WO2022001047A1 - Quinoline phenol derivative or pesticidally acceptable salt thereof, composition, and use thereof - Google Patents

Quinoline phenol derivative or pesticidally acceptable salt thereof, composition, and use thereof Download PDF

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Publication number
WO2022001047A1
WO2022001047A1 PCT/CN2020/140687 CN2020140687W WO2022001047A1 WO 2022001047 A1 WO2022001047 A1 WO 2022001047A1 CN 2020140687 W CN2020140687 W CN 2020140687W WO 2022001047 A1 WO2022001047 A1 WO 2022001047A1
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Prior art keywords
alkyl
halogenated
alkoxy
alkenyl
formula
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PCT/CN2020/140687
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French (fr)
Chinese (zh)
Inventor
葛家成
杨春河
邢阳阳
刘明东
孙鹏
胡亚卓
胡堂路
李丽
马娥
白光耀
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海利尔药业集团股份有限公司
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Publication of WO2022001047A1 publication Critical patent/WO2022001047A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D487/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00
    • C07D487/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, not provided for by groups C07D451/00 - C07D477/00 in which the condensed system contains two hetero rings
    • C07D487/04—Ortho-condensed systems
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • A01P1/00—Disinfectants; Antimicrobial compounds or mixtures thereof
    • 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
    • A01P3/00—Fungicides
    • 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
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the invention belongs to the technical field of pesticides, in particular to a quinoline phenol derivative or its acceptable salts and compositions as pesticides, and to the use of these compounds or their acceptable salts and compositions as pesticides as fungicides.
  • the present invention provides a quinoline phenol derivative or its salt acceptable as a pesticide, a composition and its use.
  • quinoline phenol derivatives especially 2,3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline derivatives or salts acceptable as pesticides are not only effective against rice Blast has excellent biological activity, has satisfactory control activity against other control objects except rice blast, and has excellent safety to crops.
  • R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 8;
  • R 3 , R 4 , R 5 are independently selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or phenyl-substituted C 1- C 6 alkyl;
  • X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 0-3.
  • R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy base;
  • R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
  • R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 7;
  • R 3 and R 4 are independently selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl;
  • R 5 is selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or benzyl;
  • X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 1-3;
  • R 3 and R 4 are both Me or Et, X is 6-t-Bu, and m is 1.
  • R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 2-5.
  • R 3 and R 4 are the same and selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl; preferably, R 3 and R 4 are the same, selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2, CCl 3, CH 2 F, CHF 2, CF 3, CH 2 Br, CHBr 2, CBr 3, OMe, OEt, vinyl, cyclopropane.
  • R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 2-5;
  • R 3 and R 4 are independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane ;
  • R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2, CCl 3, CH 2 F, CHF 2 , CF 3, CH 2 Br, CHBr 2, CBr 3, CH 2 CF 3, CH 2 CH 2 Cl, vinyl, OMe, OEt, n-PrO , i-PrO, n- BuO, i-BuO, s-BuO, t-BuO, cyclopropanyl, cyclopropanyloxy, nitro, aldehyde, carboxyl, hydroxyl;
  • X represents H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane, m is 1 or 2.
  • R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 3-4;
  • R 3 and R 4 are both Me or Et
  • R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH 2 Cl, CHCl 2 , CCl 3 , CH 2 F, CHF 2 , CF 3 , CH 2 CF 3 , CH 2 CH 2 Cl, vinyl, OMe, OEt, nitro;
  • X represents a tert-butyl group, and m is 1.
  • the pesticide-acceptable salt can be the salt obtained by reacting the quinoline phenol derivatives of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, Phosphoric acid or hydrobromic acid, etc.) or organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the acceptable salt of the pesticide can also be the quinoline of the present invention
  • the salt obtained by reacting phenolic derivatives with a chemically acceptable base wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or organic bases (such as trimethylamine, triethylamine, etc.).
  • the pesticide acceptable salt can be potassium salt, sodium salt, ammonium salt, calcium salt, pyridinium salt or choline salt.
  • the present invention also discloses a bactericidal composition, comprising a bactericidal effective amount of at least one of the above-mentioned quinoline phenol derivatives or salts acceptable as pesticides; further, a formulation carrier or formulation aid agent.
  • the present invention also discloses a method for controlling plant diseases, comprising adding a biologically effective amount of the above-mentioned quinoline phenol derivatives or at least one of the salts acceptable as pesticides or the above-mentioned bactericidal composition applied to plants.
  • the present invention also discloses the use of the above-mentioned quinoline phenol derivatives or at least one of the pesticide-acceptable salts thereof or the above-mentioned fungicidal composition in controlling plant diseases; preferably, the plant The disease is bacterial disease or fungal disease.
  • Halogen or halogen refers to fluorine, chlorine, bromine, iodine.
  • C 1 -C 6 alkyl a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
  • Halogenated C 1 -C 6 alkyl groups straight or branched chain alkyl groups with 1 to 6 carbon atoms, the hydrogen atoms on these alkyl groups may be partially or completely substituted by halogens, for example, chloromethyl, dichloromethane Chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.
  • C 2 -C 6 alkenyl straight-chain or branched alkenyl having 2 to 6 carbon atoms, such as vinyl, propenyl, and the like.
  • Halogenated C 2 -C 6 alkenyl straight-chain or branched alkenyl with 2 to 6 carbon atoms, and the hydrogen atoms on these alkenyl groups may be partially or completely substituted by halogen, for example, vinyl chloride and the like.
  • C 1 -C 6 alkoxy a straight or branched chain alkyl group with 1 to 6 carbon atoms connected to the structure through an oxygen atom bond.
  • Halogenated C1-C6 alkoxy straight-chain or branched alkoxy with 1-6 carbon atoms, the hydrogen atoms on these alkoxy groups may be partially or completely substituted by halogen, for example, chloromethoxy , dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
  • the synthesis method of the compound of formula I specifically, the compound of formula III and the compound of formula II (in the following chemical formulae, unless otherwise defined, the substituents and symbols are the same as those defined in formula I. Meaning)
  • the target product compound of formula I is obtained after the reaction is carried out in the presence or absence of a basic reagent and in the presence or absence of a solvent.
  • the compounds represented by formula II and III can be obtained commercially, or can be obtained by referring to the method described in EP407192A:
  • the solvent is selected from acetonitrile, N,N-dimethylformamide, NN-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane, acetic acid a mixture of one or more solvents in ethyl esters;
  • reaction can be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and post-treatment can be carried out according to conventional methods.
  • the compounds of formula I of the present invention or their acceptable salts and compositions as pesticides are respectively suitable as fungicides, especially suitable as fungicides or bactericides with significant efficacy, some of which are systemically effective and can be used as foliar Fungicides, fungicides for seed dressing and soil fungicides are used in crop protection. Furthermore, they are suitable for controlling harmful fungi which occur in particular on wood or plant roots, in particular by treating the fungi or bacteria with an effective amount of at least one compound of formula I as defined in the invention or a salt, composition which is acceptable as a pesticide, or Materials, plants, soil or seeds to be protected from fungal or bacterial attack.
  • the compound I of the present invention or its salts and compositions acceptable as pesticides are suitable for use on various cultivated plants such as cereals, such as wheat, rye, barley, triticale, oats or rice; sugar beets, such as sugar beets or fodder beets ; Fruits, such as pomes, stone fruits or berries, such as apples, pears, plums, peaches, almonds, cherries, strawberries or blueberries; Legumes, such as lentils, peas, alfalfa or soybeans; Oil plants, such as canola, mustard, olives , sunflower, coconut, cocoa beans, castor oil plants, oil palm, peanuts or soybeans; cucurbits such as pumpkin, cucumber or melon; fibrous plants such as cotton, flax or jute; citrus fruits such as oranges, lemons, Grapefruit or oranges; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds or bell peppers; laurels such as avocado
  • compound I or its salts and compositions acceptable as pesticides are used in field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rape, bean Control of fungal or bacterial diseases on plants, sunflowers, coffee or sugar cane; fruits; ornamental plants or vegetables such as cucumbers, tomatoes, beans or squash.
  • field crops such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rape, bean Control of fungal or bacterial diseases on plants, sunflowers, coffee or sugar cane; fruits; ornamental plants or vegetables such as cucumbers, tomatoes, beans or squash.
  • the present invention also provides fungicidal compositions comprising compounds of formula I.
  • the compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical and/or physical parameters. Examples of suitable formulation choices are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), aqueous (AS), microemulsion (ME), emulsifiable concentrate ( EC), Emulsion in Water (EW), Sprayable Solution, Suspension (SC), Dispersible Oil Suspension (OD), Powder (DP), Microcapsule Suspension (CS), Water Dispersible Granules (WG), Water Soluble Granules (SG), Large Granules (GG), Granules (GR) for broadcasting and soil application, Aerosol (AE), Ultra Low Volume (ULV) and Waxes. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
  • WP wettable powder
  • suitable additives are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners , humectants, repellents, attractants, food stimulants, compatibilizers, antifreeze agents, defoamers, colorants, tackifiers and adhesives.
  • Suitable solvents and liquid carriers are water and/or organic solvents, such as medium to high boiling mineral oil fractions, such as kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, Paraffins, tetralin, alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; dimethyl sulfoxide (DMSO); ketones, such as cyclohexanone; Esters, such as lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof .
  • medium to high boiling mineral oil fractions such as kerosene, diesel
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • Suitable solid carriers or fillers are mineral earths such as silicates, silica gel, talc, kaolin, limestone, lime, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides , such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of vegetable origin, such as grain flour, bark flour, wood flour, and nutshell flour, and mixtures thereof.
  • mineral earths such as silicates, silica gel, talc, kaolin, limestone, lime, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharides such as cellulose, starch
  • fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea
  • Suitable surfactants are surface-active substances such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof; such surfactants can be used as emulsifiers, dispersants, Solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants.
  • Suitable adjuvants are compounds which have negligible or even no pesticidal activity themselves and improve the biological properties of compound I on the target; examples are surfactants, mineral or vegetable oils and other adjuvants.
  • Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates and the like.
  • Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol, among others.
  • Suitable antifoaming agents are polysiloxanes, long chain alcohols and fatty acid salts and the like.
  • Suitable colorants are low water-soluble pigments and water-soluble dyes, which may be inorganic colorants (such as iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (such as Alizarin colorants, azo colorants and phthalocyanine colorants).
  • inorganic colorants such as iron oxide, titanium oxide, iron hexacyanoferrate
  • organic colorants such as Alizarin colorants, azo colorants and phthalocyanine colorants.
  • suitable active substances that can be mixed with the active substances of the present invention are, for example, known substances in "World New Pesticide Variety Technology Encyclopedia” (China Agricultural Science and Technology Press, 2010.9).
  • the fungicidal active substances mentioned below can be mixed with the mixture of formula I, (note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, with a designation where appropriate): nitrile pyrimidine Azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin (flufenoxystrobin), fluoxastrobin, kresoxim-methyl, metminostrobin, orysastrobin, picoxystrobin, pyraclostrobin ( pyraclostrobin), pyrametostrobin, pyraoxystrobin, trifloxystrobin
  • the pyrazole structure is introduced, and the obtained quinoline phenol derivatives or their use as pesticides
  • the acceptable salt not only has excellent biological activity against rice blast, but also has satisfactory control activity against other control objects except rice blast, and has excellent safety to crops.
  • Powder Weigh 20% of the compound of formula (I), mix 80% of kaolin clay uniformly, and pulverize to obtain the product.
  • Wettable powder Weigh 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium dodecyl sulfate, 3% of white carbon black, and kaolin and added to 100%. Mix evenly, and get the product after jet pulverization.
  • Water-dispersible granules weigh 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkylnaphthalene sulfonate formaldehyde condensate), 2% of pull-open powder BX (dibutyl) sodium naphthalene sulfonate), 3% K-12 (sodium dodecyl sulfate), 5% carboxymethyl (ethyl) cellulose, 5% diatomaceous earth, 5% glucose, kaolin were added to 100%. Mix evenly, after jet pulverization, weigh the powder, add water to mix, granulate in a granulator, then dry and sieve to obtain a granular product.
  • Suspending agent weigh 15% of the compound of formula (I), 4% FS3000 (phosphate ester type anionic surfactant), 2% NS-500LQ (non-ionic hydroxypolyethylene oxide block copolymer), 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.1% BIT (1,2-benzisothiazolin-3-one), 0.3% organo-modified siloxane defoamer, Deionized water was added to 100% to make a slurry, and the product was obtained after sanding.
  • the host crop is rice (Ludao No. 1), and the specific operations are as follows:
  • a certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use.
  • compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening.
  • Select potted rice seedlings with three leaves and one heart and consistent growth, and arrange them in order after marking for experimental use.
  • the type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and a blank control was set.
  • test materials were moved into a humidification box (room) or an artificial climate chamber.
  • the relative humidity was > 95%, and the temperature was 26-28°C, and cultivated under dark conditions. After 24 hours, they were moved in. 12h light-dark alternation, light intensity greater than 20000lx incubator (room) or greenhouse high-humidity culture, 5 to 7 days later, depending on the incidence of the blank control to conduct a graded investigation.
  • control effect is less than 50%
  • the host crop is rice (Shannong 13).
  • the specific operations are as follows:
  • a certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use.
  • compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening.
  • Select potted rice seedlings with three leaves and one heart and consistent growth, and arrange them in order after marking for experimental use.
  • the type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and blank control and other drug control were set.
  • control effect is less than 50%
  • the host crop is cucumber (Jinyou No. 1), and the potted seedling method is adopted.
  • the specific operations are as follows:
  • a certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use.
  • compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening.
  • the 2-4 leaf stage potted cucumber seedlings with uniform growth were selected as the experimental host plants for cucumber powdery mildew.
  • the type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and blank control and other drug control were set.
  • the fresh spores of powdery mildew produced on the leaves of diseased cucumbers within 24 hours were made into a suspension (concentration of 1 ⁇ 10 5 spores/mL), sprayed on the inoculated leaves, and cultivated under suitable conditions. After 7 to 10 days, the clear water control completely developed the disease, and the test results were investigated.
  • control effect is between 50-79%
  • control effect is less than 50%
  • Table 5 shows the protective test results of melon powdery mildew.
  • the compounds of the present invention can be used as fungicides for controlling plant diseases, especially for rice, wheat and/or melons.

Abstract

The present invention relates to the field of pesticides, and specifically relates to a quinoline phenol derivative or a pesticidally acceptable salt thereof, a composition, and a use thereof, the compound having the structure of formula (I). The definition of each group in formula (I) is as shown in the description. The compound with a quinoline phenol structure of the present invention has higher biological activity than known compounds, can effectively kill bacteria and has sufficient safety for crops, and does not easily generate resistance.

Description

一种喹啉酚类衍生物或其作为农药可接受的盐、组合物及其用途A kind of quinoline phenol derivative or its salt acceptable as pesticide, composition and use thereof 技术领域technical field
本发明属于农药技术领域，具体涉及一种喹啉酚类衍生物或其作为农药可接受的盐、组合物，并涉及这些化合物或其作为农药可接受的盐、组合物作为杀菌剂的用途。The invention belongs to the technical field of pesticides, in particular to a quinoline phenol derivative or its acceptable salts and compositions as pesticides, and to the use of these compounds or their acceptable salts and compositions as pesticides as fungicides.
背景技术Background technique
已知在喹啉骨架的4位上用烯丙氧基、氨基、苯甲酰基等取代基替换氢得到的喹啉类衍生物对植物病原菌具有一定的生物活性。在申请号为CN98805678.X的专利申请中描述了在喹啉骨架的2位、3位和5-8位上同时具有特定取代基的4-喹啉酚衍生物及其酸加成盐对包括稻瘟病菌、稻胡麻斑病菌、瓜类白粉病菌、马铃薯炭疽病菌等在内的各种植物病原菌显现出良好的抗菌活性。在申请号为01813588.9的专利申请中进一步描述了在喹啉骨架的2位、3位具有甲基取代基，6位上具有叔丁基取代基，8位上具有氟取代基的4-喹啉酚衍生物及其酸加成盐用于稻瘟病的防除。但是其对包括稻瘟病在内的防治对象的防除活性尚有改善的空间，并且在较低用量情况下，活性并不足以令人满意。It is known that quinoline derivatives obtained by replacing hydrogen with allyloxy, amino, benzoyl and other substituents at the 4-position of the quinoline skeleton have certain biological activities against plant pathogens. In the patent application with the application number CN98805678.X, 4-quinolinol derivatives and their acid addition salts with specific substituents on the 2-position, 3-position and 5-8 positions of the quinoline skeleton are described, including: Various plant pathogens including rice blast fungus, rice flax leaf spot fungus, melon powdery mildew fungus, potato anthracnose fungus etc. showed good antibacterial activity. In the patent application with application number 01813588.9, 4-quinoline with methyl substituents at the 2- and 3-positions of the quinoline skeleton, tert-butyl substituents at the 6-position and fluorine substituents at the 8-position is further described. Phenol derivatives and their acid addition salts are used for the control of rice blast. However, there is still room for improvement in its control activity against control objects including rice blast, and the activity is not satisfactory enough in the case of lower dosage.
技术问题technical problem
为解决现有技术中存在的上述问题，本发明提供了一种喹啉酚类衍生物或其作为农药可接受的盐、组合物及其用途。申请人意外地发现，喹啉酚类衍生物尤其是2,3-二甲基-6-叔丁基-8-氟-4-羟基喹啉衍生物或其作为农药可接受的盐不仅对稻瘟病具有极佳的生物活性，对除稻瘟病之外的其它防治对象均具有令人满意的防除活性，且对作物有极佳的安全性。In order to solve the above problems existing in the prior art, the present invention provides a quinoline phenol derivative or its salt acceptable as a pesticide, a composition and its use. The applicant has unexpectedly discovered that quinoline phenol derivatives, especially 2,3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline derivatives or salts acceptable as pesticides are not only effective against rice Blast has excellent biological activity, has satisfactory control activity against other control objects except rice blast, and has excellent safety to crops.
技术解决方案technical solutions
本发明为实现上述目的采用的技术方案是：一种喹啉酚类衍生物或其作为农药可接受的盐，其结构式如下：The technical scheme that the present invention adopts for realizing the above-mentioned purpose is: a kind of quinoline phenol derivative or its acceptable salt as pesticide, and its structural formula is as follows:
Figure PCTCN2020140687-appb-000001
Figure PCTCN2020140687-appb-000001
式(I)中，In formula (I),
R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
或者，R 1和R 2一起形成基团-(CH 2) t-，t表示2-8的整数； Alternatively, R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 8;
R 3、R 4、R 5分别独立地选自H、卤素、CN、硝基、醛基、羧基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、 卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、苯基或苯基取代的C 1-C 6烷基； R 3 , R 4 , R 5 are independently selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or phenyl-substituted C 1- C 6 alkyl;
X表示卤素、CN、硝基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基，m表示0-3的整数。 X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 0-3.
进一步地，式(I)中，R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； Further, in formula (I), R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy base;
R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
或者，R 1和R 2一起形成基团-(CH 2) t-，t表示2-7的整数； Alternatively, R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 7;
R 3、R 4分别独立地选自H、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 3-C 6环烷基； R 3 and R 4 are independently selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl;
R 5选自H、卤素、CN、硝基、醛基、羧基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、苯基或苄基； R 5 is selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or benzyl;
X表示卤素、CN、硝基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基，m表示1-3的整数； X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 1-3;
进一步地，R 3、R 4分均为Me或Et，X为6-t-Bu，m为1。 Further, R 3 and R 4 are both Me or Et, X is 6-t-Bu, and m is 1.
进一步地，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示2-5的整数。 Further, in formula (I), R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 2-5.
进一步地，式(I)中，R 3、R 4相同，选自H、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基；优选地，R 3、R 4相同，选自H、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2Br、CHBr 2、CBr 3、OMe、OEt、乙烯基、环丙烷基。 Further, in formula (I), R 3 and R 4 are the same and selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl; preferably, R 3 and R 4 are the same, selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2, CCl 3, CH 2 F, CHF 2, CF 3, CH 2 Br, CHBr 2, CBr 3, OMe, OEt, vinyl, cyclopropane.
进一步地，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示2-5的整数； Further, in formula (I), R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 2-5;
R 3、R 4分别独立地选自H、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、OMe、OEt、乙烯基、环丙烷基； R 3 and R 4 are independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane ;
R 5选自H、F、Cl、Br、CN、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2Br、CHBr 2、CBr 3、CH 2CF 3、CH 2CH 2Cl、乙烯基、OMe、OEt、n-PrO、i-PrO、n-BuO、i-BuO、s-BuO、t-BuO、环丙烷基、环丙烷氧基、硝基、醛基、羧基、羟基； R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2, CCl 3, CH 2 F, CHF 2 , CF 3, CH 2 Br, CHBr 2, CBr 3, CH 2 CF 3, CH 2 CH 2 Cl, vinyl, OMe, OEt, n-PrO , i-PrO, n- BuO, i-BuO, s-BuO, t-BuO, cyclopropanyl, cyclopropanyloxy, nitro, aldehyde, carboxyl, hydroxyl;
X表示H、F、Cl、Br、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、OMe、OEt、乙烯基、环丙烷基，m为1或2。X represents H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane, m is 1 or 2.
进一步地，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示3-4的整数； Further, in formula (I), R 1 and R 2 together form a group -(CH 2 ) t -, and t represents an integer of 3-4;
R 3、R 4均为Me或Et； R 3 and R 4 are both Me or Et;
R 5选自H、F、Cl、Br、CN、Me、Et、n-Pr、i-Pr、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2CF 3、CH 2CH 2Cl、乙烯基、OMe、OEt、硝基； R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH 2 Cl, CHCl 2 , CCl 3 , CH 2 F, CHF 2 , CF 3 , CH 2 CF 3 , CH 2 CH 2 Cl, vinyl, OMe, OEt, nitro;
X表示叔丁基，m为1。X represents a tert-butyl group, and m is 1.
进一步地，式(I)化合物具体选自：Further, the compound of formula (I) is specifically selected from:
Figure PCTCN2020140687-appb-000002
Figure PCTCN2020140687-appb-000002
Figure PCTCN2020140687-appb-000003
Figure PCTCN2020140687-appb-000003
Figure PCTCN2020140687-appb-000004
Figure PCTCN2020140687-appb-000004
所述的农药可接受的盐可以为本发明的喹啉酚类衍生物与化学上可接受的酸进行反应制得的盐，其中化学上可接受的酸可以是无机酸(如盐酸、硫酸、磷酸或氢溴酸等)或有机酸(如草酸、马来酸、富马酸、苹果酸、酒石酸、柠檬酸或苯甲酸等)；所述的农药可接受的盐也可以为本发明的喹啉酚类衍生物与化学上可接受的碱进行反应制得的盐，其中化学上可接受的碱可以是无机碱(如氢氧化钠、氢氧化钾、氢氧化钙、碳酸钠、碳酸钾、碳酸氢钠或碳酸氢钾)或有机碱(如三甲胺、三乙胺等)。The pesticide-acceptable salt can be the salt obtained by reacting the quinoline phenol derivatives of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, Phosphoric acid or hydrobromic acid, etc.) or organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.); the acceptable salt of the pesticide can also be the quinoline of the present invention The salt obtained by reacting phenolic derivatives with a chemically acceptable base, wherein the chemically acceptable base can be an inorganic base (such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate or potassium bicarbonate) or organic bases (such as trimethylamine, triethylamine, etc.).
进一步地，所述的农药可接受的盐可以为钾盐、钠盐、铵盐、钙盐、吡啶盐或胆碱盐。Further, the pesticide acceptable salt can be potassium salt, sodium salt, ammonium salt, calcium salt, pyridinium salt or choline salt.
本发明还公开了一种杀菌组合物，包括杀菌有效量的如上所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种；进一步地，还包括制剂载体或制剂助剂。The present invention also discloses a bactericidal composition, comprising a bactericidal effective amount of at least one of the above-mentioned quinoline phenol derivatives or salts acceptable as pesticides; further, a formulation carrier or formulation aid agent.
本发明还公开了一种控制植物病害的方法，包括将生物有效量的如上所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种或如上所述的杀菌组合物施用在植物上。The present invention also discloses a method for controlling plant diseases, comprising adding a biologically effective amount of the above-mentioned quinoline phenol derivatives or at least one of the salts acceptable as pesticides or the above-mentioned bactericidal composition applied to plants.
本发明还公开了如上所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种或如上所述的杀菌组合物在控制植物病害方面的用途；优选的，所述植物病害为细菌性病害或真菌性病害。The present invention also discloses the use of the above-mentioned quinoline phenol derivatives or at least one of the pesticide-acceptable salts thereof or the above-mentioned fungicidal composition in controlling plant diseases; preferably, the plant The disease is bacterial disease or fungal disease.
在上述化合物结构式的定义中，所使用的专业术语均具有如下含义：In the definition of the above compound structural formula, the professional terms used have the following meanings:
卤或卤素：指氟、氯、溴、碘。Halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
C 1-C 6烷基：碳原子数为1-6的直链或支链烷基，例如甲基、乙基、丙基、异丙基或叔丁基。 C 1 -C 6 alkyl: a straight or branched chain alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
卤代C 1-C 6烷基：碳原子数为1-6的直链或支链烷基，在这些烷基上的氢原子可部分或全部被卤素所取代，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。 Halogenated C 1 -C 6 alkyl groups: straight or branched chain alkyl groups with 1 to 6 carbon atoms, the hydrogen atoms on these alkyl groups may be partially or completely substituted by halogens, for example, chloromethyl, dichloromethane Chloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.
C 2-C 6烯基：碳原子数为2-6的直链或支链烯基，例如乙烯基、丙烯基等。 C 2 -C 6 alkenyl: straight-chain or branched alkenyl having 2 to 6 carbon atoms, such as vinyl, propenyl, and the like.
卤代C 2-C 6烯基：碳原子数为2-6的直链或支链烯基，在这些烯基上的氢原子可部分或全部被卤素所取代，例如，氯乙烯基等。 Halogenated C 2 -C 6 alkenyl: straight-chain or branched alkenyl with 2 to 6 carbon atoms, and the hydrogen atoms on these alkenyl groups may be partially or completely substituted by halogen, for example, vinyl chloride and the like.
C 1-C 6烷氧基：碳原子数为1-6的直链或支链烷基，经氧原子键连接到结构上。 C 1 -C 6 alkoxy: a straight or branched chain alkyl group with 1 to 6 carbon atoms connected to the structure through an oxygen atom bond.
卤代C1-C6烷氧基：碳原子数为1-6的直链或支链烷氧基，在这些烷氧基上的氢原子可部分或全部被卤素所取代，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。Halogenated C1-C6 alkoxy: straight-chain or branched alkoxy with 1-6 carbon atoms, the hydrogen atoms on these alkoxy groups may be partially or completely substituted by halogen, for example, chloromethoxy , dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
本发明中出现的基团缩写与本领域技术人员通常所使用的一致，例如Me代表甲基，Et代表乙基，Pr代表丙基，Bu代表丁基，n-Bu代表正丁基，i-Bu代表异丁基，s-Bu代表仲丁基，t代表叔丁基，phenyl代表苯基，OMe代表甲氧基等。The group abbreviations appearing in the present invention are consistent with those commonly used by those skilled in the art, such as Me for methyl, Et for ethyl, Pr for propyl, Bu for butyl, n-Bu for n-butyl, i- Bu stands for isobutyl, s-Bu stands for sec-butyl, t stands for tert-butyl, phenyl stands for phenyl, OMe stands for methoxy, etc.
式Ⅰ所述化合物的合成方法，具体是将式Ⅲ化合物与式Ⅱ化合物(在下列列举的化学式中，只要未另外进行定义，取代基和符号与式Ⅰ中定义的取代基和符号具有相同的意义)在有或无碱性试剂存在、有或无溶剂存在的条件下进行反应后得到目标产物式I化合物。式Ⅱ、Ⅲ所代表的化合物均可通过市售获得，或可参考EP407192A中记载的方法制得：The synthesis method of the compound of formula I, specifically, the compound of formula III and the compound of formula II (in the following chemical formulae, unless otherwise defined, the substituents and symbols are the same as those defined in formula I. Meaning) The target product compound of formula I is obtained after the reaction is carried out in the presence or absence of a basic reagent and in the presence or absence of a solvent. The compounds represented by formula II and III can be obtained commercially, or can be obtained by referring to the method described in EP407192A:
Figure PCTCN2020140687-appb-000005
Figure PCTCN2020140687-appb-000005
进一步地，溶剂选自乙腈、N,N-二甲基甲酰胺、N.N-二甲基乙酰胺、二甲亚砜、四氢呋喃、二氯甲烷、苯、甲苯、二甲苯、二氯乙烷、乙酸乙酯中的一种或多种溶剂的混合物；Further, the solvent is selected from acetonitrile, N,N-dimethylformamide, NN-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane, acetic acid a mixture of one or more solvents in ethyl esters;
进一步地，反应可以在常压或高压下进行，优选在大气压下进行，可根据常规方法进行后处理。Further, the reaction can be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and post-treatment can be carried out according to conventional methods.
本发明的式I化合物或其作为农药可接受的盐、组合物分别适合作为杀菌剂，尤其适合作为杀真菌剂或杀细菌剂具有显著的效力，它们中的一些内吸有效并且可以作为叶面杀真菌剂、拌种用杀真菌剂和土壤杀真菌剂用于作物保护中。此外，它们适合防治尤其发生在木材或植物根部的有害真菌，具体为用有效量的至少一种本发明所定义的式I化合物或其作为农药可接受的盐、组合物处理真菌或细菌，或要防止真菌或细菌侵袭的材料、植物、土壤或种子。The compounds of formula I of the present invention or their acceptable salts and compositions as pesticides are respectively suitable as fungicides, especially suitable as fungicides or bactericides with significant efficacy, some of which are systemically effective and can be used as foliar Fungicides, fungicides for seed dressing and soil fungicides are used in crop protection. Furthermore, they are suitable for controlling harmful fungi which occur in particular on wood or plant roots, in particular by treating the fungi or bacteria with an effective amount of at least one compound of formula I as defined in the invention or a salt, composition which is acceptable as a pesticide, or Materials, plants, soil or seeds to be protected from fungal or bacterial attack.
本发明化合物I或其作为农药可接受的盐、组合物适宜在各种栽培植物如禾谷类，例如小麦、黑麦、大麦、小黑麦、燕麦或稻；甜菜，例如糖用甜菜或饲料甜菜；水果，如仁果、核果或浆果，例如苹果、梨、李、桃、杏仁、樱桃、草莓或蓝莓；豆科植物，例如扁豆、豌豆、苜蓿或大豆；油料植物，例如油菜、芥菜、橄榄、向日葵、椰子、可可豆、蓖麻油植物、油棕、花生或大豆；葫芦科植物，例如南瓜、黄瓜或甜瓜；纤维植物，例如棉花、亚麻或黄麻；柑桔类水果，例如橙子、柠檬、葡萄柚或橘；蔬菜，例如菠菜、莴苣、芦笋、卷心菜、胡萝卜、洋葱、西红柿、土豆、葫芦或柿子椒；月桂类植物，例如鳄梨、肉桂或樟脑；经济价值较大的作物，例如玉米、大豆、油菜、甘蔗、油棕、烟草、坚果、咖啡、茶、香蕉、葡萄、啤酒花等；草坪；天然橡胶植物或观赏和森林植物，例如花卉、灌木、阔叶树或常绿树，例如针叶树，以及植物繁殖材料如种子、植物块茎、插条等上述材料中防治植物病害尤其是真菌性病害或细菌性病害。The compound I of the present invention or its salts and compositions acceptable as pesticides are suitable for use on various cultivated plants such as cereals, such as wheat, rye, barley, triticale, oats or rice; sugar beets, such as sugar beets or fodder beets ; Fruits, such as pomes, stone fruits or berries, such as apples, pears, plums, peaches, almonds, cherries, strawberries or blueberries; Legumes, such as lentils, peas, alfalfa or soybeans; Oil plants, such as canola, mustard, olives , sunflower, coconut, cocoa beans, castor oil plants, oil palm, peanuts or soybeans; cucurbits such as pumpkin, cucumber or melon; fibrous plants such as cotton, flax or jute; citrus fruits such as oranges, lemons, Grapefruit or oranges; vegetables such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, gourds or bell peppers; laurels such as avocados, cinnamon or camphor; economically important crops such as corn, Soybeans, canola, sugarcane, oil palm, tobacco, nuts, coffee, tea, bananas, grapes, hops, etc.; lawns; natural rubber plants or ornamental and forest plants, such as flowers, shrubs, broadleaf or evergreen trees, such as conifers, and Plant propagation materials such as seeds, plant tubers, cuttings and the like are used to control plant diseases, especially fungal diseases or bacterial diseases.
优选化合物I或其作为农药可接受的盐、组合物分别用于在大田作物，例如土豆、糖用甜菜、烟草、小麦、黑麦、大麦、燕麦、稻、玉米、棉花、大豆、油菜、豆科植物、向日葵、咖啡或甘蔗；水果；观赏植物或蔬菜如黄瓜、西红柿、菜豆或南瓜上防治真菌或细菌性病害。Preferably compound I or its salts and compositions acceptable as pesticides are used in field crops, such as potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, corn, cotton, soybean, rape, bean Control of fungal or bacterial diseases on plants, sunflowers, coffee or sugar cane; fruits; ornamental plants or vegetables such as cucumbers, tomatoes, beans or squash.
本发明还提供了包括式I化合物的杀菌剂组合物。根据通常的生物学和/或化学参数和/或物理参数，可以用多 种方式配制式I化合物。适合的制剂选择实例为：可湿性粉剂(WP)、可湿性液剂(SL)、可溶性粉剂(SP)、可分散液剂(DC)、水剂(AS)、微乳剂(ME)、乳油(EC)、水乳剂(EW)、可喷洒溶液、悬浮剂(SC)、可分散油悬浮剂(OD)、粉剂(DP)、微囊悬浮剂(CS)、水分散粒剂(WG)、水溶性粒剂(SG)、大粒剂(GG)、用于撒播和土壤施药的颗粒剂(GR)、气雾剂(AE)、超低容量剂(ULV)和蜡制品。必要的制剂助剂，例如惰性物质、表面活性剂、溶剂及其它添加剂。The present invention also provides fungicidal compositions comprising compounds of formula I. The compounds of formula I can be formulated in a variety of ways depending on the usual biological and/or chemical and/or physical parameters. Examples of suitable formulation choices are: wettable powder (WP), wettable liquid (SL), soluble powder (SP), dispersible liquid (DC), aqueous (AS), microemulsion (ME), emulsifiable concentrate ( EC), Emulsion in Water (EW), Sprayable Solution, Suspension (SC), Dispersible Oil Suspension (OD), Powder (DP), Microcapsule Suspension (CS), Water Dispersible Granules (WG), Water Soluble Granules (SG), Large Granules (GG), Granules (GR) for broadcasting and soil application, Aerosol (AE), Ultra Low Volume (ULV) and Waxes. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
合适添加剂的实例是溶剂、液体载体、固体载体或填料、表面活性剂、分散剂、乳化剂、润湿剂、辅助剂、加溶剂、渗透促进剂、保护性胶体、粘附剂、增稠剂、保湿剂、驱除剂、引诱剂、进食刺激剂、相容剂、防冻剂、消泡剂、着色剂、增粘剂和粘合剂。Examples of suitable additives are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesives, thickeners , humectants, repellents, attractants, food stimulants, compatibilizers, antifreeze agents, defoamers, colorants, tackifiers and adhesives.
合适的溶剂和液体载体是水和/或有机溶剂，如中到高沸点的矿物油馏分，例如煤油、柴油；植物或动物来源的油；脂族、环状和芳族烃类，例如甲苯、石蜡、四氢萘、烷基化萘；醇类，如乙醇、丙醇、丁醇、苄醇、环己醇；二醇类；二甲亚砜(DMSO)；酮类，例如环己酮；酯类，例如乳酸酯、碳酸酯、脂肪酸酯、γ-丁内酯；脂肪酸；膦酸酯；胺类；酰胺类，例如N-甲基吡咯烷酮，脂肪酸二甲基酰胺；以及它们的混合物。Suitable solvents and liquid carriers are water and/or organic solvents, such as medium to high boiling mineral oil fractions, such as kerosene, diesel; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, Paraffins, tetralin, alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; dimethyl sulfoxide (DMSO); ketones, such as cyclohexanone; Esters, such as lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof .
合适的固体载体或填料是矿物质土，例如硅酸盐、硅胶、滑石、高岭土、石灰石、石灰、粘土、白云石、硅藻土、膨润土、硫酸钙、硫酸镁、氧化镁；多糖类物质，例如纤维素、淀粉；肥料，例如硫酸铵、磷酸铵、硝酸铵、脲类；植物来源的产品，例如谷粉、树皮粉、木粉和坚果壳粉，以及它们的混合物。Suitable solid carriers or fillers are mineral earths such as silicates, silica gel, talc, kaolin, limestone, lime, clay, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharides , such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, urea; products of vegetable origin, such as grain flour, bark flour, wood flour, and nutshell flour, and mixtures thereof.
合适的表面活性剂是表面活性物质，如阴离子、阳离子、非离子和两性表面活性剂、嵌段聚合物、聚电解质、以及它们的混合物；该类表面活性剂可以用作乳化剂、分散剂、促溶剂、润湿剂、渗透促进剂、保护性胶体或辅助剂。Suitable surfactants are surface-active substances such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof; such surfactants can be used as emulsifiers, dispersants, Solubilizers, wetting agents, penetration enhancers, protective colloids or adjuvants.
合适的辅助剂是本身具有可忽略的农药活性或者本身甚至没有农药活性且改善化合物I对目标物的生物学性能的化合物；实例是表面活性剂、矿物油或植物油以及其他助剂。Suitable adjuvants are compounds which have negligible or even no pesticidal activity themselves and improve the biological properties of compound I on the target; examples are surfactants, mineral or vegetable oils and other adjuvants.
合适的增稠剂是多糖(例如黄原胶、羧甲基纤维素)、无机粘土(有机改性或未改性的)、聚羧酸盐和硅酸盐等。Suitable thickeners are polysaccharides (eg xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates and the like.
合适的防冻剂是乙二醇、丙二醇、尿素和甘油等。Suitable antifreeze agents are ethylene glycol, propylene glycol, urea and glycerol, among others.
合适的消泡剂是聚硅氧烷、长链醇和脂肪酸盐等。Suitable antifoaming agents are polysiloxanes, long chain alcohols and fatty acid salts and the like.
合适的着色剂(例如着红色、蓝色或绿色)是低水溶性颜料和水溶性染料，可以为无机着色剂(例如氧化铁、氧化钛、六氰合铁酸铁)和有机着色剂(例如茜素着色剂、偶氮着色剂和酞菁着色剂)。Suitable colorants (such as red, blue or green) are low water-soluble pigments and water-soluble dyes, which may be inorganic colorants (such as iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (such as Alizarin colorants, azo colorants and phthalocyanine colorants).
在混配制剂或桶混制剂中，可以和本发明的活性物质混合的合适的活性物质为，例如《世界农药新品种技术大全》(中国农业科学技术出版社，2010.9)中的已知物质。例如以下提到的杀菌剂活性物质可以和式I混合物混合，(备注：化合物的名称，或者为根据国际标准化组织(ISO)的普通名称，或者为化学名称，适当的时候有代号)：腈嘧菌酯(azoxystrobin)、甲香菌酯(coumethoxystrobin)、丁香菌酯(coumoxystrobin)、醚菌胺(dimoxystrobin)、烯肟菌酯(enestroburin)、烯肟菌胺(fenaminstrobin)、fenoxystrobin/氟菌螨酯(flufenoxystrobin)、氟嘧菌酯(fluoxastrobin)、亚胺菌(kresoxim-methyl)、叉氨苯酰胺(metominostrobin)、肟醚菌胺(orysastrobin)、啶氧菌酯(picoxystrobin)、唑菌胺酯(pyraclostrobin)、pyrametostrobin、唑菌酯(pyraoxystrobin)、肟菌酯(trifloxystrobin)、2-[2-(2,5-二甲基苯氧基甲基)苯基]-3-甲氧基丙烯酸甲酯、2-(2-(3-(2,6-二氯苯基)-1-甲基亚烯丙基氨基氧甲基)苯基)-2-甲氧亚氨基-N-甲基乙酰胺、pyribencarb、triclopyricarb/chlorodincarb、噁唑酮菌(famoxadone)、咪唑菌酮(fenamidone)；氰霜唑(cyazofamid)、 amisulbrom、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[(3-乙酰氧基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧庚环-7-基]酯、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[[3-乙酰氧基甲氧基-4-甲氧基吡啶-2-羰基]氨基]-6-甲基-4,9-二氧代-1,5-二氧庚环-7-基]酯、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[(3-异丁氧基羰氧基-4-甲氧基吡啶-2-羰基)氨基]-6-甲基-4,9-二氧代-1,5-二氧庚环-7-基]酯、2-甲基丙酸[(3S,6S,7R,8R)-8-苄基-3-[[3-(1,3-苯并间二氧杂环戊烯-5-基甲氧基)-4-甲氧基吡啶-2-羰基]氨基]-6-甲基-4,9-二氧代-1,5-二氧庚环-7-基]酯、2-甲基丙酸(3S,6S,7R,8R)-3-[[(3-羟基-4-甲氧基-2-吡啶基)羰基]氨基]-6-甲基-4,9-二氧代-8-(苯基甲基)-1,5-二氧庚环-7-基酯；麦锈灵(benodanil)、bixafen、啶酰菌胺(boscalid)、萎锈灵(carboxin)、呋菌胺(fenfuram)、氟吡菌酰胺(fluopyram)、氟酰胺(flutolanil)、氟唑菌酰胺(fluxapyroxad)、呋吡唑灵(furametpyr)、isopyrazam、丙氧灭绣胺(mepronil)、氧化萎锈灵(oxycarboxin)、penflufen、吡噻菌胺(penthiopyrad)、sedaxane、叶枯酞(tecloftalam)、溴氟唑菌(thifluzamide)、N-(4'-三氟甲硫基联苯-2-基)-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺、N-(2-(1,3,3-三甲基丁基)苯基)-1,3-二甲基-5-氟-1H-吡唑-4-甲酰胺、N-[9-(二氯亚甲基)-1,2,3,4-四氢-1,4-亚甲基萘-5-基]-3-二氟甲基-1-甲基-1H-吡唑-4-甲酰胺；3-二氟甲基-1-甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺，3-三氟甲基-1-甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺，1,3-二甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺，3-三氟甲基-1,5-二甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺，3-二氟甲基-1,5-二甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺，1,3,5-三甲基-N-(1,1,3-三甲基-2,3-二氢化茚-4-基)吡唑-4-甲酰胺；二氟林(diflumetorim)、(5,8-二氟喹唑啉-4-基)-{2-[2-氟-4-(4-三氟甲基吡啶-2-基氧基)苯基]乙基}胺；硝基苯基衍生物：乐杀螨(binapacryl)、敌螨通(dinobuton)、敌螨普(dinocap)、氟啶胺(fluazinam)；嘧菌腙(ferimzone)；有机金属化合物：三苯锡基盐，例如薯瘟锡(fentin-acetate)、三苯锡氯(fentinchloride)或毒菌锡(fentinhydroxide)；ametoctradin和硅噻菌胺(silthiofam)；戊环唑(azaconazole)、双苯三唑醇(bitertanol)、糠菌唑(bromuconazole)、环唑醇(cyproconazole)、苯醚甲环唑(difenoconazole)、烯唑醇(diniconazole)、烯唑醇M(diniconazole-M)、氧唑菌(epoxiconazole)、腈苯唑(fenbuconazole)、喹唑菌酮(fluquinconazole)、氟硅唑(flusilazole)、粉唑醇(flutriafol)、己唑醇(hexaconazole)、酰胺唑(imibenconazole)、环戊唑醇(ipconazole)、环戊唑菌(metconazole)、腈菌唑(myclobutanil)、oxpoconazole、多效唑(paclobutrazole)、戊菌唑(penconazole)、丙环唑(propiconazole)、丙硫菌唑(prothioconazole)、硅氟唑(simeconazole)、戊唑醇(tebuconazole)、氟醚唑(tetraconazole)、三唑酮(triadimefon)、唑菌醇(triadimenol)、戊叉唑菌(triticonazole)、烯效唑(uniconazole)、抑霉唑(imazalil)、稻瘟酯(pefurazoate)、丙氯灵(prochloraz)、氟菌唑(triflumizol)、异嘧菌醇(fenarimol)、氟苯嘧啶醇(nuarimol)、啶斑肟(pyrifenox)、嗪氨灵(triforine)、4-十二烷基-2,6-二甲基吗啉(aldimorph)、吗菌灵(dodemorph)、吗菌灵乙酸酯(dodemorph-acetate)、丁苯吗啉(fenpropimorph)、克啉菌(tridemorph)、苯锈啶(fenpropidin)、粉病灵(piperalin)、螺噁茂胺(spiroxamine)、苯霜灵(benalaxyl)、精苯霜灵(benalaxyl-M)、kiralaxyl、甲霜灵(metalaxyl)、精甲霜灵(metalaxyl-M)(mefenoxam)、甲呋酰胺(ofurace)、噁霜灵(oxadixyl)、环酰菌胺(fenhexamid)、土菌消(hymexazole)、异噻菌酮(octhilinone)、恶喹酸(oxolinicacid)、磺嘧菌灵(bupirimate)、苯菌灵(benomyl)、多菌灵(carbendazim)、麦穗宁(fuberidazole)、涕必灵(thiabendazole)、甲基托布津(thiophanate-methyl)、乙霉威(diethofencarb)、噻唑菌胺(ethaboxam)、戊菌隆(pencycuron)、氟吡菌胺(fluopicolide)、苯酰菌胺(zoxamide)、苯菌酮(metrafenone)、pyriofenone、环丙嘧啶(cyprodinil)、嘧菌胺(mepanipyrim)、二甲嘧菌胺(pyrimethanil)、灭瘟素(blasticidin-S)、春雷霉素(kasugamycin)、水合春雷霉素(kasugamycinhydrochloride-hydrate)、米多霉素(mildiomycin)、链霉素(streptomycin)、土霉素(oxytetracyclin)、多氧霉素(polyoxine)、井冈霉素(validamycinA)、氟菌安(fluoroimid)、异丙定(iprodione)、杀菌利(procymidone)、烯菌酮(vinclozolin)、拌种咯(fenpiclonil)、氟噁菌 (fludioxonil)、克瘟散(edifenphos)、异稻瘟净(iprobenfos)、定菌磷(pyrazophos)、稻瘟灵(isoprothiolane)、氯硝胺(dicloran)、五氯硝基苯(quintozene)、四氯硝基苯(tecnazene)、甲基立枯磷(tolclofos-methyl)、联苯、地茂散(chloroneb)、氯唑灵(etridiazole)、烯酰吗啉(dimethomorph)、氟吗啉(flumorph)、双炔酰菌胺(mandipropamid)、丁吡吗啉(pyrimorph)、苯噻菌胺(benthiavalicarb)、异丙菌胺(iprovalicarb)、valifenalate、N-(1-(1-(4-氰基苯基)乙磺酰基)丁-2-基)氨基甲酸4-氟苯基酯、百维灵(propamocarb)、霜霉威盐酸盐(propamocarb-hydrochlorid)、波尔多液(Bordeaux混合物)、醋酸铜、氢氧化铜、王铜(copperoxychloride)、碱式硫酸铜、福美铁(ferbam)、代森锰锌(mancozeb)、代森锰(maneb)、威百亩(metam)、代森联(metiram)、甲基代森锌(propineb)、福美双(thiram)、代森锌(zineb)、福美锌(ziram)、敌菌灵(anilazine)、百菌清(chlorothalonil)、敌菌丹(captafol)、克菌丹(captan)、灭菌丹(folpet)、抑菌灵(dichlofluanid)、双氯酚(dichlorophen)、磺菌胺(flusulfamide)、六氯苯(hexachlorobenzene)、五氯酚(pentachlorphenole)及其盐、四氯苯酞(phthalide)、对甲抑菌灵(tolylfluanid)、N-(4-氯-2-硝基苯基)-N-乙基-4-甲基苯磺酰胺、多果定游离碱、双胍盐(guazatine)、双胍辛胺(guazatine-acetate)、双胍辛醋酸盐(iminoctadine)、双胍辛胺三乙酸盐(iminoctadine-triacetate)、双八胍盐(iminoctadine-tris(albesilate))、二噻农(dithianon)、2,6-二甲基-1H,5H-[1,4]二噻二烯并[2,3-c:5,6-c']联吡咯-1,3,5,7(2H,6H)-四酮、井冈霉素(validamycin)、多氧霉素(polyoxinB)；黑素合成抑制剂：咯喹酮(pyroquilon)、三环唑(tricyclazole)、氯环丙酰胺(carpropamid)、双氯氰菌胺(dicyclomet)、氰菌胺(fenoxanil)、噻二唑素(acibenzolar-S-methyl)、噻菌灵(probenazole)、异噻菌胺(isotianil)、噻酰菌胺(tiadinil)、调环酸钙(prohexadione-calcium)；膦酸酯类：藻菌磷(fosetyl)、乙磷铝(fosetyl-aluminum)、亚磷酸及其盐、拌棉醇(bronopol)、灭螨蜢(chinomethionat)、环氟菌胺(cyflufenamid)、清菌脲(cymoxanil)、棉隆(dazomet)、咪菌威(debacarb)、哒菌清(diclomezine)、野燕枯(difenzoquat)、野燕枯甲基硫酸酯(difenzoquat-methylsulfate)、二苯胺、胺苯吡菌酮(fenpyrazamine)、氟联苯菌(flumetover)、磺菌胺、flutianil、磺菌威(methasulfocarb)、氯定(nitrapyrin)、异丙消(nitrothal-isopropyl)、喹啉铜(oxin-copper)、丙氧喹啉(proquinazid)、tebufloquin、叶枯酞、唑菌嗪(triazoxide)等。In compound formulations or tank-mixed formulations, suitable active substances that can be mixed with the active substances of the present invention are, for example, known substances in "World New Pesticide Variety Technology Encyclopedia" (China Agricultural Science and Technology Press, 2010.9). For example, the fungicidal active substances mentioned below can be mixed with the mixture of formula I, (note: the name of the compound, or the common name according to the International Organization for Standardization (ISO), or the chemical name, with a designation where appropriate): nitrile pyrimidine Azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin/flufenoxystrobin (flufenoxystrobin), fluoxastrobin, kresoxim-methyl, metminostrobin, orysastrobin, picoxystrobin, pyraclostrobin ( pyraclostrobin), pyrametostrobin, pyraoxystrobin, trifloxystrobin, methyl 2-[2-(2,5-dimethylphenoxymethyl)phenyl]-3-methoxyacrylate , 2-(2-(3-(2,6-dichlorophenyl)-1-methylallylideneaminooxymethyl)phenyl)-2-methoxyimino-N-methylacetamide , pyribencarb, triclopyricarb/chlorodincarb, famoxadone, fenamidone; cyazofamid, amisulbrom, 2-methylpropionic acid [(3S,6S,7R,8R)-8- Benzyl-3-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxane-7 -yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[[3-acetoxymethoxy-4-methoxypyridine-2-carbonyl ] Amino]-6-methyl-4,9-dioxo-1,5-dioxan-7-yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R)-8 -Benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-di Oxepan-7-yl]ester, 2-methylpropionic acid [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxane Penten-5-ylmethoxy)-4-methoxypyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxan-7-yl ] ester, 2-methylpropionic acid (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridine yl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxan-7-yl ester; benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furazolin (furametpyr), isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-Trifluoromethylthiobiphenyl-2-yl)-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N-(2-(1,3 ,3-trimethylbutyl)phenyl)-1,3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N-[9-(dichloromethylene)-1, 2,3,4-Tetrahydro-1,4-methylenenaphthalen-5-yl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; 3-difluoromethyl yl-1-methyl-N-(1,1,3-trimethyl-2,3-indan-4-yl)pyrazole-4-carboxamide, 3-trifluoromethyl-1-methyl base-N-(1,1,3-trimethyl-2,3-indan-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl-N-(1,1, 3-Trimethyl-2,3-indan-4-yl)pyrazole-4-carboxamide, 3-trifluoromethyl-1,5-dimethyl-N-(1,1,3- Trimethyl-2,3-indan-4-yl)pyrazole-4-carboxamide, 3-difluoromethyl-1,5-dimethyl-N-(1,1,3-trimethyl) yl-2,3-indan-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethyl-2,3-di Indan-4-yl)pyrazole-4-carboxamide; diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4 -Trifluoromethylpyridin-2-yloxy)phenyl]ethyl}amine; nitrophenyl derivatives: binapacryl, dinobuton, dinocap, fluorine fluazinam; ferimzone; organometallic compounds: triphenyltin salts, such as fentin-acetate, fentinchloride or fentinhydroxide; ametoctradin and Silthiofam (silthiofam); Penconazole (azac onazole), bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M ), epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole , ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole ( prothioconazole), simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, niconazole ( uniconazole), imazalil (imazalil), pefurazoate (pefurazoate), prochloraz (prochloraz), triflumizol (triflumizol), fenarimol (fenarimol), fluoropyrimidine (nuarimol), pyridine oxime (pyrifenox), triforine, 4-dodecyl-2,6-dimethylmorpholine (aldimorph), dodemorph, dodemorph-acetate, Fenpropimorph, tridemorph, fenpropidin, piperalin, spiroxamine, benalaxyl, benalaxyl -M), kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl, fenhexamid, soil fungus hymexazole, octhilinone, oxolinic acid, bup irimate), benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, diethofencarb, thiazolidine Ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, cyprodinil, mepanipyrim , pyrimethanil, blasticidin-S, kasugamycin, kasugamycinhydrochloride-hydrate, midiomycin, streptomycin , oxytetracyclin, polyoxine, validamycinA, fluoroimid, iprodione, procymidone, vinclozolin, Seed dressing (fenpiclonil), fludioxonil, edifenphos, iprobenfos, pyrazophos, isoprothiolane, dicloran, Pentachloronitrobenzene (quintozene), tetrachloronitrobenzene (tecnazene), tolclofos-methyl (tolclofos-methyl), biphenyl, chloroneb, etridiazole, dimethomorph (dimethomorph), flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate, N-(1 -(1-(4-cyanophenyl)ethanesulfonyl)butan-2-yl)carbamic acid 4-fluorophenyl ester, propamocarb, propamocarb-hydrochlorid, Bordeaux mixture (Bordeaux mixture), copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, ferbam, mancozeb ( mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram ), anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen , sulfonamides (flusulfamide), hexachlorobenzene (hexachlorobenzene), pentachlorophenol (pentachlorphenole) and its salts, tetrachlorophthalide (phthalide), tolylfluanid (tolylfluanid), N-(4-chloro-2 -Nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide, docodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris (albesilate), dithianon, 2,6-dimethyl-1H,5H-[1,4] Dithiadieno[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetraone, validamycin, polyoxomycin ( polyoxinB); melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, thiadiazole acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: phytophosphine (fosetyl), fosetyl-aluminum (fosetyl-aluminum), phosphorous acid and its salts, bronopol, chinomethionat, cyflufenamid, cymoxanil, danron (dazomet), debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamine, fenfenone ( fenpyrazamine), flumetover, sulfamethoxazole, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper, propoxy Quinoline (proquinazid), tebufloquin, phylloxacin, triazoxide and the like.
有益效果beneficial effect
综上所述，由于采用了上述技术方案，本发明的有益效果是：To sum up, due to the adoption of the above-mentioned technical solutions, the beneficial effects of the present invention are:
通过对2,3-二甲基-6-叔丁基-8-氟-4-羟基喹啉结构的化合物进行化学修饰，引入了吡唑结构，得到的喹啉酚类衍生物或其作为农药可接受的盐不仅对稻瘟病具有极佳的生物活性，对除稻瘟病之外的其它防治对象均具有令人满意的防除活性，且对作物有极佳的安全性。By chemically modifying the compound of 2,3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline structure, the pyrazole structure is introduced, and the obtained quinoline phenol derivatives or their use as pesticides The acceptable salt not only has excellent biological activity against rice blast, but also has satisfactory control activity against other control objects except rice blast, and has excellent safety to crops.
本发明的实施方式Embodiments of the present invention
下面将结合本发明实施例，对本发明实施例中的技术方案进行清楚、完整地描述。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
通过对所合成的化合物的经济性、多样性以及生物活性进行综合考量，优选了部分化合物列于下表中。具体的化合物结构如表1所示、具体的化合物物性数据如表2所示。表1-2中的化合物只是为了更好的说明本发明，并不会对本发明产生限定，本领域的技术人员不应将此理解为本发明上述主题的范围仅限于以下化合物。By comprehensively considering the economy, diversity and biological activity of the synthesized compounds, some of the preferred compounds are listed in the following table. The specific compound structure is shown in Table 1, and the specific compound physical property data is shown in Table 2. The compounds in Table 1-2 are only to better illustrate the present invention, and do not limit the present invention. Those skilled in the art should not interpret this as the scope of the above-mentioned subject matter of the present invention is limited to the following compounds.
Figure PCTCN2020140687-appb-000006
Figure PCTCN2020140687-appb-000006
表1式I化合物结构Table 1 The structure of the compound of formula I
Figure PCTCN2020140687-appb-000007
Figure PCTCN2020140687-appb-000007
Figure PCTCN2020140687-appb-000008
Figure PCTCN2020140687-appb-000008
Figure PCTCN2020140687-appb-000009
Figure PCTCN2020140687-appb-000009
Figure PCTCN2020140687-appb-000010
Figure PCTCN2020140687-appb-000010
表2  1H NMR数据 Table 2 1 H NMR data
Figure PCTCN2020140687-appb-000011
Figure PCTCN2020140687-appb-000011
Figure PCTCN2020140687-appb-000012
Figure PCTCN2020140687-appb-000012
制备本发明化合物的方法在以下技术方案和实施例中进行了说明。原料可以经市场购买到或者可以通过文献中已知的方法或者如详解所示进行制备。本领域技术人员应当理解，也可以利用其它合成路线合成本发明的化合物。尽管在下文中已经对合成路线中的具体原料和条件进行了说明，但是，可以很容易地将其替换为其它类似的原料及条件，这些对本发明制备方法的变型或者变体而产生的诸如化合物的各种异构体等都包括在本发明范围内。另外，如下所述制备方法可以按照本发明公开内容、使用本领域技术人员熟知的常规化学方法进行进一步修饰。例如，在反应过程中对适当的基团进行保护等等。Methods for preparing the compounds of the present invention are illustrated in the following Schemes and Examples. Starting materials are commercially available or can be prepared by methods known in the literature or as detailed. Those skilled in the art will appreciate that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although the specific starting materials and conditions in the synthetic routes have been described hereinafter, they can be easily substituted for other similar starting materials and conditions, such as compounds such as compounds produced by the modification or variation of the preparation method of the present invention. Various isomers and the like are included in the scope of the present invention. In addition, the preparation methods described below can be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protection of appropriate groups during the reaction and the like.
实施例1Example 1
化合物I-3的合成：Synthesis of compound I-3:
Figure PCTCN2020140687-appb-000013
Figure PCTCN2020140687-appb-000013
将中间体II-3(2.47g，10mmol)、二氯甲烷(30ml)加入到反应瓶内，20℃搅拌下加入中间体III-3(1.98g，10mmol)，20℃下搅拌反应加入三乙胺(2eq)，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，旋出溶剂，干燥，柱层析提纯，得到化合物I-3，3.17g，白色固体粉末，熔点：176.1-177.2℃；1H NMR(500MHz,Chloroform-d)δ7.43(dd,J＝12.8,1.8Hz,2H),4.25(t,J＝7.3Hz,2H),3.24(t,J＝7.4Hz,2H),2.99(qd,J＝7.5,1.5Hz,2H),2.77(d,J＝1.6Hz,3H),2.71(q,J＝7.5Hz,2H),2.29(d,J＝1.7Hz,3H),1.37–1.29(m,12H).Intermediate II-3 (2.47 g, 10 mmol) and dichloromethane (30 ml) were added to the reaction flask, and intermediate III-3 (1.98 g, 10 mmol) was added under stirring at 20 °C, and triethyl was added to the reaction with stirring at 20 °C. Amine (2eq), followed the reaction by TLC (ethyl acetate:petroleum ether=1:1, GF254, UV color development), after the reaction was completed, spin out the solvent, dry, and purify by column chromatography to obtain compound I-3, 3.17g , white solid powder, melting point: 176.1-177.2℃; 1H NMR (500MHz, Chloroform-d) δ7.43 (dd, J=12.8, 1.8Hz, 2H), 4.25 (t, J=7.3Hz, 2H), 3.24 (t, J=7.4Hz, 2H), 2.99 (qd, J=7.5, 1.5Hz, 2H), 2.77 (d, J=1.6Hz, 3H), 2.71 (q, J=7.5Hz, 2H), 2.29 (d, J=1.7Hz, 3H), 1.37–1.29 (m, 12H).
实施例2Example 2
化合物I-41的合成：Synthesis of compound I-41:
Figure PCTCN2020140687-appb-000014
Figure PCTCN2020140687-appb-000014
将中间体II-41(同II-2，2.47g，10mmol)、乙腈(30ml)加入到反应瓶内，20℃搅拌下加入中间体III-41(2.12g，10mmol)，20℃下搅拌反应加入三乙胺(2eq)，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，旋出溶剂，干燥，柱层析提纯，得到化合物I-41即目标化合物3.12g，白色固体粉末，熔点：158.6-159.2℃； 1H NMR(500MHz,Chloroform-d)δ7.47–7.40(m,2H),4.24–4.17(m,2H),3.16(t,J＝6.5Hz,2H),3.00(qd,J＝7.4,2.0Hz,2H),2.77(d,J＝3.1Hz,3H),2.29(d,J＝2.2Hz,3H),2.10(th,J＝5.7,2.8Hz,2H),1.94(dtt,J＝8.9,5.9,2.6Hz,2H),1.33(s,12H) Intermediate II-41 (same as II-2, 2.47 g, 10 mmol) and acetonitrile (30 ml) were added to the reaction flask, and intermediate III-41 (2.12 g, 10 mmol) was added under stirring at 20 °C, and the reaction was stirred at 20 °C Triethylamine (2eq) was added, the reaction was followed by TLC (ethyl acetate:petroleum ether=1:1, GF254, UV color development), after the reaction was completed, the solvent was spun out, dried, and purified by column chromatography to obtain compound I-41 Namely target compound 3.12g, white solid powder, melting point: 158.6-159.2℃; 1 H NMR (500MHz, Chloroform-d) δ7.47-7.40(m, 2H), 4.24-4.17(m, 2H), 3.16(t ,J=6.5Hz,2H),3.00(qd,J=7.4,2.0Hz,2H),2.77(d,J=3.1Hz,3H),2.29(d,J=2.2Hz,3H),2.10(th ,J=5.7,2.8Hz,2H),1.94(dtt,J=8.9,5.9,2.6Hz,2H),1.33(s,12H)
实施例3Example 3
化合物I-44的合成：Synthesis of compound I-44:
Figure PCTCN2020140687-appb-000015
Figure PCTCN2020140687-appb-000015
将中间体II-44(同II-2，2.47g，10mmol)、乙腈(30ml)加入到反应瓶内，20℃搅拌下加入中间体III-44(2.40g，10mmol)，20℃下搅拌反应加入三乙胺(2eq)，TLC跟踪反应(乙酸乙酯：石油醚＝1:1，GF254，UV显色)，反应完全后，旋出溶剂，干燥，柱层析提纯，得到目标化合物I-44，3.12g，类白色固体粉末，熔点：197-202℃；1H NMR(500MHz,Chloroform-d)δ7.45–7.40(m,2H),4.20(s,2H),3.29–3.22(m,2H),2.77(d,J＝1.7Hz,3H),2.31(d,J＝1.7Hz,3H),2.14–2.06(m,2H),1.96(td,J＝6.0,3.1Hz,2H),1.46(s,9H),1.33(d,J＝1.7Hz,9H).Intermediate II-44 (same as II-2, 2.47 g, 10 mmol) and acetonitrile (30 ml) were added to the reaction flask, and intermediate III-44 (2.40 g, 10 mmol) was added under stirring at 20 °C, and the reaction was stirred at 20 °C Triethylamine (2eq) was added, and the reaction was followed by TLC (ethyl acetate:petroleum ether=1:1, GF254, UV color development), after the reaction was completed, the solvent was spun out, dried, and purified by column chromatography to obtain the target compound I- 44, 3.12g, off-white solid powder, melting point: 197-202℃; 1H NMR (500MHz, Chloroform-d) δ7.45-7.40(m, 2H), 4.20(s, 2H), 3.29-3.22(m, 2H), 2.77(d, J=1.7Hz, 3H), 2.31(d, J=1.7Hz, 3H), 2.14–2.06(m, 2H), 1.96(td, J=6.0, 3.1Hz, 2H), 1.46(s, 9H), 1.33(d, J=1.7Hz, 9H).
实施例4Example 4
制剂的制备：Preparation of the formulation:
1、粉剂：称取20％的式(Ⅰ)化合物，80％的高岭土混合均匀，经粉碎而得到产品。1. Powder: Weigh 20% of the compound of formula (I), mix 80% of kaolin clay uniformly, and pulverize to obtain the product.
2、可湿性粉剂：称取20％的式(Ⅰ)化合物、8％的木质素磺酸钙、2％十二烷硫酸钠、3％白炭黑、高岭土加至100％。混合均匀，经气流粉碎后得到产品。2. Wettable powder: Weigh 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium dodecyl sulfate, 3% of white carbon black, and kaolin and added to 100%. Mix evenly, and get the product after jet pulverization.
3、水分散粒剂：称取60％的式(Ⅰ)化合物、6％木质素磺酸钠、4％NNO(烷基萘磺酸盐甲醛缩合物)、2％拉开粉BX(二丁基萘磺酸钠)、3％K-12(十二烷基硫酸钠)、5％羧甲基(乙基)纤维素、5％硅藻土、5％葡萄糖、高岭土加至100％。混合均匀，经气流粉碎后，称量好粉剂加入水混合，在造粒机中进行造粒，然后干燥、筛分，即得到颗粒状产品。3. Water-dispersible granules: weigh 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkylnaphthalene sulfonate formaldehyde condensate), 2% of pull-open powder BX (dibutyl) sodium naphthalene sulfonate), 3% K-12 (sodium dodecyl sulfate), 5% carboxymethyl (ethyl) cellulose, 5% diatomaceous earth, 5% glucose, kaolin were added to 100%. Mix evenly, after jet pulverization, weigh the powder, add water to mix, granulate in a granulator, then dry and sieve to obtain a granular product.
4、乳油：称取15％的式(Ⅰ)化合物、5％农乳700#、5％农乳500#、6％农乳1601#、10％环已酮、3％N-甲基吡咯烷酮、溶剂油150加至100％，经溶解完全并混合均匀，得到产品。4. EC: Weigh 15% of the compound of formula (I), 5% of Nongru 700#, 5% of Nongrut 500#, 6% of Nongrut 1601#, 10% of cyclohexanone, 3% of N-methylpyrrolidone, Solvent oil 150 was added to 100%, and the product was obtained after complete dissolution and uniform mixing.
5、悬浮剂：称取15％的式(Ⅰ)化合物、4％FS3000(磷酸酯型阴离子表面活性剂)、2％NS-500LQ(非离子型羟基聚环氧乙烷嵌段共聚物)、0.2％黄原胶、1％硅酸镁铝、5％乙二醇、0.1％BIT(1,2-苯并异噻唑啉-3-酮)、0.3％有机改性硅氧烷消泡剂，去离子水加至100％，制成浆料，进行砂磨后得到产品。5. Suspending agent: weigh 15% of the compound of formula (I), 4% FS3000 (phosphate ester type anionic surfactant), 2% NS-500LQ (non-ionic hydroxypolyethylene oxide block copolymer), 0.2% xanthan gum, 1% magnesium aluminum silicate, 5% ethylene glycol, 0.1% BIT (1,2-benzisothiazolin-3-one), 0.3% organo-modified siloxane defoamer, Deionized water was added to 100% to make a slurry, and the product was obtained after sanding.
以上均为重量百分比。The above are all weight percentages.
实施例5Example 5
稻瘟病保护性防治试验(Pyricularia oryzae)：Rice blast protective control test (Pyricularia oryzae):
寄主作物为水稻(鲁稻1号)，具体操作如下：The host crop is rice (Ludao No. 1), and the specific operations are as follows:
称取一定质量化合物样品，溶解于丙酮中，配制成母液备用。试验时，将化合物样品和对照药剂用0.1％吐温80的水配制成系列浓度梯度药液，用于活体筛选。选择三叶一心、长势一致的盆栽稻苗，标记后按序排放，供实验用。喷雾器类型为喷雾塔，每处理喷30ml药液，自然晾干。24h后接种病原菌，设空白对照。在已长满孢子的培养皿中，用无菌水冲洗表面孢子，用2～4层纱布过滤，制成浓度为1×10 5-1×10 6个/mL的孢子悬浮液，然后用接种喷雾器(压力0.1MPa)在稻苗上均匀喷雾，接种后的试材移入保湿箱(室)或人工气候室，相对湿度>95％，温度为26-28℃、黑暗条件下培养，24h后移入12h光暗交替、光照强度大于20000lx的培养箱(室)或温室高湿培养，5～7d后视空白对照发病情况进行分级调查。 A certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use. During the test, compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening. Select potted rice seedlings with three leaves and one heart and consistent growth, and arrange them in order after marking for experimental use. The type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and a blank control was set. In the petri dish that has been covered with spores, rinse the surface spores with sterile water, filter with 2 to 4 layers of gauze to make a spore suspension with a concentration of 1×10 5 -1×10 6 /mL, and then inoculate with A sprayer (pressure 0.1MPa) was used to spray evenly on the rice seedlings. After inoculation, the test materials were moved into a humidification box (room) or an artificial climate chamber. The relative humidity was > 95%, and the temperature was 26-28°C, and cultivated under dark conditions. After 24 hours, they were moved in. 12h light-dark alternation, light intensity greater than 20000lx incubator (room) or greenhouse high-humidity culture, 5 to 7 days later, depending on the incidence of the blank control to conduct a graded investigation.
防效级别：Prevention level:
A：防效在80％以上；A: The control effect is above 80%;
B：防效在50-79％之间；B: The control effect is between 50-79%;
C：防效不足50％；C: The control effect is less than 50%;
稻瘟病保护性试验结果如表3所示。The results of the rice blast protection test are shown in Table 3.
表3稻瘟病保护性试验结果Table 3 Rice blast protective test results
Figure PCTCN2020140687-appb-000016
Figure PCTCN2020140687-appb-000016
实施例6Example 6
稻瘟病保护性防治试验(Pyricularia oryzae)：Rice blast protective control test (Pyricularia oryzae):
寄主作物为水稻(山农13)，具体操作如下：The host crop is rice (Shannong 13). The specific operations are as follows:
称取一定质量化合物样品，溶解于丙酮中，配制成母液备用。试验时，将化合物样品和对照药剂用0.1％吐温80的水配制成系列浓度梯度药液，用于活体筛选。选择三叶一心、长势一致的盆栽稻苗，标记后按序排放，供实验用。喷雾器类型为喷雾塔，每处理喷30ml药液，自然晾干。24h后接种病原菌，设空白对照以及其它药剂对照。在已长满孢子的培养皿中，加入无菌水，刮取表面孢子，用2～4层纱布过滤，制成浓度为5×10 5-6×10 5个/mL的孢子悬浮液，然后用接种喷雾器(压力0.1MPa)在稻苗上均匀喷雾，接种后的试材移入保湿箱(室)或人工气候室，相对湿度>85％，温度为26-28℃，24h后移入有光照强度大于2000lx的培养箱(室)或温室高湿培养，5～7d后视空白 对照发病情况进行调查。 A certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use. During the test, compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening. Select potted rice seedlings with three leaves and one heart and consistent growth, and arrange them in order after marking for experimental use. The type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and blank control and other drug control were set. Add sterile water to the petri dish that has grown with spores, scrape the surface spores, filter with 2 to 4 layers of gauze, and prepare a spore suspension with a concentration of 5×10 5 -6×10 5 /mL, and then Use an inoculation sprayer (pressure 0.1MPa) to spray evenly on the rice seedlings, and move the inoculated test material into a humidification box (room) or an artificial climate room, the relative humidity is > 85%, the temperature is 26-28 ℃, and the light intensity is moved after 24 hours. More than 2000lx incubator (room) or greenhouse high-humidity culture, after 5 to 7 days, the incidence of blank control will be investigated.
防效级别：Prevention level:
0：防效在95％以上；0: The control effect is above 95%;
1：防效在90％以上；1: The control effect is above 90%;
2：防效在80％以上；2: The control effect is above 80%;
3：防效在50-79％之间；3: The control effect is between 50-79%;
4：防效不足50％；4: The control effect is less than 50%;
稻瘟病保护性试验结果如表4所示。The results of the rice blast protection test are shown in Table 4.
表4不同浓度下稻瘟病保护性试验结果Table 4 Results of rice blast protection test at different concentrations
Figure PCTCN2020140687-appb-000017
Figure PCTCN2020140687-appb-000017
Figure PCTCN2020140687-appb-000018
Figure PCTCN2020140687-appb-000018
实施例7Example 7
瓜类白粉病保护性防治试验(Sphaeotheca fuliginea)：Test of protective control of cucurbit powdery mildew (Sphaeotheca fuliginea):
寄主作物为黄瓜(津优1号)，采用盆栽幼苗法，具体操作如下：The host crop is cucumber (Jinyou No. 1), and the potted seedling method is adopted. The specific operations are as follows:
称取一定质量化合物样品，溶解于丙酮中，配制成母液备用。试验时，将化合物样品和对照药剂用0.1％吐温80的水配制成系列浓度梯度药液，用于活体筛选。选择生长整齐一致的2-4叶期盆栽黄瓜幼苗，作为黄瓜白粉病的试验寄主植物。喷雾器类型为喷雾塔，每处理喷30ml药液，自然晾干。24h后接种病原菌，设空白对照以及其它药剂对照。将发病黄瓜叶片上24h内产生的白粉病菌新鲜孢子配成悬浮液(浓度为1×10 5个孢子/mL)，喷施于接种叶片上，在适宜的条件下培养。7～10d后清水对照完全发病，调查试验结果。 A certain mass of compound samples were weighed, dissolved in acetone, and prepared into a mother solution for later use. During the test, compound samples and control agents were prepared into a series of concentration gradient liquids with 0.1% Tween 80 water for in vivo screening. The 2-4 leaf stage potted cucumber seedlings with uniform growth were selected as the experimental host plants for cucumber powdery mildew. The type of sprayer is spray tower, spray 30ml liquid medicine for each treatment, and let it dry naturally. After 24h, the pathogenic bacteria were inoculated, and blank control and other drug control were set. The fresh spores of powdery mildew produced on the leaves of diseased cucumbers within 24 hours were made into a suspension (concentration of 1×10 5 spores/mL), sprayed on the inoculated leaves, and cultivated under suitable conditions. After 7 to 10 days, the clear water control completely developed the disease, and the test results were investigated.
防效级别：Prevention level:
I：防效在90％以上；I: The control effect is above 90%;
II：防效在80％以上；II: The control effect is above 80%;
III：防效在50-79％之间；III: The control effect is between 50-79%;
IV：防效不足50％；IV: The control effect is less than 50%;
瓜类白粉病保护性试验结果如表5所示。Table 5 shows the protective test results of melon powdery mildew.
表5瓜类白粉病保护性试验结果Table 5 The protective test results of melon powdery mildew
Figure PCTCN2020140687-appb-000019
Figure PCTCN2020140687-appb-000019
Figure PCTCN2020140687-appb-000020
Figure PCTCN2020140687-appb-000020
上述实施例只是为了说明本发明的技术构思及特点，其目的是在于让本领域内的普通技术人员能够了解本发明的内容并据以实施，并不能以此限制本发明的保护范围。凡是根据本发明内容的实质所作出的等效的变化或修饰，都应涵盖在本发明的保护范围内。The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose thereof is to enable those of ordinary skill in the art to understand the content of the present invention and implement them accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the essence of the present invention shall be included within the protection scope of the present invention.
工业实用性Industrial Applicability
本发明的化合物可以作为杀菌剂使用，用于控制植物病害，尤其适合用于水稻、麦类和/或瓜类。The compounds of the present invention can be used as fungicides for controlling plant diseases, especially for rice, wheat and/or melons.

Claims (10)

  1. 一种喹啉酚类衍生物或其作为农药可接受的盐，其结构式如下：A kind of quinoline phenol derivatives or its salt acceptable as pesticide, its structural formula is as follows:
    Figure PCTCN2020140687-appb-100001
    Figure PCTCN2020140687-appb-100001
    式(I)中，In formula (I),
    R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
    R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷硫基、卤代C 1-C 6烷硫基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkylthio, halogenated C 1 -C 6 alkylthio, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
    或者，R 1和R 2一起形成基团-(CH 2) t-，t表示2-8的整数； Alternatively, R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 8;
    R 3、R 4、R 5分别独立地选自H、卤素、CN、硝基、醛基、羧基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、苯基或苯基取代的C 1-C 6烷基； R 3 , R 4 , R 5 are independently selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halo C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halo C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or phenyl-substituted C 1- C 6 alkyl;
    X表示卤素、CN、硝基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基，m表示0-3的整数。 X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 0-3.
  2. 如权利要求1所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，式(I)中，A kind of quinoline phenol derivative as claimed in claim 1 or its salt acceptable as pesticide, is characterized in that, in formula (I),
    R 1表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 1 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
    R 2表示H、C 1-C 6烷基、卤代C 1-C 6烷基、C 1-C 6烷氧基或卤代C 1-C 6烷氧基； R 2 represents H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halogenated C 1 -C 6 alkoxy;
    或者，R 1和R 2一起形成基团-(CH 2) t-，t表示2-7的整数； Alternatively, R 1 and R 2 together form a group -(CH 2 ) t -, where t represents an integer from 2 to 7;
    R 3、R 4分别独立地选自H、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基或C 3-C 6环烷基； R 3 and R 4 are independently selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl;
    R 5选自H、卤素、CN、硝基、醛基、羧基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基、卤代C 1-C 6烷氧基、C 3-C 6环烷基、苯基或苄基； R 5 is selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, halogenated C 2 -C 6 alkenyl, C 1 -C 6 alkoxy, halogenated C 1 -C 6 alkoxy, C 3 -C 6 cycloalkyl, phenyl or benzyl;
    X表示卤素、CN、硝基、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基，m表示1-3的整数； X represents halogen, CN, nitro, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 ring Alkyl, m represents an integer of 1-3;
    优选的，R 3、R 4分均为Me或Et，X为6-t-Bu，m为1。 Preferably, R 3 and R 4 are both Me or Et, X is 6-t-Bu, and m is 1.
  3. 如权利要求2所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示2-5的整数。 A kind of quinoline phenol derivative as claimed in claim 2 or its salt acceptable as pesticide is characterized in that, in formula (I), R 1 and R 2 together form group -(CH 2 ) t - , t represents an integer from 2 to 5.
  4. 如权利要求3所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，式(I)中，R 3、R 4相 同，选自H、C 1-C 6烷基、卤代C 1-C 6烷基、C 2-C 6烯基、卤代C 2-C 6烯基、C 1-C 6烷氧基或C 3-C 6环烷基；优选地，R 3、R 4相同，选自H、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2Br、CHBr 2、CBr 3、OMe、OEt、乙烯基、环丙烷基。 A kind of quinoline phenol derivative as claimed in claim 3 or its salt acceptable as pesticide is characterized in that, in formula (I), R 3 and R 4 are the same, and are selected from H, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 2 -C 6 alkenyl group, a halo-C 2 -C 6 alkenyl, C 1 -C 6 alkoxy or C 3 -C 6 cycloalkyl; preferably Typically, R 3 and R 4 are the same and selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2 , CCl 3 , CH 2 F, CHF 2, CF 3, CH 2 Br, CHBr 2, CBr 3, OMe, OEt, vinyl, cyclopropyl.
  5. 如权利要求1所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示2-5的整数； A kind of quinoline phenol derivatives as claimed in claim 1 or its salt acceptable as pesticide is characterized in that, in formula (I), R 1 and R 2 together form group -(CH 2 ) t - , t represents an integer from 2 to 5;
    R 3、R 4分别独立地选自H、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、OMe、OEt、乙烯基、环丙烷基； R 3 and R 4 are independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane ;
    R 5选自H、F、Cl、Br、CN、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2Br、CHBr 2、CBr 3、CH 2CF 3、CH 2CH 2Cl、乙烯基、OMe、OEt、n-PrO、i-PrO、n-BuO、i-BuO、s-BuO、t-BuO、环丙烷基、环丙烷氧基、硝基、醛基、羧基、羟基； R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH 2 Cl, CHCl 2, CCl 3, CH 2 F, CHF 2 , CF 3, CH 2 Br, CHBr 2, CBr 3, CH 2 CF 3, CH 2 CH 2 Cl, vinyl, OMe, OEt, n-PrO , i-PrO, n- BuO, i-BuO, s-BuO, t-BuO, cyclopropanyl, cyclopropanyloxy, nitro, aldehyde, carboxyl, hydroxyl;
    X表示H、F、Cl、Br、Me、Et、n-Pr、i-Pr、n-Bu、i-Bu、s-Bu、t-Bu、OMe、OEt、乙烯基、环丙烷基，m为1或2。X represents H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane, m is 1 or 2.
  6. 如权利要求5所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，式(I)中，R 1和R 2一起形成基团-(CH 2) t-，t表示3-4的整数； A kind of quinoline phenol derivatives as claimed in claim 5 or its salt acceptable as pesticide is characterized in that, in formula (I), R 1 and R 2 together form group -(CH 2 ) t - , t represents an integer from 3 to 4;
    R 3、R 4均为Me或Et； R 3 and R 4 are both Me or Et;
    R 5选自H、F、Cl、Br、CN、Me、Et、n-Pr、i-Pr、CH 2Cl、CHCl 2、CCl 3、CH 2F、CHF 2、CF 3、CH 2CF 3、CH 2CH 2Cl、乙烯基、OMe、OEt、硝基； R 5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH 2 Cl, CHCl 2 , CCl 3 , CH 2 F, CHF 2 , CF 3 , CH 2 CF 3 , CH 2 CH 2 Cl, vinyl, OMe, OEt, nitro;
    X表示叔丁基，m为1。X represents a tert-butyl group, and m is 1.
  7. 如权利要求1-6中任一项所述的一种喹啉酚类衍生物或其作为农药可接受的盐，其特征在于，选自：A kind of quinoline phenol derivative as described in any one of claim 1-6 or its salt acceptable as pesticide, is characterized in that, is selected from:
    Figure PCTCN2020140687-appb-100002
    Figure PCTCN2020140687-appb-100002
    Figure PCTCN2020140687-appb-100003
    Figure PCTCN2020140687-appb-100003
  8. 一种杀菌组合物，其特征在于，包括杀菌有效量的权利要求1-7任意一项所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种；优选的，还包括制剂载体或制剂助剂。A bactericidal composition, characterized in that it comprises at least one of the quinoline phenol derivatives described in any one of claims 1-7 or at least one of their acceptable salts as pesticides in a bactericidal effective amount; preferably, also Including formulation carriers or formulation adjuvants.
  9. 一种控制植物病害的方法，其特征在于，包括将生物有效量的如权利要求1-7任一项所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种或如权利要求8所述的杀菌组合物施用在植物上。A method for controlling plant diseases, characterized in that, comprising adding a biologically effective amount of the quinoline phenol derivatives according to any one of claims 1-7 or at least one of the acceptable salts thereof as pesticides or The fungicidal composition of claim 8 is applied to plants.
  10. 如权利要求1-7任一项所述的喹啉酚类衍生物或其作为农药可接受的盐中的至少一种或如权利要求8所述的杀菌组合物在控制植物病害方面的用途；优选的，所述植物病害为细菌性病害或真菌性病害；再优选的，所述植物病害为植物感染稻梨孢菌的病害。Use of the quinoline phenol derivatives as claimed in any one of claims 1 to 7 or at least one of their acceptable salts as pesticides or the fungicidal composition as claimed in claim 8 in controlling plant diseases; Preferably, the plant disease is a bacterial disease or a fungal disease; more preferably, the plant disease is a disease in which a plant is infected with P. oryzae.
PCT/CN2020/140687 2020-07-01 2020-12-29 Quinoline phenol derivative or pesticidally acceptable salt thereof, composition, and use thereof WO2022001047A1 (en)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0407192A2 (en) * 1989-07-07 1991-01-09 Meiji Seika Kabushiki Kaisha 4-Acyloxyquinoline derivatives and insecticidal or acaricidal compositions containing same
CN1259124A (en) * 1997-06-02 2000-07-05 罗纳-普朗克油化农业株式会社 4-quinolinol derivatives and agrohorticultural bactericides containing the same as active ingredient
WO2003010145A1 (en) * 2001-07-20 2003-02-06 Bayer Cropscience Ag Biphenyl-substituted 4-hydroxy-quinolones and their use as pesticides and herbicides
CN1444562A (en) * 2000-05-30 2003-09-24 明治制果株式会社 Rice blast control agents
CN108863889A (en) * 2018-08-09 2018-11-23 西北农林科技大学 L-Glutimic acid derivative and its preparation method and application
CN109320452A (en) * 2017-07-31 2019-02-12 东莞东阳光科研发有限公司 Quinoline derivatives and its preparation method and application

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0407192A2 (en) * 1989-07-07 1991-01-09 Meiji Seika Kabushiki Kaisha 4-Acyloxyquinoline derivatives and insecticidal or acaricidal compositions containing same
CN1259124A (en) * 1997-06-02 2000-07-05 罗纳-普朗克油化农业株式会社 4-quinolinol derivatives and agrohorticultural bactericides containing the same as active ingredient
CN1444562A (en) * 2000-05-30 2003-09-24 明治制果株式会社 Rice blast control agents
WO2003010145A1 (en) * 2001-07-20 2003-02-06 Bayer Cropscience Ag Biphenyl-substituted 4-hydroxy-quinolones and their use as pesticides and herbicides
CN109320452A (en) * 2017-07-31 2019-02-12 东莞东阳光科研发有限公司 Quinoline derivatives and its preparation method and application
CN108863889A (en) * 2018-08-09 2018-11-23 西北农林科技大学 L-Glutimic acid derivative and its preparation method and application

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