WO2023202545A1 - 二苯基吡唑类化合物作为除草剂增效剂的用途 - Google Patents

二苯基吡唑类化合物作为除草剂增效剂的用途 Download PDF

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WO2023202545A1
WO2023202545A1 PCT/CN2023/088824 CN2023088824W WO2023202545A1 WO 2023202545 A1 WO2023202545 A1 WO 2023202545A1 CN 2023088824 W CN2023088824 W CN 2023088824W WO 2023202545 A1 WO2023202545 A1 WO 2023202545A1
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alkyl
group
membered
herbicide
synergist
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PCT/CN2023/088824
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French (fr)
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刘吉元
张雅林
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西北农林科技大学
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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
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01P—BIOCIDAL, PEST REPELLANT, PEST ATTRACTANT OR PLANT GROWTH REGULATORY ACTIVITY OF CHEMICAL COMPOUNDS OR PREPARATIONS
    • A01P13/00—Herbicides; Algicides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
    • C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
    • C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the invention belongs to the technical field of pesticides, and specifically relates to the use of diphenylpyrazole compounds as herbicide synergists.
  • Weed damage is one of the main biological factors affecting the yield and quality of agricultural crops such as rice and wheat.
  • weeds in farmland mainly including barnyard grass, knotweed, sedge, Japanese wheatgrass, ryegrass, wild oats and setaria. Since 2,4-D was first used to control wheat fields and broadleaf weeds in 1946, chemical weeding on farmland has become an important part of modern agricultural production around the world.
  • Sulfonamides and aryloxyphenoxypropionates are two very representative types of herbicides that can control a variety of grass weeds (such as barnyardgrass, sedge, Japanese wheatgrass, ryegrass, etc.) and broadleaf weeds.
  • sulfonamides belong to the acetolactate synthase inhibitors, mainly including difluoresulfen, penoxsulam, fluflaflufen and saflufenacil; while aryloxyphenoxypropionates belong to the acetyl lactate synthase inhibitors.
  • Coenzyme A carboxylase inhibitors mainly include carboxypropyl, quizalofop, clodinafop-propyl, and cyhalofop-ethyl. These two types of herbicides have the remarkable characteristics of high efficiency, broad spectrum, and safety.
  • CYPs Cytochrome P450 monooxygenases
  • GSTs glutathione S-transferases
  • the resistance of Abutilon theophrasti to atrazine is due to the increased conjugation of glutathione with herbicides, which improves the detoxification ability of herbicides.
  • Alopecurus myosuroides enhanced metabolism and elimination of reactive oxygen species mediated by GSTs have been confirmed to be the main mechanisms of resistance.
  • the present invention proposes a new inhibitor targeting farmland weed GSTs.
  • the inhibitor has broad inhibitory activity against a variety of farmland weeds GSTs, and can effectively delay the in vivo metabolism of farmland weeds GSTs to herbicides, thereby reducing the metabolic resistance of farmland weeds to herbicides and effectively improving multifloral ryegrass,
  • Common farmland weeds such as wheatgrass and barnyardgrass in Japan are resistant to sulfonamide-based acetolactate synthase inhibitors and aryloxyphenoxypropionate-based acetyl-CoA carboxylase inhibitors, making them suitable for use as herbicide synergists. agent.
  • the object of the present invention is to provide the use of diphenyl pyrazole compounds of the following general formula (I) or their pesticide-acceptable salts as herbicide synergists.
  • the weight ratio of the herbicide to the synergist is 1:0.01-3000; more preferably, the weight ratio of the herbicide to the synergist is 1:0.02-2000; more preferably, the herbicide is 1:0.02-2000.
  • the weight ratio of the herbicide to the synergist is 1:0.03-2000; more preferably, the weight ratio of the herbicide to the synergist is 1:0.03-1500.
  • the relative resistance multiple of the weed to the herbicide is greater than 5; preferably, the relative resistance multiple of the weed to the herbicide is greater than 10; More preferably, the relative resistance multiple of the weeds to the herbicide is greater than 20; more preferably, the relative resistance multiple of the weed to the herbicide is greater than 30.
  • the synergist is a weed GSTs inhibitor.
  • the synergist has obvious inhibitory activity on the total enzymes of GSTs in weeds such as multiflora ryegrass, Japanese wheatgrass, barnyardgrass and other weeds.
  • the synergist delays or reduces the resistance of weeds to herbicides.
  • the herbicide is selected from: Category A: acetyl-CoA carboxylase inhibitor herbicides published by the Herbicide Resistance Action Committee (HRAC, The International Herbicide Resistance Action Committee); and Category B: acetolactate synthase Inhibitor herbicides.
  • acetyl-CoA carboxylase inhibitor herbicides include: Cyclohexanediones herbicides and Aryloxphenoxy-propionates herbicides;
  • the acetolactate synthase inhibitor herbicides include: triazolopyrimidine-type 1 herbicides, triazolopyrimidine-type 2 (Triazolopyrimidine-type 2) herbicides, imidazolinones (Imidazolinone) herbicides, Triazolinones (Triazolinones) herbicides, Sulfonylurea (Sulfonylurea) herbicides, Sulfonanilide (Sulfonanilides) herbicides, Pyrimidinyl benzoates (Pyrimidinyl benzoates) herbicides .
  • the herbicide is selected from the group consisting of clodinafop-propargyl and penoxsulam.
  • the weeds are selected from: wheat field weeds and rice field weeds.
  • the weeds are selected from the group consisting of Lolium multiflorum, Alopecurus japonicus, and Echinochloa crusgalli.
  • the weight ratio of clodinafop-propargyl to the synergist is 1:0.01-50; more preferably, the weight ratio of clodinafop-propargyl to the synergist is 1:0.02 ⁇ 30; More preferably, the weight ratio of clodinafop-propargyl and synergist is 1:0.02 ⁇ 20; More preferably, the weight ratio of clodinafop-propargyl and synergist is 1:0.02 ⁇ 10; More preferably, the weight ratio of clodinafop-propargyl and synergist is 1:0.03-6 (for example, it can be 1:0.03-2 or 1:0.25-4).
  • the weight ratio of penoxsulam to the synergist is 1:0.1 to 3000; more preferably, the weight ratio of penoxsulam to the synergist is The weight ratio of penoxsulam and synergist is 1:0.3 ⁇ 2000; more preferably, the weight ratio of penoxsulam and synergist is 1:0.5 ⁇ 1500 (for example, it can be 1:0.7 ⁇ 1450).
  • the application dosage of clodinafop-propargyl and synergist is 30 to 1000 mg/L: 150 to 250 mg/L, more preferably 30 to 1000 mg/L.
  • the application dosage of clodinafop-propargyl and synergist is 80 to 600 mg/L: 10 to 300 mg/L, more preferably 90 to 500 mg/L.
  • the application dosage of penoxsulam and synergist is 0.1 to 50 mg/L: 20 to 300 mg/L, more preferably 0.1 to 45 mg. /L: 20 to 250 mg/L, more preferably 0.12 to 40 mg/L: 22 to 220 mg/L (for example, 0.14 to 36 mg/L: 25 to 200 mg/L), more preferably 0.14 to 36 mg/L: 40 ⁇ 60mg/L.
  • the application dosage of clodinafop and synergist is 50 to 800 mg/L: 200 mg/L (i.e. clodinfen and synergist)
  • the dosage ratio of synergists is 1:0.25 ⁇ 4).
  • the application dosage of clodinafop-propargyl and synergist is 100-400 mg/L: 12.5-200 mg/L (i.e. The weight ratio of grass ester and synergist is 1:0.03 ⁇ 2).
  • the application dosage of penoxsulam and synergist is 0.14-36 mg/L: 25-200 mg/L (i.e. The weight ratio of penoxsulam and synergist is 1:0.7 ⁇ 1430); preferably, it is 0.14 ⁇ 36mg/L:40 ⁇ 60mg/L.
  • the diphenyl pyrazole compound of general formula (I) or its pesticide acceptable salt is:
  • R 1 can be:
  • the 6-14-membered aryl group, 5-14-membered heterocyclyl group or 5-14-membered heteroaryl group is unsubstituted or substituted by one or more of the following substituents: O, -OH, halogen, cyano group, nitro group , -CH(O), amino, -C 1 ⁇ 6 alkyl, -OC 1 ⁇ 6 alkyl, -C 1 ⁇ 6 alkyl -NH-C 1 ⁇ 6 alkyl, -C 1 ⁇ 6 alkyl- N(C 1 ⁇ 6 alkyl) 2 , -C(O)-OC 1 ⁇ 6 alkyl, -NH-C(O)-C 1 ⁇ 6 alkyl, -SO 2 -C 1 ⁇ 6 alkyl, -SO 2 -NH 2 , -SO 2 -NH-C 1 ⁇ 6 alkyl group, -SO 2 -N(C 1 ⁇ 6 alkyl) 2 , -6 ⁇ 14 membered aryl group, -5 ⁇
  • the heterocyclyl group (including 5 to 14 members, 5 to 10 members, and 5 to 8 members) contains 1 to 4 heteroatoms selected from N, S and O; the heteroaryl group (including 5 to 14 members) , 5 to 10 yuan, 5 to 8 yuan) containing 1 to 4 heteroatoms selected from N, S and O.
  • R 2 can be: -H, -halogen, -amino, -NO 2 , -CF 3 , -C 1 ⁇ 6 alkyl, -C 1 ⁇ 6 alkyl -OH, -OR 4 , -C(O)- R 4 , -C(O)-NH 2 , -NH-C(O)-R 4 , -C(O)-OR 4 or -C(O)-ON(R 4 ) 2 ;
  • R 4 can be: H or C 1-6 alkyl.
  • the substituent of the amide group is connected to the N atom of the amino group and/or is the same as the C atom of the carbonyl group; and when there are two substituents, the two substituents may be the same or different.
  • halogen refers to fluorine, chlorine, bromine or iodine as a substituent.
  • a halogen atom is used as a substituent, the number of substitutions There is more than one item, including 1, 2 or 3, etc.
  • alkyl group refers to a linear or branched alkyl group derived from an alkane by removing one hydrogen atom.
  • alkenyl group refers to a linear, branched or cyclic alkenyl group containing a carbon-carbon double bond.
  • alkynyl group refers to a linear, branched or cyclic alkynyl group containing a carbon-carbon triple bond.
  • cycloalkyl is a fully hydrogenated non-aromatic ring composed of a single, double or tricyclic ring.
  • a cycloalkyl group may be a monocyclic ring typically containing 3 to 7 ring atoms. Examples include, but are not limited to, cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkyl includes bridged bicycloalkyl systems.
  • alkyloxy group refers to a group derived from “alkyl” connected to other moieties through -O-.
  • aryl group refers to a cyclic aromatic group whose ring atoms are carbon atoms, including monocyclic aryl groups and condensed ring aryl groups.
  • Monocyclic aryl refers to a fully unsaturated aryl group
  • fused-cyclic aryl refers to an aryl group formed by two or more ring structures sharing two adjacent carbon atoms with each other, and at least one ring is fully unsaturated.
  • Aromatic cyclic group is a cyclic aromatic group whose ring atoms are carbon atoms, including monocyclic aryl groups and condensed ring aryl groups.
  • Monocyclic aryl refers to a fully unsaturated aryl group
  • fused-cyclic aryl refers to an aryl group formed by two or more ring structures sharing two adjacent carbon atoms with each other, and at least one ring is fully unsaturated.
  • Aromatic cyclic group is
  • heterocyclyl refers to a saturated or unsaturated non-aromatic group containing 1, 2, 3 or 4 heteroatoms (N, O or S) and composed of 1 to 3 rings.
  • heteroaryl refers to an aromatic ring structure, including monocyclic heteroaryl and condensed ring heteroaryl. Wherein at least one of the ring atoms is a heteroatom (N, O or S) and the remaining ring atoms are independently selected from carbon, oxygen, nitrogen and sulfur.
  • R 1 can be:
  • the heterocyclic group contains 1 to 3 heteroatoms selected from N, S and O; the heteroaryl group contains 1 to 3 heteroatoms selected from N, S and O.
  • R 2 can be: -H or halogen.
  • R 1 can be:
  • R 3 is selected from: -6 to 10-membered aryl, -5 to 10-membered heterocyclyl, -5 to 10-membered Heteroaryl; the R 3 is unsubstituted or substituted by one or more of the following substituents: O, -OH, halogen, cyano, nitro, -CH(O), -S-OH, amino, -C 1 ⁇ 3 alkyl, -OC 1 ⁇ 3 alkyl, nitro, sulfonic acid group, -C 1 ⁇ 3 alkyl-halogen, -C 1 ⁇ 3 alkyl-HS, -C 1 ⁇ 3 alkyl-NH 3 + , -C 1 ⁇ 3 alkyl-OH;
  • the heterocyclic group contains 1 to 3 heteroatoms selected from N, S and O; the heteroaryl group contains 1 to 3 heteroatoms selected from N, S and O;
  • R 2 can be: -H.
  • R 1 can specifically be:
  • the diphenyl pyrazole compound of general formula (I) or its pesticide-acceptable salt is the following compound or its pesticide-acceptable salt:
  • the preparation method of the diphenylpyrazole compound of general formula (I) or its pesticide acceptable salt of the present invention includes the following methods:
  • Compound A is hydrolyzed into its carboxylic acid form compound B, and then compound B and compound H 2 NR 1 are passed through a condensing agent.
  • a condensing agent In the solvent, an organic base or an inorganic base is added, and the mixture is condensed into compound (I) by stirring or heating at room temperature; where , the definitions of R 1 and R 2 are the same as mentioned above;
  • compound A is reacted with hydrazine hydrate to generate hydrazide compound C, or compound A is hydrolyzed into compound B, compound B reacts with hydrazine hydrate to generate hydrazide compound C, and then compound C and compound COOH-R 5 are passed through a condensing agent, in Add an organic base or inorganic base to the solvent, and stir or heat to condense at room temperature to form compound (I); wherein, R 2 is the same as above, and R 5 is: (a)-C 1 to 6 alkyl-R 3 , -C 3 ⁇ 8 cycloalkyl-R 3 , -C 2 ⁇ 6 alkenyl-R 3 , -C 2 ⁇ 6 alkynyl-R 3 , -NH-R 3 , -N( R 3 ) 2 , -C (O)-R 3 , -NH-C 1 ⁇ 6 alkyl-R 3 , -C 1 ⁇ 6 alkyl-NH-R 3 ,
  • the condensation agents include but are not limited to: active esters, carbodiimides, onium salts, organic phosphorus, and other condensation agents.
  • the solvents include but are not limited to: N,N-dimethylformamide, dichloromethane, acetonitrile, and tetrahydrofuran.
  • the organic base includes but is not limited to: triethylamine, diisopropylethylamine, etc.
  • the inorganic base includes but is not limited to: sodium carbonate, potassium carbonate, sodium hydroxide, sodium bicarbonate, etc.
  • the present invention provides a diphenyl pyrazole compound of general formula (I) or a pesticide-acceptable salt thereof, which can be used as a herbicide synergist.
  • the synergist is a weed GSTs inhibitor and has a wide range of effects on weed GSTs. Inhibitory activity, significantly improves the sensitivity of weed-resistant strains to a variety of herbicides and the effectiveness of herbicides, and plays an important role in weed resistance management.
  • Figure 1 is a graph showing the inhibition curve of compound PXG22 on the total enzyme activity of Lolium multiflorum GSTs.
  • Figure 2 is a graph showing the inhibition curve of compound PXG22 on the total enzyme activity of Japanese Kanmai Niang GSTs.
  • Figure 3 is a graph showing the inhibition curve of compound PXG22 on the total enzyme activity of barnyardgrass GSTs.
  • hydrazide compound C1 First add compound A1 into a 100 ml three-necked bottle (preparation reference of A1: J.Org.Chem.2010, 75, 3,984–987. HNMR (400MHz, CDCl3): ⁇ 3. 83(s,3H),7.33-7.36(m,2H),7.41-7.50(m,7H),7.87(m,2H). The same below), 10g, 100ml absolute ethanol, 20ml hydrazine hydrate, heated to reflux overnight , cooling and suction filtration to obtain compound C1, 9.5g, yield 95%.
  • Preparation Example 2 Compound PXG22 and pesticide-appropriate excipients are prepared into a microemulsion, and then added to water together with the herbicide to obtain an application preparation.
  • Lolium multiflorum and Alopecurus japonicus Mix the sieved soil that has not been used with any herbicides and the nutrient medium at a ratio of 1:1 and put it into a plastic pot. Use the bottom of the pot. Infiltration irrigation methods keep the soil moist. Sow 10 germinated weed seeds in each pot and cover with 0.5-1cm of soil. After sowing, wait for the seedlings of multiflora ryegrass and Japanese ryegrass to reach 15cm, and then collect the weeds.
  • Echinochloa crusgalli Echinochloa crusgalli seeds were collected from rice fields in Hefengqiao Township, Shangcheng County, Xinyang City, Henan province in 2019. Mix the sifted soil that has not been used with any herbicides and the nutrient medium at a ratio of 1:1 and put it into a plastic pot. Use the infiltration irrigation method at the bottom of the pot to keep the soil moist. Sow 8 seeds of weeds for germination in each pot and cover them with soil 0.5-1cm. Place in a greenhouse (temperature: 30°C during the day, 20°C at night; photoperiod: 12D/12L) for cultivation. After sowing, wait until the barnyardgrass grows to the 3-4 leaf stage, and then collect the weeds.
  • ⁇ A 340c is the change of control group A 340 within 5 minutes
  • ⁇ A 340t is the change of experimental group A 340 within 5 minutes.
  • the diphenylpyrazole compound of the general formula (I) of the present invention or its pesticide-acceptable salt has obvious inhibitory activity on the total enzymes of GSTs of various farmland weeds, and can reduce the incidence of Japanese wheatgrass and multiflora. Total enzyme activity of GSTs in farmland weeds such as ryegrass and barnyardgrass.
  • the multifloral ryegrass used for the test was collected from the wheat fields of Liuzhuang, Yicheng District, Zhumadian in 2019.
  • the relative resistance multiple of the multifloral ryegrass used for the test to clodinafoprin was 28.12, indicating high resistance (Table 1).
  • the detection method refers to the "Pesticide Indoor Bioassay Test Guidelines" with slight modifications. Mix the sifted soil that has not been used with any herbicides and the nutrient medium at a ratio of 1:1 and put it into a plastic pot. Use the infiltration irrigation method at the bottom of the pot to keep the soil moist. Sow 10 germinated Lolium multiflorum seeds in each pot and cover them with 0.5-1cm of soil.
  • the fresh weight inhibition rate is calculated as follows:
  • Fresh weight inhibition rate (%) (fresh weight of control weeds – fresh weight of treated weeds)/fresh weight of control weeds ⁇ 100
  • DPS software was used to conduct a significance test (Duncan's new multiple range method) analysis, and the ED 50 (The effective rate of herbicide causing 50% inhibition in fresh weight) of propargyl on the fresh weight of Lolium multiflorum was calculated.
  • the fresh weight inhibition rate of 800 mg/L propargyl on multifloral ryegrass reached 56.86%, which was significantly higher than other treatments and the control (without the addition of compound PXG22);
  • the ED 50 is 306.04mg/L, which is at least 61.75% lower than the ED 50 when clodinafop-propargyl is used alone.
  • the diphenyl pyrazole compound of the general formula (I) of the present invention or its pesticide acceptable salt has a significant synergistic effect on the control of multiflora ryegrass by clodinafop-propyl.
  • the Japanese wheatgrass used for the test was collected from the Xinyang Luoshan wheat field in 2019.
  • the relative resistance fold of the Japanese wheatgrass used for the test to clodinafop-propargyl was 41.51, indicating high resistance (Table 3).
  • the detection method refers to the "Pesticide Indoor Bioassay Test Guidelines" with slight modifications. Mix the sifted soil that has not been used with any herbicides and the nutrient medium at a ratio of 1:1 and put it into a plastic pot. Use the infiltration irrigation method at the bottom of the pot to keep the soil moist. Sow 10 germinated Japanese wheatgrass seeds in each pot and cover them with 0.5-1cm of soil.
  • Fresh weight inhibition rate (%) (fresh weight of control weeds – fresh weight of treated weeds)/fresh weight of control weeds ⁇ 100
  • DPS software was used to conduct a significance test (Duncan's new multiple range method) analysis, and the ED 50 of propargyl on the fresh weight of Japanese wheatgrass was calculated.
  • the ED 50 of clodinafopil when used alone against Japanese phylloxera is 523.96 mg/L.
  • clodinyl and compound PXG22 are mixed and sprayed, different amounts of compound PXG22 have a synergistic effect on clodinyl.
  • compound PXG22 is added in an amount of 12.5 to 200 mg/L, the synergistic effect on clodinafop-propargyl at doses of 100 mg/L, 200 mg/L, and 400 mg/L is significant.
  • the ED 50 of clodinafop-propargyl against Japanese wheatgrass are 389.67 mg/L, 412.44 mg/L, 321.60 mg/L, 289.00 mg/L and 282.62 mg/L respectively.
  • the ED 50 of Japanese wheatgrass was reduced by 25.63%, 21.28%, 38.62%, 44.84%, and 46.06% respectively when compared with clodinafopil when used alone.
  • the diphenyl pyrazole compound of the general formula (I) of the present invention or its pesticide acceptable salt has a significant synergistic effect on clodinafop-propargyl in the control of Japanese wheatgrass.
  • the barnyardgrass Echinochloa crusgalli used for the test was collected from the rice fields of Hefengqiao Township, Shangcheng County, Xinyang City, Henan province in 2019.
  • the relative resistance multiple of the barnyardgrass used for the test to penoxsulam was 28.37, indicating high resistance (Table 5).
  • the detection method refers to "Pesticides Guidelines for indoor bioassay testing, with minor modifications. Mix the sifted soil that has not been used with any herbicides and the nutrient medium at a ratio of 1:1 and put it into a plastic pot. Use the infiltration irrigation method at the bottom of the pot to keep the soil moist.
  • a spray tower to spray the stems and leaves (3WP-2000 walking spray tower from the Nanjing Agricultural Mechanization Research Institute of the Ministry of Agriculture, TP6501 fan-shaped nozzle, spray The height is 300mm, and the liquid volume is 450L/hm 2 ).
  • Compound PXG22 is added to the prepared herbicide, mixed and then sprayed. After spraying, the mixture is placed in a greenhouse to continue culturing.
  • Fresh weight inhibition rate (%) (fresh weight of control weeds – fresh weight of treated weeds)/fresh weight of control weeds ⁇ 100
  • DPS software was used to conduct a significance test (Duncan's new multiple range method) analysis, and the ED 50 of penoxsulam on the fresh weight of barnyard grass was calculated.
  • the ED 50 of penoxsulam against barnyardgrass is 3.44mg/L, 1.84mg/L, 1.90mg/L and 2.74 respectively. mg/L, compared with penoxsulam alone, the ED50 of barnyardgrass was reduced by 31.91%, 63.49%, 62.38% and 45.71% respectively.
  • the compound PXG22 is added at a concentration of 50 mg/L, it has the best synergistic effect on penoxsulam in controlling barnyardgrass.
  • the diphenyl pyrazole compound of the general formula (I) of the present invention or its pesticide-acceptable salt has a significant synergistic effect on penoxsulam in controlling barnyardgrass.

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Abstract

本发明提供通式（I）所示的二苯基吡唑类化合物或其农药上可接受的盐作为除草剂增效剂的用途，其为靶向农田杂草GSTs的抑制剂，可有效延缓农田杂草GSTs对除草剂的体内代谢，从而降低农田杂草对除草剂的代谢抗性，有效改善常见农田杂草对A类除草剂和B类除草剂的抗药性，适合用作除草剂的增效剂。

Description

二苯基吡唑类化合物作为除草剂增效剂的用途 技术领域
本发明属于农药技术领域，具体涉及二苯基吡唑类化合物作为除草剂增效剂的用途。
背景技术
杂草危害是影响水稻、小麦等农业作物产量与质量的主要生物因素之一。我国农田杂草种类繁多，主要有稗、节节草、莎草、日本看麦娘、黑麦草、野燕麦以及狗尾草等。自1946年2,4-D最先被用于防除麦田及阔叶杂草以来，农田化学除草已成为全球现代农业生产的重要组成部分。磺酰胺类和芳氧苯氧丙酸酯类是非常有代表性的两类除草剂，可防治多种禾本科杂草(如稗、莎草、日本看麦娘、黑麦草等)和阔叶杂草(如田菁、鸭舌草、竹节花等)。其中，磺酰胺类属于乙酰乳酸合成酶抑制剂，主要有双氟磺草胺、五氟磺草胺、啶黄草胺和唑嘧磺草胺等；而芳氧苯氧丙酸酯类属于乙酰辅酶A羧化酶抑制剂，主要有精噁唑禾草灵、精喹禾灵、炔草酯和氰氟草酯等。这两类除草剂具有高效、广谱、安全的显著特点，目前已广泛应用于麦田、稻田以及玉米田等农田常见杂草的防除，在果园、菜地等农业场所的杂草防除中也有着较多应用。然而，由于过度依赖和长期使用相对有限的化学除草剂，杂草抗药性问题越来越突出，已成为农田杂草高效治理的主要制约因素之一。杂草抗药性的发生和发展不仅严重影响了除草剂的使用寿命，同时还会导致除草剂使用次数和剂量的增加，给人类造成巨大损失。如何有效治理杂草抗药性已成为杂草防除领域亟待解决的难题。
杂草种群的个体多实性、易变性及多型性是其对除草剂产生抗性的内在因素。除草剂的筛选压力会促使杂草体内做出一系列代谢反应，通过阻止除草剂活性分子达到靶标位点、消除除草剂的毒害作用或者两方面综合作用等使得杂草能够忍受除草剂的伤害。细胞色素P450单加氧酶(CYPs)和谷胱甘肽S-转移酶(GSTs)是与除草剂代谢有关的生物酶。其中，GSTs既可直接代谢除草剂活性分子，又可催化CYPs代谢产物与谷胱甘肽的轭合，在除草剂代谢过程中扮演着重要角色。苘麻Abutilon theophrasti对莠去津产生抗性是由于谷胱甘肽与除草剂轭合作用的增加，提高了对除草剂的解毒能力。在鼠尾看麦娘Alopecurus myosuroides中，GSTs介导的代谢作用增强和活性氧消除已被证实是其抗性产生的主要机制。此外，在抗芳氧苯氧丙酸酯类除草剂精噁唑禾草灵的马唐、瑞士黑麦草、野燕麦等杂草中也存在GSTs活性升高的现象，被认为是抗性产生的原因之一。
鉴于GSTs在除草剂代谢中的重要作用，降低杂草体内GSTs的活性可有效延缓除草剂在防治对象体内的代谢速度。研发靶向杂草GSTs的抑制剂不但可以提高除草剂的防治效果，还可延缓抗药性的产生，延长除草剂的使用寿命，对杂草的化学防除具有重要意义。
发明内容
本发明提出一种靶向农田杂草GSTs的新型抑制剂。该抑制剂对多种农田杂草GSTs具有广泛的抑制活性，可有效延缓农田杂草GSTs对除草剂的体内代谢，从而降低农田杂草对除草剂的代谢抗性，有效改善多花黑麦草、日本看麦娘和稗等常见农田杂草对磺酰胺类乙酰乳酸合成酶抑制剂和芳氧苯氧丙酸酯类乙酰辅酶A羧化酶抑制剂的抗药性，适合用作除草剂的增效剂。
因此，本发明的目的是提供下述通式(I)二苯基吡唑类化合物或其农药学上可接受的盐作为除草剂增效剂的用途。
优选地，所述除草剂与增效剂的重量份用量比例为1:0.01～3000；更优选地，除草剂与增效剂的重量份用量比例为1:0.02～2000；更优选地，除草剂与增效剂的重量份用量比例为1:0.03～2000；更优选地，除草剂与增效剂的重量份用量比例为1:0.03～1500。
所述杂草对除草剂的相对抗性倍数大于5；优选地，杂草对除草剂的相对抗性倍数大于10； 更优选地，杂草对除草剂的相对抗性倍数大于20；更优选地，杂草对除草剂的相对抗性倍数大于30。
优选地，所述增效剂为杂草GSTs抑制剂。优选地，所述增效剂对多花黑麦草、日本看麦娘、稗等杂草的GSTs总酶有明显的抑制活性。
优选地，所述增效剂延缓或者降低杂草对除草剂的抗药性。
所述除草剂选自：除草剂抗性行动委员会(HRAC，The International Herbicide Resistance Action Committee)公布的第A类：乙酰辅酶A羧化酶抑制剂类除草剂；和第B类：乙酰乳酸合成酶抑制剂类除草剂。
所述乙酰辅酶A羧化酶抑制剂类除草剂包括：环己二酮(Cyclohexanediones)类除草剂、芳氧苯氧基丙酸酯(Aryloxphenoxy-propionates)类除草剂；
所述乙酰乳酸合成酶抑制剂类除草剂包括：三唑并嘧啶-1型(Triazolopyrimidine–type 1)类除草剂、三唑并嘧啶-2型(Triazolopyrimidine–type 2)类除草剂、咪唑啉酮(Imidazolinone)类除草剂、三唑啉酮(Triazolinones)类除草剂、磺脲(Sulfonylurea)类除草剂、磺酰苯胺(Sulfonanilides)类除草剂、嘧啶基苯甲酸酯(Pyrimidinyl benzoates)类除草剂。
优选地，所述除草剂选自：炔草酯、五氟磺草胺。
所述杂草选自：麦田杂草、稻田杂草。
优选地，所述杂草选自：多花黑麦草(Lolium multiflorum)、日本看麦娘(Alopecurus japonicus)、稗(Echinochloa crusgalli)。
优选地，当所述除草剂为炔草酯时，炔草酯与增效剂的重量份用量比例为1:0.01～50；更优选地，炔草酯与增效剂的重量份用量比例为1:0.02～30；更优选地，炔草酯与增效剂的重量份用量比例为1:0.02～20；更优选地，炔草酯与增效剂的重量份用量比例为1:0.02～10；更优选地，炔草酯与增效剂的重量份用量比例为1:0.03～6(例如，可以为1:0.03～2或1:0.25～4)。
优选地，当所述除草剂为五氟磺草胺时，五氟磺草胺与增效剂的重量份用量比例为1:0.1～3000；更优选地，五氟磺草胺与增效剂的重量份用量比例为1:0.3～2000；更优选地，五氟磺草胺与增效剂的重量份用量比例为1:0.5～1500(例如，可以为1:0.7～1450)。
优选地，当除草剂为炔草酯，杂草为多花黑麦草时，炔草酯与增效剂的施用量为30～1000mg/L:150～250mg/L，更优选为30～1000mg/L:180～220mg/L，更优选为40～900mg/L:190～210mg/L(例如，可以为50～800mg/L:200mg/L)。
优选地，当除草剂为炔草酯，杂草为日本看麦娘时，炔草酯与增效剂的施用量为80～600mg/L:10～300mg/L，更优选为90～500mg/L:10～250mg/L，更优选为90～450mg/L:12～220mg/L(例如，可以为100～400mg/L:12.5～200mg/L)。
优选地，当除草剂为五氟磺草胺，杂草为稗时，五氟磺草胺与增效剂的施用量为0.1～50mg/L:20～300mg/L，更优选为0.1～45mg/L:20～250mg/L，更优选为0.12～40mg/L:22～220mg/L(例如，可以为0.14～36mg/L:25～200mg/L)，更优选为0.14～36mg/L:40～60mg/L。
在一个具体实施方式中：当除草剂为炔草酯、杂草为多花黑麦草时，炔草酯与增效剂的施用量为50～800mg/L:200mg/L(即炔草酯与增效剂的重量份用量比例为1:0.25～4)。
在另一具体实施方式中：当除草剂为炔草酯，杂草为日本看麦娘时，炔草酯与增效剂的施用量为100～400mg/L:12.5～200mg/L(即炔草酯与增效剂的重量份用量比例为1:0.03～2)。
在又一具体实施方式中：当除草剂为五氟磺草胺，杂草为稗时，五氟磺草胺与增效剂的施用量为0.14～36mg/L:25～200mg/L(即五氟磺草胺与增效剂的重量份用量比例为1:0.7～1430)；优选为0.14～36mg/L:40～60mg/L。
所述通式(I)二苯基吡唑类化合物或其农药学上可接受的盐为：
其中：
R1可以为：
(1)未取代或者被下述一个或多个取代基取代的酰胺基-NH-CH(O)；
(a)-C1～6烷基-R3、-C3～8环烷基-R3、-C2～6烯基-R3、-C2～6炔基-R3、-NH-R3、-N(R3)2、-C(O)-R3、-NH-C1～6烷基-R3、-C1～6烷基-NH-R3、-C1～6烷基-N(R3)2、-C1～6烷基-O-R3、-C3～8环烷基-O-R3、-O-C1～6烷基-R3、-C1～6烷基-O-C1～6烷基-R3、-C(O)-NH-R3、-C(O)-N(R3)2、-NH-C(O)-R3、-C1～6烷基-NH-C(O)-R3、-C1～6烷基-NH-C(O)-O-R3、-NH-C(O)-C1～6烷基-R3、-NH-C(O)-C1～6烷基-O-R3、-C(O)-NH-C1～6烷基-R3或-C1～6烷基-S-R3；
所述R3各自独立地选自：H、O、S、＝NH、氨基、卤素、氰基、-C1～6烷基、-C3～8环烷基、-S-C1～6烷基、-S-OH、-SO2-C1～6烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基和-金刚烷基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-C2～6烯基、-C2～6炔基、-O-C1～6烷基、硝基、磺酸基、-C1～6烷基-卤素、-C1～6烷基-HS、-C1～6烷基-NH3 +、-C1～6烷基-OH、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2；
(b)-6～14元芳基、-5～14元杂环基或-5～14元杂芳基；
所述6～14元芳基、5～14元杂环基或5～14元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-O-C1～6烷基、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2、-C(O)-O-C1～6烷基、-NH-C(O)-C1～6烷基、-SO2-C1～6烷基、-SO2-NH2、-SO2-NH-C1～6烷基、-SO2-N(C1～6烷基)2、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基；
(2)酰胺基-NH-CH(O)的N原子与C原子通过-C3～6亚烷基-、-NH-C2～6亚烷基-、-NH-C(O)-C1～6亚烷基-、-C1～6亚烷基-NH-C(O)-、-NH-C1～6亚烷基-C(O)-或-C1～6亚烷基-C(O)-连接成环状结构；该环状结构任选被下述取代基取代：-C1～6烷基、-C3～8环烷基、-C3～8环烷基-C1～6烷基、-O-C1～6烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基、-C1～6烷基-6～14元芳基、-C1～6烷基-5～14元杂环基、-C1～6烷基-5～14元杂芳基、三氟乙基；所述6～14元芳基、5～14元杂环基和5～14元杂芳基任选被-O-C1～6烷基取代；或者，所述环状结构进一步与5～8元芳基、5～8元杂环基或5～8元杂芳基并合为稠环。
所述杂环基(包括5～14元、5～10元、5～8元)含有1～4个选自N、S和O中的杂原子；所述杂芳基(包括5～14元、5～10元、5～8元)含有1～4个选自N、S和O中的杂原子。
R2可以为：-H、-卤素、-氨基、-NO2、-CF3、-C1～6烷基、-C1～6烷基-OH、-O-R4、-C(O)-R4、-C(O)-NH2、-NH-C(O)-R4、-C(O)-O-R4或-C(O)-O-N(R4)2；R4可以为：H或C1～6烷基。
所述酰胺基的取代基与氨基的N原子相连和/或与羰基的C原子相同；且为2个取代基时，2个取代基可以相同或不同。
所述“卤素”是指作为取代基的氟、氯、溴或碘。当卤原子作为取代基的时候，其取代的数 目为一个以上，包括1个、2个或3个等。
所述“烷基”是指烷烃上去除一个氢原子衍生的直链或支链的烷基。
所述“烯基”是指含有碳碳双键的直链或支链或环状的烯基。
所述“炔基”是指含有碳碳三键的直链或支链或环状的炔基。
所述“环烷基”是由单、双或三环构成的完全氢化的非芳香族环。因此，环烷基可为典型地含有3至7个环原子的单环。实例包括但不限于环丙基、环丁基、环戊基及环己基。同时，“环烷基”也包括桥联双环烷基系统。
所述“烷基氧基”是指“烷基”通过-O-与其它部分相连接所衍生的基团。
所述“芳基”是指环原子为碳原子的环状芳香基团，包括单环芳基和稠环芳基。单环芳基是指全部不饱和的芳基，稠环芳基是指由两个或两个以上环状结构彼此共用两个相邻的碳原子所形成的，至少有一个环全部不饱和的芳香环的环状基团。
所述“杂环基”是指含有1、2、3或4个杂原子(N、O或S)，由1至3个环构成的饱和或不饱和的非芳香基团。
所述“杂芳基”是指芳香族环结构，包括单环杂芳基和稠环杂芳基。其中所述环原子中的至少一者为杂原子(N、O或S)且其余环原子独立地选自碳、氧、氮及硫。
优选地，R1可以为：
(1)被下述一个或多个取代基取代的酰胺基-NH-CH(O)，
(a)-C1～3烷基-R3、-C3～6环烷基-R3、-C2～5烯基-R3、-C1～3烷基-NH-R3、-C1～3烷基-O-R3、或-O-C1～3烷基-R3；所述R3各自独立地选自：H、O、S、＝NH、氨基、卤素、氰基、-C1～3烷基、-C3～6环烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、-S-OH、氨基、-C1～3烷基、-C2～5烯基、-C2～5炔基、-O-C1～3烷基、硝基、磺酸基、-C1～3烷基-卤素、-C1～3烷基-OH；
(b)-6～14元芳基、-5～14元杂环基或-5～14元杂芳基；所述6～14元芳基、5～14元杂环基或5～14元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～3烷基、-O-C1～3烷基、-C1～3烷基-NH-C1～3烷基、-C1～3烷基-N(C1～3烷基)2、-C(O)-O-C1～3烷基、-NH-C(O)-C1～3烷基、-SO2-C1～3烷基、-SO2-NH2、-SO2-NH-C1～3烷基、-SO2-N(C1～3烷基)2；
(2)酰胺基-NH-CH(O)的N原子与C原子通过-C3～6亚烷基-、-NH-C2～4亚烷基-、-NH-C(O)-C1～3亚烷基-、-C1～3亚烷基-NH-C(O)-、-NH-C1～3亚烷基-C(O)-或-C1～3亚烷基-C(O)-连接成环状结构，该环状结构任选被下述取代基取代：-C1～3烷基、-C3～6环烷基、-C3～6环烷基-C1～3烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基、-C1～3烷基-6～14元芳基、-C1～3烷基-5～14元杂环基、-C1～3烷基-5～14元杂芳基、三氟乙基；所述6～14元芳基、5～14元杂环基、5～14元杂芳基任选被-O-C1～3烷基取代；
所述杂环基含有1～3个选自N、S和O中的杂原子；所述杂芳基含有1～3个选自N、S和O中的杂原子。
R2可以为：-H或卤素。
更优选地，R1可以为：
(1)-NH-C(O)-C1～3烷基-R3；所述R3选自：-6～10元芳基、-5～10元杂环基、-5～10元杂芳基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、-S-OH、氨基、-C1～3烷基、-O-C1～3烷基、硝基、磺酸基、-C1～3烷基-卤素、-C1～3烷基-HS、-C1～3烷基-NH3 +、-C1～3烷基-OH；
(2)-NH-C(O)-6～10元芳基、-NH-C(O)-5～10元杂环基或-NH-C(O)-5～10元杂芳基；所述6～10元芳基、5～10元杂环基或5～10元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～3烷基、-O-C1～3烷基；
所述杂环基含有1～3个选自N、S和O中的杂原子；所述杂芳基含有1～3个选自N、S和O中的杂原子；
R2可以为：-H。
更优选地，R1具体可以为：
在具体实施方案中，所述的通式(I)二苯基吡唑类化合物或其农药学上可接受的盐为以下化合物或其农药学上可接受的盐：


优选地，为下述化合物或其农药学上可接受的盐：

本发明通式(I)二苯基吡唑类化合物或其农药学上可接受的盐的制备方法，包括以下方法：
将化合物A水解成其羧酸形式化合物B，然后化合物B与化合物H2N-R1通过缩合剂，在溶剂中，加入有机碱或无机碱，通过室温搅拌或加热，缩合成化合物(I)；其中，R1和R2的定义与前述相同；
或者，
将化合物A与水合肼反应生成酰肼类化合物C，或者将化合物A水解成化合物B，化合物B与水合肼反应生成酰肼类化合物C，然后化合物C与化合物COOH-R5通过缩合剂，在溶剂中，加入有机碱或无机碱，通过室温搅拌或加热缩合成化合物(I)；其中，R2的定义与前述相同，R5为：(a)-C1～6烷基-R3、-C3～8环烷基-R3、-C2～6烯基-R3、-C2～6炔基-R3、-NH-R3、-N(R3)2、-C(O)-R3、-NH-C1～6烷基-R3、-C1～6烷基-NH-R3、-C1～6烷基-N(R3)2、-C1～6烷基-O-R3、-C3～8环烷基-O-R3、-O-C1～6烷基-R3、-C1～6烷基-O-C1～6烷基-R3、-C(O)-NH-R3、-C(O)-N(R3)2、-NH-C(O)- R3、-C1～6烷基-NH-C(O)-R3、-C1～6烷基-NH-C(O)-O-R3、-NH-C(O)-C1～6烷基-R3、-NH-C(O)-C1～6烷基-O-R3、-C(O)-NH-C1～6烷基-R3或-C1～6烷基-S-R3；
所述R3各自独立地选自：H、O、S、＝NH、氨基、卤素、氰基、-C1～6烷基、-C3～8环烷基、-S-C1～6烷基、-S-OH、-SO2-C1～6烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基、-金刚烷基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-C2～6烯基、-C2～6炔基、-O-C1～6烷基、硝基、磺酸基、-C1～6烷基-卤素、-C1～6烷基-HS、-C1～6烷基-NH3 +、-C1～6烷基-OH、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2；(b)-6～14元芳基、-5～14元杂环基或-5～14元杂芳基；所述6～14元芳基、5～14元杂环基或5～14元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-O-C1～6烷基、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2、-C(O)-O-C1～6烷基、-NH-C(O)-C1～6烷基、-SO2-C1～6烷基、-SO2-NH2、-SO2-NH-C1～6烷基、-SO2-N(C1～6烷基)2、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基；所述杂环基含有1～4个选自N、S和O中的杂原子；所述杂芳基含有1～4个选自N、S和O中的杂原子。
所述缩合剂包括但不限于：活性酯、碳二亚胺类、鎓盐类、有机磷类、其它的缩合剂。
所述溶剂包括但不限于：N,N-二甲基甲酰胺、二氯甲烷、乙腈、四氢呋喃。
所述有机碱包括但不限于：三乙胺、二异丙基乙基胺等。
所述无机碱包括但不限于：碳酸钠、碳酸钾、氢氧化钠、碳酸氢钠等。
化合物A的合成参考文献(J.Org.Chem.2010,75,3,984–987)获得。
本申请是中国专利申请CN2021107606474和PCT国际申请PCT/CN/2021/105643的后续申请，前述两件申请的所有内容以引用的方式并入到本申请中。
本发明提供通式(I)二苯基吡唑类化合物或其农药学上可接受的盐可以作为除草剂增效剂，该增效剂是杂草GSTs抑制剂，对杂草GSTs有广泛的抑制活性，显著提高杂草抗性品系对多种除草剂的敏感性和除草剂的有效性，对杂草抗药性治理有重要作用。
附图说明
图1为化合物PXG22对多花黑麦草GSTs总酶活性的抑制曲线图。
图2为化合物PXG22对日本看麦娘GSTs总酶活性的抑制曲线图。
图3为化合物PXG22对稗GSTs总酶活性的抑制曲线图。
具体实施方式
下面通过实施例对本发明进行说明，但本发明并不限于此。下述实施例中所示实验方法，如无特殊说明，均为常规方法。所示试剂和材料，均为市售产品。
制备实施例1：化合物PXG22的制备
方法1：
(1)酰肼化合物C1的制备：向100ml的三口瓶中先投化合物A1(A1的制备参考文献：J.Org.Chem.2010,75,3,984–987。HNMR(400MHz,CDCl3):δ3.83(s,3H),7.33-7.36(m,2H),7.41-7.50(m,7H),7.87(m,2H)。下同)，10g，无水乙醇100ml，水合肼20ml，加热回流过夜，冷却抽滤，得化合物C1，9.5g，收率95％。
(2)向100ml三口瓶中投化合物F22(羧酸)(3.40g,1eq)，DMF 10ml，EDCI(4.14g,1.2eq)，碳酸钾(6.21g,2.5eq)，搅拌10分钟后投化合物C1(酰肼)(5.5g,1.1eq)，室温搅拌过夜，TLC反应完全，后处理，用水稀释，滤出形成的沉淀物并干燥，粗化合物经反相HPLC纯化，无需另外用洗脱液甲醇-水处理，合并选定的馏分并浓缩，得到目标产物PXG22。
或者，方法2：
(1)化合物B1的制备：向100ml的三口瓶中先投化合物A1，10g，无水乙醇100ml，10％NaOH 28.7ml(2eq)，加热回流5小时，反应完全冷却，用10％盐酸调节pH＝2-3，抽滤，得化合物B1，8g收率85％。
(2)向100ml三口瓶中投化合物B1(羧酸)(6.5g,1eq)，DMF10ml，EDCI(5.75g,1.2eq)，碳酸钾(8.63g,2.5eq)，搅拌10分钟后投化合物G22(酰肼)(5.58g,1.1eq)，室温搅拌过夜，TLC反应完全，后处理，用水稀释，滤出形成的沉淀物并干燥，粗化合物经反相HPLC纯化，无需另外用洗脱液甲醇-水处理，合并选定的馏分并浓缩，得到目标产物PXG22。
MS(ES-API)cacld.for C26H19N5O3found 450.2[M+1]+；HNMR(400MHz,DMSO):δ1.05(s,1H),2.45(m,5H),3.2(s,5H),6.6(s,1H),7.05-7.5(m,15H),8.05(s,1H),10.0(s,1H),10.4(s,1H),12.05(s,1H).
制备实施例2：将化合物PXG22与农药学上合适的辅料制备成微乳，然后和除草剂一起加入到水中，即得施用制剂。
实验实施例1：化合物PXG22对多花黑麦草、日本看麦娘及稗的GSTs总酶的抑制活性检测
多花黑麦草(Lolium multiflorum)和日本看麦娘(Alopecurus japonicus)：将未使用过任何除草剂的过筛土与营养基质按1:1混匀后装入塑料盆钵中，采用盆钵底部渗灌方法保持土壤湿润。每盆播种催芽的杂草种子10粒并覆土0.5-1cm。播种后待多花黑麦草和日本看麦娘出苗至15cm，收集杂草。
稗(Echinochloa crusgalli)：稗的种子2019年采集于河南信阳市商城县河凤桥乡水稻田。 将未使用过任何除草剂的过筛土与营养基质按1:1混匀后装入塑料盆钵中，采用盆钵底部渗灌方法保持土壤湿润。每盆播种催芽的杂草8粒并覆土0.5-1cm。置于温室(温度：白天30℃，夜间20℃；光照周期：12D/12L)培养。播种后待稗生长至3-4叶期，收集杂草。
在研钵中使用液氮将杂草研磨，加入1mL的100mM磷酸钠缓冲液(pH7.2，含1mM EDTA)进行匀浆。将匀浆液转移至1.5mL离心管中在4℃、14,000g下离心30min，将上清液转移至新的离心管中作为酶源。使用BCA蛋白浓度测定试剂盒对所得上清溶液进行蛋白浓度测定。
取100μL包含有1mM GSH的磷酸钠缓冲液(100mM，pH7.2)于96孔板中，每孔分别加入5μg GSTs总酶和1μL化合物PXG22(化合物PXG22的终浓度分别为200μM、100μM、50μM、25μM、12.5μM、6.25μM)，均匀混合后于30℃静置10min。之后每孔加入100μL含有1mM CDNB的磷酸钠缓冲液(100mM，pH7.2)。混匀后立刻放入酶标仪中每隔1min测定一次340nm波长下的吸光度(A340)，连续测定5min，记录各测定点的吸光值。每组测定重复三次，以100℃灭活5min的GSTs总酶作为阴性对照。使用GraphPad Prism 5软件分析化合物PXG22对多花黑麦草和日本看麦娘GSTs总酶的抑制中浓度(IC50)。使用下述公式计算相对抑制率：
其中，ΔA340c为对照组A340在5min内的变化，ΔA340t为实验组A340在5min内的变化。
结果：实验结果如图1-图3所示，化合物PXG22对多花黑麦草、日本看麦娘及稗的GSTs总酶均有明显的抑制活性，其IC50分别是34.27μM、48.89μM和40.67μM。
结论：本发明通式(I)二苯基吡唑类化合物或其农药学上可接受的盐对多种农田杂草的GSTs总酶具有明显的抑制活性，可降低日本看麦娘、多花黑麦草、稗等农田杂草GSTs总酶的活性。
实验实施例2：化合物PXG22对炔草酯防除多花黑麦草的增效作用
检测所用多花黑麦草于2019年采集自驻马店驿城区刘庄小麦田，检测所用多花黑麦草对炔草酯的相对抗性倍数为28.12，表现为高抗(表1)。检测方法参照《农药室内生物测定试验准则》，略作修改。将未使用过任何除草剂的过筛土与营养基质按1:1混匀后装入塑料盆钵中，采用盆钵底部渗灌方法保持土壤湿润。每盆播种催芽的多花黑麦草种子10粒并覆土0.5-1cm。置于温室(温度：白天20℃，夜间10℃；光照周期：12D/12L)培养。播种后待多花黑麦草出苗整齐后进行定苗，定苗后待多花黑麦草生长至3-4叶期使用喷雾塔进行茎叶喷雾处理(农业部南京农业机械化研究所3WP-2000型行走式喷雾塔，TP6501型扇形喷头，喷雾高度300mm，药液量450L/hm2)。将化合物PXG22添加至配好的除草剂中，混匀后喷雾处理，喷施后置于温室中继续培养。
施药后21d，称量植株地上部分的鲜重，计算多花黑麦草在不同处理下的鲜重抑制率。鲜重抑制率计算方法如下：
鲜重抑制率(％)＝(对照杂草鲜重-处理杂草鲜重)/对照杂草鲜重×100
采用DPS软件进行差异显著性检验(Duncan氏新复极差法)分析，并计算炔草酯对多花黑麦草鲜重的ED50(The effective rate of herbicide causing 50％inhibition in fresh weight)。试验数据分析采用probit模型进行分析，拟合方程如下：y＝a+bx。
表1多花黑麦草对炔草酯的敏感性
注：1该种群为标注敏感种群；2抗性分级标准：敏感，相对抗性倍数<2；低水平抗性，2<相对抗性倍数<5；中等水平抗性，5<相对抗性倍数<10；高水平抗性，相对抗性倍数>10(Beckie and Tardif,2012)。
结果：实验结果如表2所示。化合物PXG22单独使用对多花黑麦草的生长具有轻微的促进作用，但无较大影响。仅喷施炔草酯对多花黑麦草的鲜重抑制率不理想，使用剂量为800mg/L，鲜重抑制率仅为29.08％；此时，炔草酯对多花黑麦草的ED50>800mg/L。当炔草酯与化合物PXG22混合喷施后，不同添加量的化合物PXG22对炔草酯的增效作用有差异。当化合物PXG22添加量为12.5mg/L、25mg/L、50mg/L和100mg/L时，对炔草酯使用剂量50mg/L、100mg/L、200mg/L、400mg/L、800mg/L有一定的增效作用。当化合物PXG22添加量达到200mg/L时，对炔草酯使用剂量50mg/L、100mg/L、200mg/L、400mg/L、800mg/L的增效作用显著。特别地，对于800mg/L的炔草酯对多花黑麦草的鲜重抑制率达到56.86％，显著高于其他处理及对照(不添加化合物PXG22)；而此时炔草酯对多花黑麦草的ED50为306.04mg/L，比炔草酯单独使用时的ED50降低了至少61.75％。
表2化合物PXG22对炔草酯防除多花黑麦草的增效效果

注：同列数据后不同小写字母表示不同药剂处理间差异显著(P＜0.05)。
结论：本发明通式(I)二苯基吡唑类化合物或其农药学上可接受的盐对炔草酯防除多花黑麦草有显著的增效作用。
实验实施例3：化合物PXG22对炔草酯防除日本看麦娘的增效作用
检测所用日本看麦娘于2019年采集自信阳罗山小麦田，检测所用日本看麦娘对炔草酯的相对抗性倍数为41.51，表现为高抗(表3)。检测方法参照《农药室内生物测定试验准则》，略作修改。将未使用过任何除草剂的过筛土与营养基质按1:1混匀后装入塑料盆钵中，采用盆钵底部渗灌方法保持土壤湿润。每盆播种催芽的日本看麦娘种子10粒并覆土0.5-1cm。置于温室(温度：白天20℃，夜间10℃；光照周期：12D/12L)培养。播种后待日本看麦娘出苗整齐后进行定苗，在日本看麦娘生长至3-4叶期使用喷雾塔进行茎叶喷雾处理(农业部南京农业机械化研究所3WP-2000型行走式喷雾塔，TP6501型扇形喷头，喷雾高度300mm，药液量450L/hm2)。将化合物PXG22添加至配好的除草剂中，混匀后喷雾处理，喷施后置于温室中继续培养。
施药后21d，称量植株地上部分的鲜重，计算日本看麦娘在不同处理下的鲜重抑制率。鲜重抑制率计算方法如下：
鲜重抑制率(％)＝(对照杂草鲜重-处理杂草鲜重)/对照杂草鲜重×100
采用DPS软件进行差异显著性检验(Duncan氏新复极差法)分析，并计算炔草酯对日本看麦娘鲜重的ED50。试验数据分析采用probit模型进行分析，拟合方程如下：y＝a+bx。
表3日本看麦娘对炔草酯的敏感性
注：1该种群为标注敏感种群；2抗性分级标准：敏感，相对抗性倍数<2；低水平抗性，2<相对抗性倍数<5；中等水平抗性，5<相对抗性倍数<10；高水平抗性，相对抗性倍数>10(Beckie and Tardif,2012)。
结果：实验结果如表4所示。化合物PXG22单独使用对日本看麦娘的生长具有轻微的抑制作用，但无较大影响。仅喷施炔草酯对日本看麦娘的鲜重抑制率不理想；虽然炔草酯使用剂量为800mg/L，鲜重抑制率为77.07％；但使用剂量为50mg/L、100mg/L、200mg/L和400mg/L，鲜重抑制率仅分别为-3.34％、6.03％、6.37％、30.89％。炔草酯单独使用对日本看麦娘草的ED50为523.96mg/L。当炔草酯与化合物PXG22混合喷施后，不同添加量的化合物PXG22对炔草酯均具有增效作用。当化合物PXG22添加量为12.5～200mg/L时，对炔草酯使用剂量100mg/L、200mg/L、400mg/L的增效作用显著。化合物PXG22的添加量为12.5～200mg/L时，炔草酯对日本看麦娘的ED50分别为389.67mg/L、412.44mg/L、321.60mg/L、289.00mg/L和282.62mg/L，较炔草酯单独使用时对日本看麦娘的ED50分别降低了25.63％、21.28％、38.62％、44.84％、46.06％。
表4化合物PXG22对炔草酯防除日本看麦娘的增效效果

注：同列数据后不同小写字母表示不同药剂处理间差异显著(P＜0.05)。
结论：本发明通式(I)二苯基吡唑类化合物或其农药学上可接受的盐对炔草酯防除日本看麦娘有显著的增效作用。
实验实施例4：化合物PXG22对五氟磺草胺防除稗的增效作用
检测所用稗Echinochloa crusgalli于2019年采集自河南省信阳市商城县河凤桥乡水稻田，检测所用稗对五氟磺草胺的相对抗性倍数为28.37，表现为高抗(表5)。检测方法参照《农药 室内生物测定试验准则》，略作修改。将未使用过任何除草剂的过筛土与营养基质按1:1混匀后装入塑料盆钵中，采用盆钵底部渗灌方法保持土壤湿润。每盆播种催芽的稗种子8粒并覆土0.5～1cm。置于温室(温度：白天30℃，夜间20℃；光照周期：12D/12L)培养。播种后待稗出苗整齐后进行定苗，在稗生长至3-4叶期使用喷雾塔进行茎叶喷雾处理(农业部南京农业机械化研究所3WP-2000型行走式喷雾塔，TP6501型扇形喷头，喷雾高度300mm，药液量450L/hm2)。将化合物PXG22添加至配好的除草剂中，混匀后喷雾处理，喷施后置于温室中继续培养。
施药后21d，称量植株地上部分的鲜重，计算稗在不同处理下的鲜重抑制率。鲜重抑制率计算方法如下：
鲜重抑制率(％)＝(对照杂草鲜重-处理杂草鲜重)/对照杂草鲜重×100
采用DPS软件进行差异显著性检验(Duncan氏新复极差法)分析，并计算五氟磺草胺对稗鲜重的ED50。试验数据分析采用probit模型进行分析，拟合方程如下：y＝a+bx。
表5五氟磺草胺对稗的敏感性
注：1该种群参考自：[1]王琼.水稻田3种主要稗属(Echinochloa spp.)杂草对五氟磺草胺的抗药性研究[D].南京农业大学,2015。2抗性分级标准：敏感，相对抗性倍数<2；低水平抗性，2<相对抗性倍数<5；中等水平抗性，5<相对抗性倍数<10；高水平抗性，相对抗性倍数>10(Beckie and Tardif,2012)。
结果：实验结果如表6所示。化合物PXG22单独使用对稗的生长具有轻微的抑制作用，但无较大影响。仅喷施五氟磺草胺对稗的鲜重抑制率不理想；五氟磺草胺使用剂量为0.14mg/L、0.56mg/L、2.22mg/L、8.89mg/L和35.56mg/L时，对稗的鲜重抑制率分别为9.89％、19.07％、29.20％、57.45％和81.88％。五氟磺草胺单独使用时对稗的ED50为5.04mg/L。当五氟磺草胺与化合物PXG22混合喷施后，不同添加量的化合物PXG22对五氟磺草胺的增效作用不同。当化合物PXG22添加量为12.5mg/L时，对五氟磺草胺防除稗增效作用不明显，ED50为6.22mg/L。当化合物PXG22添加量为25～200mg/L时，对五氟磺草胺防除稗具有显著增效作用。化合物PXG22添加量为25mg/L、50mg/L、100mg/L和200mg/L时，五氟磺草胺对稗的ED50分别为3.44mg/L、1.84mg/L、1.90mg/L和2.74mg/L，较五氟磺草胺单独使用时对稗的ED50分别降低了31.91％、63.49％、62.38％和45.71％。其中，化合物PXG22添加浓度为50mg/L时，对五氟磺草胺防除稗的增效作用最佳。
表6化合物PXG22对五氟磺草胺防除稗的增效效果

注：同列数据后不同小写字母表示不同药剂处理间差异显著(P＜0.05)。
结论：本发明通式(I)二苯基吡唑类化合物或其农药学上可接受的盐对五氟磺草胺防除稗有显著的增效作用。
基于以上发明内容的描述，本领域技术人员能够全面地应用本发明，所有相同原理或类似的改动均应视为包括在本发明的范围之内。

Claims (10)

  1. 如下通式(I)二苯基吡唑类化合物或其农药学上可接受的盐作为除草剂增效剂的用途；
    其中：R1为：
    (1)未取代或者被下述一个或多个取代基取代的酰胺基-NH-CH(O)；
    (a)-C1～6烷基-R3、-C3～8环烷基-R3、-C2～6烯基-R3、-C2～6炔基-R3、-NH-R3、-N(R3)2、-C(O)-R3、-NH-C1～6烷基-R3、-C1～6烷基-NH-R3、-C1～6烷基-N(R3)2、-C1～6烷基-O-R3、-C3～8环烷基-O-R3、-O-C1～6烷基-R3、-C1～6烷基-O-C1～6烷基-R3、-C(O)-NH-R3、-C(O)-N(R3)2、-NH-C(O)-R3、-C1～6烷基-NH-C(O)-R3、-C1～6烷基-NH-C(O)-O-R3、-NH-C(O)-C1～6烷基-R3、-NH-C(O)-C1～6烷基-O-R3、-C(O)-NH-C1～6烷基-R3或-C1～6烷基-S-R3；
    所述R3各自独立地选自：H、O、S、＝NH、氨基、卤素、氰基、-C1～6烷基、-C3～8环烷基、-S-C1～6烷基、-S-OH、-SO2-C1～6烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基和-金刚烷基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-C2～6烯基、-C2～6炔基、-O-C1～6烷基、硝基、磺酸基、-C1～6烷基-卤素、-C1～6烷基-HS、-C1～6烷基-NH3 +、-C1～6烷基-OH、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2；
    (b)-6～14元芳基、-5～14元杂环基或-5～14元杂芳基；
    所述6～14元芳基、5～14元杂环基或5～14元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～6烷基、-O-C1～6烷基、-C1～6烷基-NH-C1～6烷基、-C1～6烷基-N(C1～6烷基)2、-C(O)-O-C1～6烷基、-NH-C(O)-C1～6烷基、-SO2-C1～6烷基、-SO2-NH2、-SO2-NH-C1～6烷基、-SO2-N(C1～6烷基)2、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基；
    (2)酰胺基-NH-CH(O)的N原子与C原子通过-C3～6亚烷基-、-NH-C2～6亚烷基-、-NH-C(O)-C1～6亚烷基-、-C1～6亚烷基-NH-C(O)-、-NH-C1～6亚烷基-C(O)-或-C1～6亚烷基-C(O)-连接成环状结构；该环状结构任选被下述取代基取代：-C1～6烷基、-C3～8环烷基、-C3～8环烷基-C1～6烷基、-O-C1～6烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基、-C1～6烷基-6～14元芳基、-C1～6烷基-5～14元杂环基、-C1～6烷基-5～14元杂芳基、三氟乙基；所述6～14元芳基、5～14元杂环基和5～14元杂芳基任选被-O-C1～6烷基取代；或者，所述环状结构进一步与5～8元芳基、5～8元杂环基或5～8元杂芳基并合为稠环；
    所述杂环基含有1～4个选自N、S和O中的杂原子；所述杂芳基含有1～4个选自N、S和O中的杂原子；
    R2为：-H、卤素、氨基、-NO2、-CF3、-C1～6烷基、-C1～6烷基-OH、-O-R4、-C(O)-R4、-C(O)-NH2、-NH-C(O)-R4、-C(O)-O-R4或-C(O)-O-N(R4)2；R4为：H或C1～6烷基。
  2. 根据权利要求1所述的用途，其中，除草剂与增效剂的重量份用量比例为1:0.01～3000；优选地，除草剂与增效剂的重量份用量比例为1:0.02～2000；更优选地，除草剂与增效剂的重量 份用量比例为1:0.03～2000；更优选地，除草剂与增效剂的重量份用量比例为1:0.03～1500。
  3. 根据权利要求1所述的用途，其中，杂草对除草剂的相对抗性倍数大于5；优选地杂草对除草剂的相对抗性倍数大于10；更优选地，杂草对除草剂的相对抗性倍数大于20；更优选地，杂草对除草剂的相对抗性倍数大于30。
  4. 根据权利要求1所述的用途，其中，所述增效剂为杂草GSTs抑制剂；优选地，所述增效剂延缓或者降低杂草对除草剂的抗药性。
  5. 根据权利要求1所述的用途，其中，所述除草剂选自：除草剂抗性行动委员会公布的第A类：乙酰辅酶A羧化酶抑制剂类除草剂，和第B类：乙酰乳酸合成酶抑制剂类除草剂；
    所述第A类乙酰辅酶A羧化酶抑制剂类除草剂包括：环己二酮类除草剂、芳氧苯氧基丙酸酯类除草剂；
    所述第B类乙酰乳酸合成酶抑制剂类除草剂包括：三唑并嘧啶-1型类除草剂、三唑并嘧啶-2型类除草剂、咪唑啉酮类除草剂、三唑啉酮类除草剂、磺脲类除草剂、磺酰苯胺类除草剂、嘧啶基苯甲酸酯类除草剂；
    优选地，所述除草剂选自：炔草酯、五氟磺草胺。
  6. 根据权利要求1所述的用途，其中，杂草选自：麦田杂草、稻田杂草；
    优选地，所述杂草选自：多花黑麦草(Lolium multiflorum)、日本看麦娘(Alopecurus japonicus)、稗(Echinochloa crusgalli)。
  7. 根据权利要求1所述的用途，其中，
    当所述除草剂为炔草酯时，炔草酯与增效剂的重量份用量比例为1:0.01～50；优选地，炔草酯与增效剂的重量份用量比例为1:0.02～30；更优选地，炔草酯与增效剂的重量份用量比例为1:0.02～20；更优选地，炔草酯与增效剂的重量份用量比例为1:0.02～10；更优选地，炔草酯与增效剂的重量份用量比例为1:0.03～6；或
    当所述除草剂为五氟磺草胺时，五氟磺草胺与增效剂的重量份用量比例为1:0.1～3000；优选地，五氟磺草胺与增效剂的重量份用量比例为1:0.3～2000；更优选地，五氟磺草胺与增效剂的重量份用量比例为1:0.5～1500。
  8. 根据权利要求1所述的用途，其中，
    当除草剂为炔草酯，杂草为多花黑麦草时，炔草酯与增效剂的施用量为30～1000mg/L:150～250mg/L，优选为30～1000mg/L:180～220mg/L，更优选为40～900mg/L:190～210mg/L；或
    当除草剂为炔草酯，杂草为日本看麦娘时，炔草酯与增效剂的施用量为80～600mg/L:10～300mg/L，优选为90～500mg/L:10～250mg/L，更优选为90～450mg/L:12～220mg/L；或
    当除草剂为五氟磺草胺，杂草为稗时，五氟磺草胺与增效剂的施用量为0.1～50mg/L:20～300mg/L，优选为0.1～45mg/L:20～250mg/L，更优选为0.12～40mg/L:22～220mg/L，更优选为0.14～36mg/L:40～60mg/L。
  9. 根据权利要求1所述的用途，其中，通式(I)中：
    R1为：
    (1)被下述一个或多个取代基取代的酰胺基-NH-CH(O)，
    (a)-C1～3烷基-R3、-C3～6环烷基-R3、-C2～5烯基-R3、-C1～3烷基-NH-R3、-C1～3烷基-O-R3或-O-C1～3烷基-R3；所述R3各自独立地选自：H、O、S、＝NH、氨基、卤素、氰基、-C1～3烷基、-C3～6环烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、-S-OH、氨基、-C1～3烷基、-C2～5烯基、-C2～5炔基、-O-C1～3烷基、硝基、磺酸基、-C1～3烷基-卤素、-C1～3烷基-OH；
    (b)-6～14元芳基、-5～14元杂环基或-5～14元杂芳基；所述6～14元芳基、5～14元杂 环基或5～14元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～3烷基、-O-C1～3烷基、-C1～3烷基-NH-C1～3烷基、-C1～3烷基-N(C1～3烷基)2、-C(O)-O-C1～3烷基、-NH-C(O)-C1～3烷基、-SO2-C1～3烷基、-SO2-NH2、-SO2-NH-C1～3烷基、-SO2-N(C1～3烷基)2；
    (2)酰胺基-NH-CH(O)的N原子与C原子通过-C3～6亚烷基-、-NH-C2～4亚烷基-、-NH-C(O)-C1～3亚烷基-、-C1～3亚烷基-NH-C(O)-、-NH-C1～3亚烷基-C(O)-或-C1～3亚烷基-C(O)-连接成环状结构，该环状结构任选被下述取代基取代：-C1～3烷基、-C3～6环烷基、-C3～6环烷基-C1～3烷基、-6～14元芳基、-5～14元杂环基、-5～14元杂芳基、-C1～3烷基-6～14元芳基、-C1～3烷基-5～14元杂环基、-C1～3烷基-5～14元杂芳基、三氟乙基；所述6～14元芳基、5～14元杂环基和5～14元杂芳基任选被-O-C1～3烷基取代；
    所述杂环基含有1～3个选自N、S和O中的杂原子；所述杂芳基含有1～3个选自N、S和O中的杂原子；
    R2为：-H或卤素；
    优选地，
    R1为：
    (1)-NH-C(O)-C1～3烷基-R3；所述R3选自：-6～10元芳基、-5～10元杂环基、-5～10元杂芳基；所述R3未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、-S-OH、氨基、-C1～3烷基、-O-C1～3烷基、硝基、磺酸基、-C1～3烷基-卤素、-C1～3烷基-HS、-C1～3烷基-NH3 +、-C1～3烷基-OH；
    (2)-NH-C(O)-6～10元芳基、-NH-C(O)-5～10元杂环基或-NH-C(O)-5～10元杂芳基；所述6～10元芳基、5～10元杂环基或5～10元杂芳基未取代或者被下述一个或多个取代基取代：O、-OH、卤素、氰基、硝基、-CH(O)、氨基、-C1～3烷基、-O-C1～3烷基；
    所述杂环基含有1～3个选自N、S和O中的杂原子；所述杂芳基含有1～3个选自N、S和O中的杂原子；
    R2为：-H。
  10. 根据权利要求1所述的用途，其中，所述通式(I)二苯基吡唑类化合物或其农药学上可接受的盐为以下化合物或其农药学上可接受的盐：



    优选地，为下述化合物或其农药学上可接受的盐：
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