, and the residue was passed through the column. The precipitate was isolated to give a white solid (21.90 g, yield: 83.0% Nuclear magnetic data 1H NMR (300 MHz, CDC1 3 ): 5 ppm 7.13 (1H, d), 7.29 (2H, d), 7.47 (2H, d), 7.99 (1H, d), 8.44 (lH, d).
2) (4-(5- (三氟甲基吡啶 -2-氧基)苯基)甲胺的制备
Figure imgf000030_0002
2) Preparation of (4-(5-(trifluoromethylpyridin-2-yloxy)phenyl)methanamine
Figure imgf000030_0002
将 2.64g ( O.Olmol) 中间体 4- (5_ (三氟甲基）吡啶 _2_氧基）苯腈、 Raney镍 (1.0g)、 25% 氨水 10ml和乙醇 50ml组成的混合物在氢氛围、室温下搅拌反应 3-10小时， TLC监测反应完 毕后， 滤除 Raney镍， 减压蒸除溶剂得粘稠状液体， 冷却后得白色固体 2.00g， 收率 75.8%， 熔点 88-89 °C。  a mixture of 2.64 g (O.Olmol) of intermediate 4-(5-(trifluoromethyl)pyridine-2-oxy)benzonitrile, Raney nickel (1.0 g), 25% aqueous ammonia 10 ml and ethanol 50 ml in hydrogen atmosphere The reaction was stirred at room temperature for 3-10 hours. After the reaction was completed by TLC, Raney nickel was filtered off, and the solvent was evaporated under reduced pressure to give a viscous liquid. After cooling, a white solid of 2.00 g, yield 75.8%, melting point 88-89 ° C.
实施例 2: 中间体 2-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)乙胺的制备方法  Example 2: Preparation of intermediate 2-(4-(5-(trifluoromethyl)pyridine-2-oxy)phenyl)ethylamine
1 ) 2-(4-(5-三氟甲基)吡啶 -2-氧基)苯基)乙腈的制备
Figure imgf000030_0003
1) Preparation of 2-(4-(5-trifluoromethyl)pyridin-2-yloxy)phenyl)acetonitrile
Figure imgf000030_0003
18.15g ( O. lmol) 2-氯 -5-三氟甲基吡啶与 15.96g ( 0.12mol) 对羟基苯乙腈加入 200ml丁 酮中， 加入 27.60g ( 0.2mol) 碳酸钾， 搅拌下加热至回流， 反应 4-10小时， TLC监测反应完 毕后， 减压蒸除溶剂， 加入 300ml乙酸乙酯萃取， 依次用 5%氢氧化钠水溶液、饱和食盐水各 50ml洗涤， 脱溶后残余物通过柱层析分离得到白色固体 22.50g， 收率 80.9%， 熔点 48-49°C。 18.15 g (0.1 mol) of 2-chloro-5-trifluoromethylpyridine and 15.96 g (0.12 mol) of p-hydroxyphenylacetonitrile were added to 200 ml of methyl ethyl ketone, and 27.60 g (0.2 mol) of potassium carbonate was added thereto, and the mixture was heated to reflux with stirring. , reaction 4-10 hours, TLC monitoring reaction completed After completion, the solvent was evaporated under reduced pressure, and ethyl acetate (3 ml, EtOAc) 80.9%, melting point 48-49 ° C.
2) 2-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)乙胺的制备
Figure imgf000031_0001
2) Preparation of 2-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)ethylamine
Figure imgf000031_0001
将 2.78g ( O.Olmol) 中间体 2-(4-(5- (三氟甲基)吡啶 -2-氧基)苯基)乙腈、 Raney镍 (1.0g)、 25%氨水 10ml和乙醇 50ml组成的混合物在氢氛围、室温下搅拌反应 3-15小时， TLC监测反 应完毕后，滤除 Raney镍，减压蒸除溶剂得粘稠状液体，冷却后得白色固体 2.20g，收率 78.0%， 熔点 82-83 °C o  2.78 g (O.Olmol) of the intermediate 2-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)acetonitrile, Raney nickel (1.0 g), 25% aqueous ammonia 10 ml, and ethanol 50 ml The mixture was stirred for 3-15 hours under a hydrogen atmosphere at room temperature. After the TLC was monitored, the Raney nickel was filtered off, and the solvent was evaporated under reduced pressure to give a viscous liquid. After cooling, a white solid (2.20 g, yield 78.0%) , melting point 82-83 °C o
实施例 3 : 中间体 3-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)丙胺的制备  Example 3: Preparation of intermediate 3-(4-(5-(trifluoromethyl)pyridine-2-yloxy)phenyl)propylamine
1 ) 3-(4-(5- (三氟甲基)吡啶 -2-氧基)苯基)丙腈的制备
Figure imgf000031_0002
1) Preparation of 3-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)propanenitrile
Figure imgf000031_0002
18.15g ( O. lmol) 2-氯 -5-三氟甲基吡啶与 17.64g ( 0.12mol) 对羟基苯丙腈加入 200ml丁 酮中， 加入 27.60g ( 0.2mol) 碳酸钾， 搅拌下加热至回流， 反应 4-10小时， TLC监测反应完 毕后， 减压蒸除溶剂， 加入 300ml乙酸乙酯萃取， 依次用 5%氢氧化钠水溶液、饱和食盐水各 50ml洗涤， 脱溶后残余物通过柱层析分离得到无色油状物 23.50g， 收率 80.1%。  18.15 g (0.1 mol) of 2-chloro-5-trifluoromethylpyridine and 17.64 g (0.12 mol) of p-hydroxyphenylpropanenitrile were added to 200 ml of methyl ethyl ketone, and 27.60 g (0.2 mol) of potassium carbonate was added thereto, and heated under stirring. After refluxing, the reaction was carried out for 4-10 hours. After the reaction was completed by TLC, the solvent was evaporated under reduced pressure, and extracted with ethyl acetate (300 ml), and then washed with 5% sodium hydroxide aqueous solution and saturated brine, respectively, and the residue was passed through the column. Chromatography gave 23.50 g of colorless oil (yield: 80.1%).
2) 3-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)丙胺的
Figure imgf000031_0003
2) 3-(4-(5-(Trifluoromethyl)pyridin-2-yloxy)phenyl)propylamine
Figure imgf000031_0003
将 2.92g ( O.Olmol) 中间体 3-(4-(5- (三氟甲基)吡啶 -2-氧基)苯基)丙腈、 Raney镍 (1.0g)、 25%氨水 10ml和乙醇 50ml组成的混合物在氢氛围、室温下搅拌反应 3-15小时， TLC监测反 应完毕后，滤除 Raney镍，减压蒸除溶剂得粘稠状液体，冷却后得白色固体 2.30g，收率 77.7%， 熔点 95-96 °C。  2.92 g (O.Olmol) of intermediate 3-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)propanenitrile, Raney nickel (1.0 g), 25% aqueous ammonia 10 ml and ethanol The mixture of 50 ml of the mixture was stirred for 3-15 hours under a hydrogen atmosphere at room temperature. After the reaction was completed by TLC, Raney nickel was filtered off, and the solvent was evaporated under reduced pressure to give a viscous liquid, which was cooled to give a white solid 2.30 g. %, melting point 95-96 °C.
实施 4: 化合物 53的制备
Figure imgf000031_0004
Example 4: Preparation of Compound 53
Figure imgf000031_0004
53  53
将 (4-(5- (三氟甲基)吡啶 -2-氧基)苯基)甲胺 0.27g ( O.OOlmol)和三乙胺 0.12g ( 0.0012mol) 加入 20mL二氯甲烷中， 室温搅拌下滴加 0.21g ( O.OOl lmol) 1，3-二甲基 -4-氯 -5-吡唑甲酰氯的 Add (4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)methanamine 0.27 g (0.01 mol) and triethylamine 0.12 g (0.0012 mol) to 20 mL of dichloromethane at room temperature 0.21 g (O.OOl lmol) of 1,3-dimethyl-4-chloro-5-pyrazolecarbonyl chloride was added dropwise with stirring.
10mL二氯甲烷溶液， 然后继续室温搅拌反应 1小时， TLC监测反应完毕后， 将反应混合物 倾入 20mL水中， 分出有机层， 有机层依次经 5%稀盐酸、 饱和碳酸氢钠水溶液、 饱和食盐水 各 10mL洗涤， 无水硫酸镁干燥， 减压脱溶， 残余物经柱层析分离得纯品 0.40g， 收率 94.2%， 熔点 154-156°C。 10 mL of dichloromethane solution, and then the reaction was stirred at room temperature for 1 hour. After the TLC monitoring reaction was completed, the reaction mixture was poured into 20 mL of water, and the organic layer was separated. The organic layer was successively subjected to 5% diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine. The mixture was washed with 10 mL of water, dried over anhydrous magnesium sulfate, and evaporated to dryness. The residue was purified by column chromatography to yield 0.40 g, yield 94.2%, mp 154-156 ° C.
实施例 5 :
Figure imgf000031_0005
Example 5:
Figure imgf000031_0005
54  54
将 (4-(5- (三氟甲基)吡啶 -2-氧基)苯基)甲胺 0.27g ( O.OOlmol)和三乙胺 0.12g ( 0.0012mol) 加入 20mL二氯甲烷中， 室温搅拌下滴加 0.23g (O.OOllmol) 1-甲基 -3-乙基 -4-氯 -5-吡唑甲酰 氯的 10mL二氯甲烷溶液， 然后继续室温搅拌反应 1小时， TLC监测反应完毕后， 将反应混 合物倾入 20mL水中， 分出有机层， 有机层依次经 5%稀盐酸、 饱和碳酸氢钠水溶液、 饱和食 盐水各 10mL 洗涤， 无水硫酸镁干燥， 减压脱溶， 残余物经柱层析分离得纯品 0.41g， 收率 93.5%, 熔点 146-148°C o (4-(5-(Trifluoromethyl)pyridin-2-yloxy)phenyl)methanamine 0.27 g (0.01 mol) and triethylamine 0.12 g (0.0012 mol) Add 20 mL of dichloromethane, and add 0.23 g (0.01 mol) of 1-methyl-3-ethyl-4-chloro-5-pyrazolecarbonyl chloride in 10 mL of dichloromethane under stirring at room temperature, and then continue to stir at room temperature. After the reaction was completed for 1 hour, the reaction mixture was poured into 20 mL of water and the organic layer was separated. The organic layer was washed successively with 5% diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and brine, and dried over anhydrous magnesium sulfate. , decomposed under reduced pressure, and the residue was purified by column chromatography to yield 0.41 g of pure product, yield 93.5%, melting point 146-148 °C o
实施例 6:
Figure imgf000032_0001
Example 6
Figure imgf000032_0001
将 2-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)乙胺 0.28g(0.001mol)和三乙胺 0.12g(0.0012mol) 加入 20mL二氯甲烷中， 室温搅拌下滴加 0.21g (O.OOl lmol) 1，3-二甲基 -4-氯 -5-吡唑甲酰氯的 0.28 g (0.001 mol) of 2-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)ethylamine and 0.12 g (0.0012 mol) of triethylamine were added to 20 mL of dichloromethane. 0.21 g (0.01 lmol) of 1,3-dimethyl-4-chloro-5-pyrazolecarbonyl chloride was added dropwise with stirring at room temperature.
10mL二氯甲烷溶液， 然后继续室温搅拌反应 1小时， TLC监测反应完毕后， 将反应混合物 倾入 20mL水中， 分出有机层， 有机层依次经 5%稀盐酸、 饱和碳酸氢钠水溶液、 饱和食盐水 各 10mL洗涤， 无水硫酸镁干燥， 减压脱溶， 残余物经柱层析分离得纯品 0.40g， 收率 92.0%， 熔点 124-126°C。 10 mL of dichloromethane solution, and then the reaction was stirred at room temperature for 1 hour. After the TLC monitoring reaction was completed, the reaction mixture was poured into 20 mL of water, and the organic layer was separated. The organic layer was successively subjected to 5% diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine. The mixture was washed with 10 mL of water, dried over anhydrous magnesium sulfate, and evaporated to dryness. The residue was purified by column chromatography to yield 0.40 g of pure product, yield 92.0%, melting point 124-126 °C.
实施 7: 化合物
Figure imgf000032_0002
Implementation 7: Compounds
Figure imgf000032_0002
519  519
将 3-(4-(5- (三氟甲基)吡啶 -2-氧基） 苯基)丙胺 0.30g(0.001mol)和三乙胺 0.12g(0.0012mol) 加入 20mL二氯甲烷中，室温搅拌下滴加 0.19g(0.0011mol)l，3，4-三甲基 -5-吡唑甲酰氯的 10mL 二氯甲烷溶液，然后继续室温搅拌反应 1小时， TLC监测反应完毕后，将反应混合物倾入 20mL 水中， 分出有机层， 有机层依次经 5%稀盐酸、 饱和碳酸氢钠水溶液、 饱和食盐水各 10mL洗 涤，无水硫酸镁干燥，减压脱溶，残余物经柱层析分离得纯品 0.38g，收率 88.0%，熔点 97-98°C。  Add 0.30 g (0.001 mol) of 3-(4-(5-(trifluoromethyl)pyridin-2-yloxy)phenyl)propylamine and 0.12 g (0.0012 mol) of triethylamine to 20 mL of dichloromethane at room temperature 0.19 g (0.0011 mol) of a solution of 1,3,4-trimethyl-5-pyrazolecarbonyl chloride in 10 mL of dichloromethane was added dropwise with stirring, and the reaction was further stirred at room temperature for 1 hour. After the reaction was completed by TLC, the reaction mixture was stirred. The organic layer was poured into 20 mL of water, and the organic layer was washed successively with 5% diluted hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, dried over anhydrous magnesium sulfate, and then evaporated and evaporated. Pure product 0.38 g was obtained, the yield was 88.0%, and the melting point was 97-98 °C.
通式 （I) 的其他化合物可以用本发明提供的制备方法制得。  Other compounds of the formula (I) can be obtained by the preparation methods provided by the present invention.
部分化合物熔点和核磁数据 (^HNMR, 300MHz, 内标 TMS， 溶剂 CDC13)如下： The melting point and nuclear magnetic data (^HNMR, 300MHz, internal standard TMS, solvent CDC1 3 ) of some compounds are as follows:
化合物 53:熔点 154-156°C o5ppm 2.25(3H, s)， 4.15(3H, s)， 4.67(2H, d)， 7.03(2H, d)， 7.15(2H, d)， 7.43(2H, d)， 7.91(1H, d)， 8.44(1H， s)。  Compound 53: mp 154-156 ° C o 5 ppm 2.25 (3H, s), 4.15 (3H, s), 4.67 (2H, d), 7.03 (2H, d), 7.15 (2H, d), 7.43 (2H, d ), 7.91(1H, d), 8.44(1H, s).
化合物 54： 熔点 146-148°C o 5ppm 1.25(3H, t)， 2.61-2.65(2H, m)， 4.16(3H, s)， 4.67(2H, d)， 7.04(2H, d)， 7.15(2H, d)， 7.43(2H, d)， 7.90(1H, d)， 8.42(1H, s)。  Compound 54: mp 146-148°C o 5ppm 1.25 (3H, t), 2.61-2.65 (2H, m), 4.16 (3H, s), 4.67 (2H, d), 7.04 (2H, d), 7.15 ( 2H, d), 7.43(2H, d), 7.90(1H, d), 8.42(1H, s).
化合物 64: 熔点为 184-185°C。 δ ppm 2.25(3H， s)， 4.15(3H, s), 4.68(2H， d)， 7.11(lH，s)， 7.18(2H, d), 7.44(2H，d)， 7.99(1H， d)， 8.27(lH，d)。 Compound 64: mp 184-185 ° C. δ pp m 2.25(3H, s), 4.15(3H, s), 4.68(2H, d), 7.11(lH,s), 7.18(2H, d), 7.44(2H,d), 7.99(1H, d ), 8.27 (lH, d).
化合物 115： 熔点 147-148°C o 5ppm 2.13 (3H, s)， 2.18(3H, s)， 4.03(3H, s)， 4.66(2H, d)， 6.04(1H, s)， 7.03(2H, d)， 7.15(2H, d)， 7.41(2H, d)， 7.91(1H, d)， 8.43(1H, s)。  Compound 115: mp 147-148°C o 5ppm 2.13 (3H, s), 2.18 (3H, s), 4.03 (3H, s), 4.66 (2H, d), 6.04 (1H, s), 7.03 (2H, d), 7.15(2H, d), 7.41(2H, d), 7.91(1H, d), 8.43(1H, s).
化合物 151 : 熔点为 183-184°C。 δ ppm 2.24(3H， s)， 4.15(3H, s), 4.66(2H， d)， 7.10(1H, s), 7.15(2H, d), 7.40(2H，d)， 7.85(lH，s)。 Compound 151: mp 183-184 ° C. δ pp m 2.24(3H, s), 4.15(3H, s), 4.66(2H, d), 7.10(1H, s), 7.15(2H, d), 7.40(2H,d), 7.85(lH,s ).
化合物 155: 161-163 °C o 5ppm 2.22(3H, s), 2.98(2H，t)， 3.68-3.84(2H, m), 4.12(3H, s), 6.78(lH，s)， 7.01(1H, d), 7.11(2H, d), 7.37(2H, d), 8.33(1H, d), 8.84(lH，s)。  Compound 155: 161-163 °C o 5ppm 2.22(3H, s), 2.98(2H,t), 3.68-3.84(2H, m), 4.12(3H, s), 6.78(lH,s), 7.01(1H , d), 7.11(2H, d), 7.37(2H, d), 8.33(1H, d), 8.84(lH, s).
化合物 157: 熔点为 161-162°C。 δ ppm 2.24(3H， s)， 4.14(3H, s), 4.66(2H， d)， 7.08(1H， s)， 7.14(2H, d), 7.41(2H, d), 7.78(1H, d), 7.96(lH，d)。 Compound 157: mp 161-162 ° C. δ pp m 2.24(3H, s), 4.14(3H, s), 4.66(2H, d), 7.08(1H, s), 7.14(2H, d), 7.41(2H, d), 7.78(1H, d ), 7.96 (lH, d).
化合物 169： 熔点 124-126°C。 5ppm 2.22(3H, s)， 2.90-3.00(2H, m)， 3.75(2H, d)， 4.12(3H, s)， 7.00-7.13(3H, m)， 7.27-7.33(3H, m)， 7.90(1H, d)， 8.44(1H， s)。  Compound 169: mp 124-126 ° C. 5ppm 2.22(3H, s), 2.90-3.00(2H, m), 3.75(2H, d), 4.12(3H, s), 7.00-7.13(3H, m), 7.27-7.33(3H, m), 7.90 (1H, d), 8.44 (1H, s).
化合物 170： 熔点 145-146°C o 5ppm 1.23(3H, t), 2.60-2.63(2H, m),2.96(2H, t), 3.74-3.76(2H, m), 4.12(3H, s), 6.78(1H, s), 7.01(1H， s)， 7.11(2H, d), 7.30(2H, d), 7.78(1H, d), 8.42(lH，s)。 化合物 176： 熔点 157-158°C o 5ppm 1.22(3H, t), 2.57-2.64(2H, m),2.96(2H, t), 3.74-3.79(2H, m)， 4.13(3H, s), 7.12(2H, d)， 7.30(2H, d)， 7.85(1H, s)。 Compound 170: melting point 145-146 ° C o 5 ppm 1.23 (3H, t), 2.60-2.63 (2H, m), 2.96 (2H, t), 3.74-3.76 (2H, (m), 4.12 (3H, s) ). Compound 176: mp 157-158°C o 5ppm 1.22 (3H, t), 2.57-2.64 (2H, m), 2.96 (2H, t), 3.74-3.79 (2H, m), 4.13 (3H, s), 7.12(2H, d), 7.30(2H, d), 7.85(1H, s).
化合物 181 : 熔点为 173-175°C。 5ppm 2.21(3H, s), 2.93-3.01 (2H, t), 3.71-3.77(2H, q), 4.12(3H, s), 6.75(lH，s)， 7.13(2H, d), 7.33(2H, d), 7.99(1H， s)， 8.27(lH，s)。  Compound 181 : melting point 173-175 ° C. 5ppm 2.21(3H, s), 2.93-3.01 (2H, t), 3.71-3.77(2H, q), 4.12(3H, s), 6.75(lH,s), 7.13(2H, d), 7.33(2H , d), 7.99 (1H, s), 8.27 (lH, s).
化合物 184： 熔点 124-126°C o 5ppm 1.23(3H, t), 2.60-2.63(2H, m),2.98(2H, t), 3.75-3.77(2H, m)， 4.13(3H, s), 6.77(1H, s)， 7.14(2H, d)， 7.34(2H, d)， 7.99(1H, s)， 8.27(1H, s)。  Compound 184: m.p. 124-126°C o 5ppm 1.23 (3H, t), 2.60-2.63 (2H, m), 2.98 (2H, t), 3.75-3.77 (2H, m), 4.13 (3H, s), 6.77 (1H, s), 7.14 (2H, d), 7.34 (2H, d), 7.99 (1H, s), 8.27 (1H, s).
化合物 189： 熔点 167-169°C o 5ppm 2.24(3H, s),2.95(2H, t)， 3.66-3.70(2H, m)， 4.10(3H, s)， 6.15(1H, s)， 7.15(2H, d)， 7.29(2H, s)， 7.94-7.97(2H, m)， 8.30(1H, s)。  Compound 189: Melting point 167-169 ° C o 5 ppm 2.24 (3H, s), 2.95 (2H, t), 3.66-3.70 (2H, m), 4.10 (3H, s), 6.15 (1H, s), 7.15 ( 2H, d), 7.29 (2H, s), 7.94-7.97 (2H, m), 8.30 (1H, s).
化合物 195： 熔点 174-176°C。 5ppm 2.27 (3H, s),2.96(2H, t)， 3.70-3.73(2H, m)， 4.13(3H, s)， Compound 195: Melting point 174-176 °C. 5ppm 2.27 (3H, s), 2.96 (2H, t), 3.70-3.73 (2H, m), 4.13(3H, s),
6.16(1H, s)， 7.22-7.28(3H, m)， 7.88(1H, s)。 6.16(1H, s), 7.22-7.28(3H, m), 7.88(1H, s).
化合物 199： 熔点 147-148°C o 5ppm 2.24(3H, s),2.92(2H, t)， 3.63-3.67(2H, m)， 4.10(3H, s)， 6.05(lH，s)， 6.16(lH，s)， 7.11(2H, d), 7.28(2H, d), 7.79(1H, s), 7.96(lH，s)。  Compound 199: Melting point 147-148 ° C o 5 ppm 2.24 (3H, s), 2.92 (2H, t), 3.63-3.67 (2H, m), 4.10 (3H, s), 6.05 (lH, s), 6.16 ( lH, s), 7.11 (2H, d), 7.28 (2H, d), 7.79 (1H, s), 7.96 (lH, s).
化合物 203： 熔点 172-173 °C。 5ppm 2.25(3H, s),2.94(2H, t)， 3.67-3.69(2H, m)， 4.11(3H, s)， 6.15(lH，s)， 7.14(2H, d), 7.30(2H, d), 7.99(1H, s), 8.27(lH，s)。  Compound 203: melting point 172-173 °C. 5ppm 2.25(3H, s), 2.94(2H, t), 3.67-3.69(2H, m), 4.11(3H, s), 6.15(lH,s), 7.14(2H, d), 7.30(2H, d ), 7.99(1H, s), 8.27(lH, s).
化合物 499： 熔点 169-170°C。 5ppm 1.97(3H, s)， 2.15(3H, s)， 2.98(2H, t)， 3.74-3.76(2H,m), 3.98(3H, s)， 5.78(1H, s))， 7.02(1H, d)， 7.11(2H, d)， 7.31(2H, d)， 7.92(1H, d)， 8.42(1H, s)。  Compound 499: mp 169-170 ° C. 5ppm 1.97(3H, s), 2.15(3H, s), 2.98(2H, t), 3.74-3.76(2H,m), 3.98(3H, s), 5.78(1H, s)), 7.02(1H, d), 7.11(2H, d), 7.31(2H, d), 7.92(1H, d), 8.42(1H, s).
化合物 519： 熔点 97-98 °C o 5ppm 1.63(3H, s)， 1.98-2.01(2H, m)， 2.13(3H, s)， 2.74(2H,t), 3.50-3.52(2H, m)， 4.00(3H, s))， 5.76(1H, s)， 7.00(2H, d)， 7.09(2H, d)， 7.89(1H, d)， 8.44(1H， s)。  Compound 519: Melting point 97-98 ° C o 5 ppm 1.63 (3H, s), 1.98-2.01 (2H, m), 2.13 (3H, s), 2.74 (2H, t), 3.50-3.52 (2H, m), 4.00(3H, s)), 5.76(1H, s), 7.00(2H, d), 7.09(2H, d), 7.89(1H, d), 8.44(1H, s).
化合物 591 :熔点为 163-165°C。 δ ppm 2.21 (3H, s) , 2.91 (2H, t) , 3.64-3.74(2H, m) , 4.10(3H, s)， 6.70(lH，s)， 6.79(2H，d)， 7.20(2H, d), 8.31(1H, s) Compound 591: Melting point: 163-165 °C. δ pp m 2.21 (3H, s) , 2.91 (2H, t) , 3.64-3.74(2H, m) , 4.10(3H, s), 6.70(lH,s), 6.79(2H,d), 7.20(2H , d), 8.31(1H, s)
化合物 969: 熔点 201 -202 °C。 δ ppm 4.24(3H, s)， 4.74(2H, d)， 7.22(1H, s)， 7.46(4H, dd)， 7.64(2H, d)， 7.77(2H, d)。 Compound 969: Melting point 201 - 202 °C. δ ppm 4.24(3H, s), 4.74(2H, d), 7.22(1H, s), 7.46(4H, dd), 7.64(2H, d), 7.77(2H, d).
化合物 972:熔点 100-lOrC。 Sppm 1.23(3H, t)， 1.42(3H, t)， 2.59-2.67(2H, m)， 4.00-4.07(2H, m), 4.15(3H, s), 4.56(2H, d), 6.88(2H， d)， 7.27(2H，d)。  Compound 972: Melting point 100-lOr. Sppm 1.23(3H, t), 1.42(3H, t), 2.59-2.67(2H, m), 4.00-4.07(2H, m), 4.15(3H, s), 4.56(2H, d), 6.88(2H , d), 7.27 (2H, d).
化合物 974：熔点 196-197°C o 5 ppm 4.24(3H, s), 4.61(2H, d)， 6.38(1H, s)， 6.78(1H, s)， 7.21-7.26(2H, m), 7.35-7.41(4H, m), 7.67-7.70(2H, m)。 Compound 974: melting point 196-197 ° C o 5 ppm 4.24 (3H, s), 4.61 (2H, d), 6.38 (1H, s), 6.78 (1H, s), 7.21-7.26 (2H, m), 7.35 -7.41 (4H, m), 7.67-7.70 (2H, m).
化合物 973： 熔点 85-87 °C o 5ppml.24(3H, t)， 2.60-2.68(2H, m)， 4.14(3H, s)， 4.64(2H, d)， 7.10(1H, s)， 7.21(2H, d)， 7.39(2H, d)。  Compound 973: m.p. 85-87 °C o 5ppml.24 (3H, t), 2.60-2.68 (2H, m), 4.14 (3H, s), 4.64 (2H, d), 7.10 (1H, s), 7.21 (2H, d), 7.39 (2H, d).
化合物 977： 熔点 88-89°C o 5ppm 0.97(3H, t)， 1.23(3H, t)， 1.45-1.47(2H, m)， 1.56(3H, d),1.71-1.78(2H, m)， 2.62(2H, m)， 3.95(2H, t)， 4.10(3H, s)， 5.18-5.22(1H, m)， 6.88(2H, d)， 7.27(2H, d)。  Compound 977: mp 88-89 ° C o 5 ppm 0.97 (3H, t), 1.23 (3H, t), 1.45-1.47 (2H, m), 1.56 (3H, d), 1.71-1.78 (2H, m), 2.62(2H, m), 3.95(2H, t), 4.10(3H, s), 5.18-5.22(1H, m), 6.88(2H, d), 7.27(2H, d).
化合物 1024： 熔点 87-89 °C o 5ppml.24(3H, t)， 2.59-2.67(2H, m)， 3.89(6H, s)， 4.15(3H, s)， 4.58(2H, d)， 6.84-6.87(3H, m), 6.93(1H, s)。  Compound 1024: mp 87-89 °C o 5ppml.24 (3H, t), 2.59-2.67 (2H, m), 3.89 (6H, s), 4.15 (3H, s), 4.58 (2H, d), 6.84 -6.87 (3H, m), 6.93 (1H, s).
化合物 1025:熔点 87-88°C。Sppm 2.24(2H, m)， 4.14(3H, s), 4.64(2H, d)， 7.08(1H, s)， 7.27(2H: d)，7.38(2H，d)。 Compound 1025: mp 87-88 ° C. Sppm 2.24 (2H, m), 4.14 (3H, s), 4.64 (2H, d), 7.08 (1H, s), 7.27 (2H : d), 7.38 (2H, d).
化合物 1026:熔点 83-84 °C。 Sppm 0.93(3H, t)， 1.35-1.44(4H, m)， 1.78-1.82(2H, m)， 2.23(3H, s), 3.94(2H, m), 4.14(3H, s), 4.56(2H, d), 6.88(2H, d), 6.92(1H, s), 7.27(2H，d)。  Compound 1026: Melting point 83-84 °C. Sppm 0.93(3H, t), 1.35-1.44(4H, m), 1.78-1.82(2H, m), 2.23(3H, s), 3.94(2H, m), 4.14(3H, s), 4.56(2H , d), 6.88 (2H, d), 6.92 (1H, s), 7.27 (2H, d).
化合物 1027: 熔点 82-83°C。 Sppm 0.93(3H， t)， 1.23(3H, t), 1.37-1.43(4H, m), 1.76-1.81(2H, m)， 2.59-2.66(2H, m)， 3.95(2H, m)， 4.15(3H, s)， 4.56(2H, d)， 6.87(2H, d)， 6.90(1H， s)， 7.27(2H, d)。  Compound 1027: mp 82-83 ° C. Sppm 0.93(3H, t), 1.23(3H, t), 1.37-1.43(4H, m), 1.76-1.81(2H, m), 2.59-2.66(2H, m), 3.95(2H, m), 4.15 (3H, s), 4.56 (2H, d), 6.87 (2H, d), 6.90 (1H, s), 7.27 (2H, d).
化合物 1028： 熔点 97-98 °C o 5ppm 1.42(3H, t)， 2.23(2H, s)， 4.02-4.04(2H, m)， 4.14(3H, s)， 4.56(2H，d)， 6.88(2H，d)， 6.95(1H， s)， 7.27(2H，d)。  Compound 1028: Melting point 97-98 °C o 5 ppm 1.42 (3H, t), 2.23 (2H, s), 4.02-4.04 (2H, m), 4.14 (3H, s), 4.56 (2H, d), 6.88 ( 2H, d), 6.95 (1H, s), 7.27 (2H, d).
化合物 1029： 熔点 58-59°C o 5ppm 1.21(3H, t), 1.23-1.31(10H, m), 1.35(3H, t),1.56-1.58(2H, m)， 1.59(3H, d),2.61(2H, m)， 3.94(2H, t)， 4.12(3H, s)， 5.08-5.12(1H, m)， 6.89(2H, d)， 7.28(2H, d)。  Compound 1029: mp 58-59 ° C o 5 ppm 1.21 (3H, t), 1.23-1.31 (10H, m), 1.35 (3H, t), 1.56-1.58 (2H, m), 1.59 (3H, d), 2.61 (2H, m), 3.94 (2H, t), 4.12 (3H, s), 5.08-5.12 (1H, m), 6.89 (2H, d), 7.28 (2H, d).
制剂实施例 配方中各组分以重量计量， 活性化合物折百后计量加入。 实施例 8 60%可湿性粉剂 Formulation Example The components in the formulation are measured by weight and the active compound is metered in at a hundred percent basis. Example 8 60% wettable powder
化合物 53 60%  Compound 53 60%
十二烷基萘磺酸钠 2%  Sodium dodecylnaphthalene sulfonate 2%
木质素磺酸钠 9%  Sodium lignosulfonate 9%
高岭土 补足至 100%  Kaolin is made up to 100%
各组分 （均为固体） 混合在 在粉碎机中粉碎， 直到颗粒达到标准。  The components (both solids) are mixed and comminuted in a pulverizer until the granules reach the standard.
实施例 9 30%含水悬浮液  Example 9 30% aqueous suspension
化合物 53 30%  Compound 53 30%
十二烷基萘磺酸钠 4%  Sodium dodecyl naphthalene sulfonate 4%
半纤维素 2%  Hemicellulose 2%
环氧丙烷 8%  Propylene oxide 8%
水 补足至 100%  Water to 100%
将化合物 53与应加入水量的 80%和十二烷基萘磺酸钠在球磨机中 （1mm珠） 中一起粉 碎。 其它组分溶解在其余的水中， 然后搅拌加入其它组分。  Compound 53 was pulverized together with 80% of the water to be added and sodium dodecylnaphthalene sulfonate in a ball mill (1 mm beads). The other components were dissolved in the remaining water, and then the other components were stirred.
实施例 10 10%浓悬浮剂  Example 10 10% concentrated suspension
化合物 54 10%  Compound 54 10%
乙二醇 5%  Ethylene glycol 5%
壬基苯酚聚乙二醇醚 3%  Nonylphenol polyglycol ether 3%
木质素磺酸钠 5%  Sodium lignosulfonate 5%
羧甲基纤维素 1%  Carboxymethyl cellulose 1%
75%硅油水乳液 0.4%  75% silicone oil emulsion 0.4%
水 补足至 100%  Water to 100%
将化合物 54及其他组分充分混合， 由此得到的浓悬浮剂， 用水稀释所得悬浮剂可得到 任何所需浓度的稀释液。  The compound 54 and the other components are thoroughly mixed, and the thus obtained suspension concentrate is diluted with water to obtain a diluent of any desired concentration.
生物活性测定实施例 Biological activity assay example
实施例 11 杀菌活性测定  Example 11 Determination of bactericidal activity
用本发明化合物对植物的多种菌病害进行了试验。 试验的方法如下：  A variety of bacterial diseases of plants have been tested with the compounds of the invention. The test method is as follows:
(1)活体保护活性测定  (1) Determination of in vivo protective activity
试验采用盆栽幼苗测定法。 选择生长一致的两叶期盆栽黄瓜幼苗， 作为黄瓜霜霉病试验 材料； 选择生长一致的两叶期盆栽玉米幼苗， 作为玉米锈病试验材料； 选择生长一致的两叶 期盆栽小麦苗， 作为小麦白粉病试验试验材料。 用本发明化合物按照设计浓度进行叶面喷雾 处理， 另设喷清水的空白对照， 3 次重复， 处理后第二天进行病害接种。 接种后， 将植物放 在人工气候室中 （温度： 昼 25 °C、 夜 20°C， 相对湿度： 95〜99%)保湿培养， 24小时后将植 物试材移入温室培养，将不需要保湿培养的植物直接在温室内接种并培养。 待对照充分发病后 (通常为一周时间） 进行化合物防病效果评估。 病害分级参照中华人民共和国国家标准 《农 药田间药效试验准则》， 以病情指数计算防治效果。  The test was carried out using a potted seedling assay. The two-leaf stage potted cucumber seedlings with uniform growth were selected as test materials for cucumber downy mildew; the two-leaf potted corn seedlings with uniform growth were selected as test materials for corn rust; the two-leaf potted wheat seedlings with uniform growth were selected as wheat white powder. Disease test material. The compound of the present invention was subjected to foliar spray treatment at a designed concentration, and a blank control of sprayed water was additionally provided, three times of repetition, and the disease was inoculated the next day after the treatment. After inoculation, the plants are placed in an artificial climate chamber (temperature: 昼25 °C, night 20 °C, relative humidity: 95~99%). Moisturizing culture after 24 hours, the plant samples are transferred to the greenhouse for cultivation, and no moisturizing is required. The cultured plants are inoculated and cultured directly in the greenhouse. Compound anti-disease effects were assessed after a sufficient onset of control (usually one week). The disease classification is based on the National Standard of the People's Republic of China on the Field Drug Effectiveness Test Guidelines, and the disease prevention index is used to calculate the control effect.
部分测试结果如下：  Some test results are as follows:
黄瓜霜霉病的防效：  Cucumber downy mildew prevention:
药液浓度为 400ppm时， 化合物 53、 54、 115、 169、 170、 972、 973、 1024、 1025、 1027、 1028等的防效为 100%; 化合物 189、 591等的防效为 98%; 化合物 519的防效为 95%; 化合物 157 的防效为 85%;  When the concentration of the chemical solution is 400 ppm, the control effect of the compounds 53, 54, 115, 169, 170, 972, 973, 1024, 1025, 1027, 1028, etc. is 100%; the control effect of the compound 189, 591, etc. is 98%; The control effect of 519 is 95%; the control effect of compound 157 is 85%;
药液浓度为 lOOppm时， 化合物 53、 54、 115、 169、 170、 972、 973、 1024、 1027等的 防效为 100%; 化合物 1025的防效为 80%;  When the concentration of the chemical solution is lOOppm, the control effects of the compounds 53, 54, 115, 169, 170, 972, 973, 1024, 1027, etc. are 100%; the control effect of the compound 1025 is 80%;
药液浓度为 50ppm时， 化合物 53、 54、 169、 1024等的防效为 100%; 化合物 115、 972 的防效分别为 98%和 95%； 药液浓度为 12.5ppm时， 化合物 53、 54等的防效为 100%; 化合物 1024的防效为 85%; 药液浓度为 3.125ppm时， 化合物 53的防效达到 95%。 When the concentration of the chemical solution is 50 ppm, the control effects of the compounds 53, 54, 169, 1024, etc. are 100%; the control effects of the compounds 115, 972 are 98% and 95%, respectively; When the concentration of the chemical solution is 12.5 ppm, the control effect of the compound 53, 54 and the like is 100%; the control effect of the compound 1024 is 85%; and when the concentration of the chemical liquid is 3.125 ppm, the control effect of the compound 53 is 95%.
玉米锈病的防效：  Control of corn rust:
药液浓度为 400ppm时， 化合物 115、 169、 519、 972、 973、 1024、 1025、 1026、 1027、 1028等的防效为 100%， 化合物 189等的防效为 95%;  When the concentration of the chemical solution is 400 ppm, the control effects of the compounds 115, 169, 519, 972, 973, 1024, 1025, 1026, 1027, 1028, etc. are 100%, and the control effect of the compound 189 or the like is 95%;
药液浓度为 lOOppm时， 化合物 972、 973、 1024、 1026、 1027等的防效为 100%; 化合 物 1025的防效为 95%;  When the concentration of the chemical solution is lOOppm, the control effect of the compounds 972, 973, 1024, 1026, 1027, etc. is 100%; the control effect of the compound 1025 is 95%;
药液浓度为 25ppm时， 化合物 973、 1024、 1027等的防效为 100%; 化合物 1026的防效 为 90%;  When the concentration of the chemical solution is 25 ppm, the control effect of the compounds 973, 1024, 1027, etc. is 100%; the control effect of the compound 1026 is 90%;
药液浓度为 6.25ppm时， 化合物 973、 1024的防效达到 90%以上。  When the concentration of the chemical solution is 6.25 ppm, the compound 973 and 1024 have a control effect of 90% or more.
小麦白粉病的防效：  Control of wheat powdery mildew:
药液浓度为 400ppm时， 化合物 499、 973、 1024、 1025等的防效为 100%。  When the concentration of the chemical solution is 400 ppm, the control effects of the compounds 499, 973, 1024, and 1025 are 100%.
(2)离体抑菌活性测定  (2) Determination of in vitro antibacterial activity
测定方法如下： 采用高通量筛选方法， 即将待测化合物样品用适合的溶剂 （溶剂的种类 如丙酮、 甲醇、 DMF等， 并且依据其对样品的溶解能力而选择） 溶解， 配制成 所需浓度待 测液。 在超净工作环境下， 将待测液加入到 96孔培养板的微孔中， 再将病原菌繁殖体悬浮液 加入其中， 处理后的培养板放置在恒温培养箱中培养， 24小时后进行调查。 调查时目测病原 菌繁殖体萌发或生长情况， 并根据对照处理的萌发或生长情况， 评价化合物抑菌活性。  The determination method is as follows: The high-throughput screening method is adopted, that is, the sample of the test compound is dissolved in a suitable solvent (such as acetone, methanol, DMF, etc., and selected according to the solvency of the sample) to prepare a desired concentration. The liquid to be tested. In the ultra-clean working environment, the test solution is added to the micropores of the 96-well culture plate, and the pathogen propagule suspension is added thereto, and the treated plate is placed in a constant temperature incubator for cultivation, and then investigated after 24 hours. . The germination or growth of the pathogen of the pathogen was visually observed at the time of the investigation, and the bacteriostatic activity of the compound was evaluated based on the germination or growth of the control treatment.
部分化合物的离体抑菌活性 （以抑制率表示） 测试结果如下：  The in vitro antibacterial activity of some compounds (expressed as inhibition rate) The test results are as follows:
水稻稻瘟病的防效：  Control of rice blast disease:
药液浓度为 25ppm时， 化合物 115、 181、 499、 519、 973、 1024、 1028等的防效为 100%； 化合物 155、 972、 1025、 1027的防效均为 80%；  When the concentration of the chemical solution is 25 ppm, the control effects of the compounds 115, 181, 499, 519, 973, 1024, 1028, etc. are 100%; the control effects of the compounds 155, 972, 1025, 1027 are all 80%;
药液浓度为 8.3ppm时， 化合物 115、 499、 519、 973的防效为 100%;  When the concentration of the chemical solution is 8.3 ppm, the control effect of the compounds 115, 499, 519, and 973 is 100%;
药液浓度为 0.9ppm时， 化合物 115、 519的防效为 100%; 化合物 973的防效为 80%;  When the concentration of the chemical solution is 0.9 ppm, the control effect of the compound 115 and 519 is 100%; the control effect of the compound 973 is 80%;
药液浓度为 0.3ppm时， 化合物 115、 519的防效为 100%;  When the concentration of the chemical solution is 0.3 ppm, the control effect of the compound 115 and 519 is 100%;
药液浓度为 0.03ppm时， 化合物 115、 519的防效为 100%。  When the concentration of the chemical solution was 0.03 ppm, the control effect of the compound 115 and 519 was 100%.
黄瓜灰霉病的防效：  Control effect of cucumber gray mold:
药液浓度为 25ppm时， 化合物 115、 519等的防效为 100%; 化合物 499的防效为 80%; 药液浓度为 8.3ppm时， 化合物 519的防效为 100%; 化合物 115的防效为 80%;  When the concentration of the chemical solution is 25 ppm, the control effect of the compound 115, 519, etc. is 100%; the control effect of the compound 499 is 80%; when the concentration of the chemical solution is 8.3 ppm, the control effect of the compound 519 is 100%; 80%;
药液浓度为 2.8ppm时， 化合物 519的防效为 80%。  When the concentration of the chemical solution was 2.8 ppm, the compound 519 had an effect of 80%.
选取部分本发明化合物 53、 54与唑虫酰胺、 CK1至 CK5及根据现有技术合成的 CK6至 CK9 进行了对黄  Selecting some of the compounds of the present invention 53 and 54 and oxazolamide, CK1 to CK5 and CK6 to CK9 synthesized according to the prior art were carried out on yellow
Figure imgf000035_0001
Figure imgf000035_0001
CK9 表 4黄瓜霜霉病保护活性对比试验 CK9 Table 4 Comparative test of protective activity of cucumber downy mildew
Figure imgf000036_0001
实施例 12 田间防治黄瓜霜霉病的试验
Figure imgf000036_0001
Example 12 Test for Controlling Cucumber Downy Mildew in Field
试验于 2011年 7月在辽宁省沈阳市于洪区一田间小区进行，试验参照中华人民共和国国 家标准 《农药田间药效试验准则》 的相关标准执行。 本发明化合物 54 (实施例 10的 10%浓 悬浮剂， 下同） 的处理浓度为 400、 100 ppm, 对照药剂 50%烯酰吗啉可湿性粉剂 （市售） 的 浓度为 200 ppm。 小区面积 20m2， 随机排列， 2次重复。 喷液量约为 600L/hm2， 另以清水作 为空白对照。 化合物 54防治黄瓜霜霉病田间小区试验结果见表 5。 The test was carried out in July 2011 in Yitian District, Yuhong District, Shenyang City, Liaoning Province. The test was carried out in accordance with the relevant standards of the National Standard for Pesticide Field Efficacy Test of the People's Republic of China. The concentration of the compound of the present invention 54 (10% concentrated suspension of Example 10, the same hereinafter) was 400, 100 ppm, and the concentration of the control agent 50% dimethomorph wettable powder (commercially available) was 200 ppm. The area of the plot is 20m 2 , randomly arranged, and repeated twice. The amount of liquid spray is about 600 L/hm 2 , and fresh water is used as a blank control. The results of the test of compound 54 against cucumber downy mildew field plot are shown in Table 5.
表 5 本发明化合物 54防治黄瓜霜霉病田间小区试验结果  Table 5 Test results of the compound of the present invention 54 for controlling the field of cucumber downy mildew
防 治 效果 （¾> )  Prevention effect (3⁄4> )
供试药剂 刑里 (ppm)  Test Pharmacy (ppm)
I II 平均  I II average
400 74 85 80  400 74 85 80
化合物 54  Compound 54
100 68 64 66  100 68 64 66
烯酰吗啉 200 45 50 48 空白对照 (病指） ( 82 ) ( 74 ) ( 78 ) 田间试验药效计算方法如下: 指数 (%) -∑(调S査总叶t数? Xx最^局病J级i数 )χΐο° Dimethomorph 200 45 50 48 blank control (disease) ( 82 ) ( 74 ) ( 78 ) The field test efficacy calculation method is as follows: index ( % ) - ∑ ( tune S check total leaf t number? X x most ^ Bureau disease J grade i number ) χΐο °
防治效果 (Q =对麵' 指数 纖  Control effect (Q = opposite 'index fiber
对照病情指数  Control disease index

Claims

权 利 要 求 书 Claim
1、 一种吡唑酰胺类化合物作 构如通式 （I-A) 所示: 1. A pyrazole amide compound is represented by the formula (I-A):
Figure imgf000037_0001
Figure imgf000037_0001
( I-A )  ( I-A )
式中:  In the formula:
选自氢、 C C6烷基、 ^代 CrC6烷基、 d-C6烷氧基 CrC3烷基、氰基 CrC6烷基或 C3-C6 环烷基； Is selected from hydrogen, CC 6 alkyl, C r C 6 substituting ^ alkyl, dC 6 alkoxy C r C 3 alkyl, cyano C r C 6 alkyl or C 3 -C 6 cycloalkyl;
R2选自氢、 卤素、氰基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 氰基 6烷基、 氰基 6烷氧基、 未取代的或被 1-5个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 羟基、 氨基、 巯基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基或 卤代 6烷氧基； R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, cyano 6 alkyl , cyano 6 alkoxy, unsubstituted or substituted by 1 to 5 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, hydroxy, amino, decyl, C r C 6 alkyl, Halogenated C r C 6 alkyl, C r C 6 alkoxy or halo 6 alkoxy;
R3选自氢、 卤素、 氰基、 硝基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6 烷氧基、 6烷硫基或 crc6烷基磺酰基； R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, 6 alkane Thio or c r c 6 alkylsulfonyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 卤素、氰基、硝基、羟基、氨基、 CrC6烷基、 卤代 CrC6烷基、 CrC6烷氧基、 卤代 CrC6烷氧基、 ¾ 6环烷基、 C2-C6烯基、 C2-C6块基、 ¾ 6烯氧基、 ^代 ¾ 6烯氧基、 C2-C6块氧基、 卤代 C2-C6块氧基、 CrC6浣硫基、 卤代 CrC6烷硫基、 CrC6烷氧基 CrC6烷 、 Ci-C6 Ci-C6 Ci-C6 ¾¾¾¾¾ Ci-C6 \ ί Ci-C6 ¾¾¾¾¾ Ci-C6 Selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 6 alkyl, halogenated C r C 6 alkyl, C r C 6 alkoxy, halogenated C r C 6 alkoxy, 3⁄4 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 block, 3⁄6 6 alkenyloxy, ^ 3 6 unalkenyloxy, C 2 -C 6 -oxyl, halogenated C 2 - C 6 -oxyl group, C r C 6 thiol group, halogenated C r C 6 alkylthio group, C r C 6 alkoxy C r C 6 alkane, Ci-C 6 Ci-C 6 Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6 \ ί Ci-C 6 3⁄43⁄43⁄43⁄43⁄4 Ci-C 6
CrC6烷基亚磺酰基、 卤代 crc6烷基亚磺酰基、 crc6烷基磺酰基、 卤代 crc6烷基磺酰基、 C C6烷基氨基、 卤代 CrC6烷基氨基或 C2-C6二烷基氨基； n选自 0至 4的整数； 当 n大于 1 时， 可相同或不同； C r C 6 alkylsulfinyl, halo c r c 6 alkylsulfinyl, c r c 6 alkylsulfonyl, halo c r c 6 alkylsulfonyl, CC 6 alkylamino, halogenated C r C 6 alkylamino or C 2 -C 6 dialkylamino; n is selected from an integer from 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
2、 根据权利要求 1所述的用途， 其特征在于： 通式 (I-A)中  2. Use according to claim 1, characterized by: in the formula (I-A)
选自氢、 CrC4烷基或 C3-C6环烷基； Selected from hydrogen, C r C 4 alkyl or C 3 -C 6 cycloalkyl;
R2选自氢、 卤素、氰基、 CrC4烷基、 卤代 CrC4烷基、 4烷氧基、 卤代 ^ 4烷氧基、 氰基 -¾烷基、 氰基 -¾烷氧基、 未取代的或被 1-3个独立选自以下基团进一步取代的苯 基： 卤素、 氰基、 硝基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 4烷氧基；R 2 is selected from the group consisting of hydrogen, halogen, cyano, C r C 4 alkyl, halogenated C r C 4 alkyl, 4 alkoxy, halo- 4 -alkoxy, cyano-3⁄4 alkyl, cyano- 3⁄4 alkoxy, unsubstituted or substituted by 1 to 3 phenyl groups independently selected from the group consisting of halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halo 4 alkoxy;
R3选自氢、 卤素、 氰基、 硝基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基或卤代 CrC4 烷氧基； R 3 is selected from the group consisting of hydrogen, halogen, cyano, nitro, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halogenated C r C 4 alkoxy;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氢、 卤素、 氰基、 硝基、 羟基、 氨基、 CrC4烷基、 卤代 CrC4烷基、 CrC4烷氧基 或卤代 CrC4烷氧基； n选自 0至 4的整数； 当 n大于 1时， 可相同或不同； Selected from hydrogen, halogen, cyano, nitro, hydroxy, amino, C r C 4 alkyl, halogenated C r C 4 alkyl, C r C 4 alkoxy or halogenated C r C4 alkoxy; n An integer selected from 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
3、 根据权利要求 2所述的用途， 其特征在于： 通式 (I-A)中  3. Use according to claim 2, characterized in that: in the formula (I-A)
选自氢、 甲基、 乙基、 环丙基或环己基；  Selected from hydrogen, methyl, ethyl, cyclopropyl or cyclohexyl;
R2选自氢、 氯、 溴、 甲基、 乙基、 氯甲基、 二氟甲基、 三氟甲基、 甲氧基甲基、 甲氧基、 乙氧基、 一氟甲氧基、 三氟甲氧基、 三氟乙氧基、 氰基甲基、 氰基甲氧基、 苯基、 对氯苯基、 对氟苯基、 对甲基苯基、 对三氟甲基苯基、 对甲氧基苯基、 对三氟甲氧基苯基、 2，4-二氯苯基 或 2，4-二甲基苯基； R3选自氢、 氯、 溴或甲基； R 2 is selected from the group consisting of hydrogen, chlorine, bromine, methyl, ethyl, chloromethyl, difluoromethyl, trifluoromethyl, methoxymethyl, methoxy, ethoxy, monofluoromethoxy, Trifluoromethoxy, trifluoroethoxy, cyanomethyl, cyanomethoxy, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, P-methoxyphenyl, p-trifluoromethoxyphenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl; R 3 is selected from the group consisting of hydrogen, chlorine, bromine or methyl;
E 、 R5选自氢： E and R 5 are selected from hydrogen:
选自氢、 氟、 氯、 溴、 碘、 氰基、 硝基、 羟基、 氨基、 甲基、 乙基、 正丙基、 异丙基、 正丁基、 异丁基、 仲丁基、 叔丁基、 三氟甲基、 二氟一氯甲基、 甲氧基、 乙氧基或三氟甲氧 基； n选自 0至 4的整数； 当 n大于 1时， 可相同或不同；  Selected from hydrogen, fluorine, chlorine, bromine, iodine, cyano, nitro, hydroxy, amino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl a group, a trifluoromethyl group, a difluoro-chloromethyl group, a methoxy group, an ethoxy group or a trifluoromethoxy group; n is selected from an integer of 0 to 4; when n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-、 -CH2CH2CH2-、 -CH(CH3)-或 -CH(CN) -。 A is selected from -CH 2 -, -CH 2 CH 2 -, -CH 2 CH 2 CH 2 -, -CH(CH 3 )- or -CH(CN)-.
4、 根据权利要求 3所述的用途， 其特征在于： 通式 (I-A)中  4. Use according to claim 3, characterized in that: in the formula (I-A)
选自甲基、 乙基或环丙基；  Selected from methyl, ethyl or cyclopropyl;
R2选自甲基、 乙基、 苯基、 对氯苯基、 对氟苯基、 对甲基苯基、 对三氟甲基苯基、 对甲 氧基苯基、 对三氟甲氧基苯基、 2，4-二氯苯基或 2，4-二甲基苯基； R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl, p-fluorophenyl, p-methylphenyl, p-trifluoromethylphenyl, p-methoxyphenyl, p-trifluoromethoxy Phenyl, 2,4-dichlorophenyl or 2,4-dimethylphenyl;
R3选自氢、 氯或甲基； R 3 is selected from the group consisting of hydrogen, chlorine or methyl;
E 、 R5选自氢； E and R 5 are selected from hydrogen;
选自氢、 氯、 溴、 甲基、 氰基、 三氟甲基、 二氟一氯甲基、 甲氧基、 乙氧基或三氟甲 氧基； n选自 0至 4的整数： 当 n大于 1时， 可相同或不同；  Selected from hydrogen, chlorine, bromine, methyl, cyano, trifluoromethyl, difluoromonochloromethyl, methoxy, ethoxy or trifluoromethoxy; n is selected from 0 to 4 integers: When n is greater than 1, it may be the same or different;
A选自 -CH2-、 -CH2CH2-或 -CH2CH2CH2-。 A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
5、 根据权利要求 4所述的用途， 其特征在于： 通式 (I-A)中  5. Use according to claim 4, characterized in that: in the formula (I-A)
选自甲基；  Selected from methyl;
R2选自甲基、 乙基、 苯基、 对氯苯基或对氟苯基； R 2 is selected from the group consisting of methyl, ethyl, phenyl, p-chlorophenyl or p-fluorophenyl;
R3选自氢、 氯或甲基； R 3 is selected from the group consisting of hydrogen, chlorine or methyl;
、 R5选自氢； , R 5 is selected from hydrogen;
选自氯、 三氟甲基或二氟一氯甲基； n选自 1至 3的整数；  Selected from chlorine, trifluoromethyl or difluoromonochloromethyl; n is selected from the integers from 1 to 3;
A选自 -CH2-、 -CH2CH2-或 -CH2CH2CH2-。 A is selected from -CH 2 -, -CH 2 CH 2 - or -CH 2 CH 2 CH 2 -.
6、 根据权利要求 1所述的用途， 其特征在于： 以通式 (I-A)所示的吡唑酰胺类化合物作为 组合物的活性组分， 组合物中活性组分的重量百分含量为 0.1-99%。  6. The use according to claim 1, characterized in that the pyrazole amide compound represented by the formula (IA) is used as an active component of the composition, and the weight percent of the active component in the composition is 0.1. -99%.
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