CN113880840A - Quinolinophenol derivative or salt thereof acceptable as pesticide, composition and application thereof - Google Patents

Quinolinophenol derivative or salt thereof acceptable as pesticide, composition and application thereof Download PDF

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CN113880840A
CN113880840A CN202010621034.8A CN202010621034A CN113880840A CN 113880840 A CN113880840 A CN 113880840A CN 202010621034 A CN202010621034 A CN 202010621034A CN 113880840 A CN113880840 A CN 113880840A
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halo
radical
alkyl
alkoxy
formula
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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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Hailir Pesticides and Chemicals Group Co Ltd
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Priority to PCT/CN2020/140687 priority patent/WO2022001047A1/en
Publication of CN113880840A publication Critical patent/CN113880840A/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

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Engineering & Computer Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Environmental Sciences (AREA)
  • Plant Pathology (AREA)
  • General Health & Medical Sciences (AREA)
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  • Agronomy & Crop Science (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention belongs to the field of pesticides, and particularly relates to a quinolyl phenol derivative or a salt and a composition thereof acceptable as pesticides and an application thereof, wherein the compound has a structure shown in a formula (I):

Description

Quinolinophenol derivative or salt thereof acceptable as pesticide, composition and application thereof
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a quinolyl derivative or a salt and a composition thereof acceptable as pesticides, and application of the compounds or the salt and the composition thereof acceptable as pesticides as bactericides.
Background
It is known that quinoline derivatives obtained by substituting a substituent such as allyloxy group, amino group, or benzoyl group for hydrogen at the 4-position of the quinoline skeleton have a certain biological activity against plant pathogenic bacteria. Patent application No. cn98805678.x describes that 4-quinol derivatives having specific substituents at positions 2,3 and 5-8 of the quinoline skeleton and acid addition salts thereof exhibit excellent antibacterial activity against various plant pathogenic bacteria including rice blast fungus, rice flaccid mildew fungus, melon powdery mildew fungus, potato anthracnose fungus, etc. Further described in application No. 01813588.9 is a 4-quinolenol derivative having methyl substituents at the 2-and 3-positions of the quinoline skeleton, a t-butyl substituent at the 6-position, and a fluorine substituent at the 8-position, and an acid addition salt thereof for use in the control of rice blast. However, there is room for improvement in the control activity against a control target including rice blast, and the activity is not satisfactory at a lower dose.
Technical problem
In order to solve the problems in the prior art, the invention provides a quinolyl phenol derivative or a salt thereof acceptable as a pesticide, a composition and application thereof. The applicant has unexpectedly found that a quinolyl phenol derivative, particularly a 2, 3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline derivative or a pesticidally acceptable salt thereof, has not only excellent biological activity against rice blast but also satisfactory control activity against other control subjects than rice blast and excellent safety against crops.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is as follows: a quinolyl phenol derivative or a pesticidally acceptable salt thereof, having the formula:
Figure BDA0002565164940000011
in the formula (I), the compound is shown in the specification,
R1representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R2representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or, R1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 8;
R3、R4、R5each independently selected from H, halogen, CN, nitro, aldehyde group, carboxyl and C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl or phenyl substituted C1-C6An alkyl group;
x represents halogen, CN, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6Cycloalkyl, and m represents an integer of 0 to 3.
Further, in the formula (I), R1Representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R2representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or, R1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 7;
R3、R4each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy or C3-C6A cycloalkyl group;
R5selected from H, halogen, CN, nitryl, aldehyde group, carboxyl and C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl or benzyl;
x represents halogen, CN, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6Cycloalkyl, m represents an integer of 1 to 3;
further, R3、R4All are Me or Et, X is 6-t-Bu, and m is 1.
Further, in the formula (I), R1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 5.
Further, in the formula (I), R3、R4Same, selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group; preferably, R3、R4The same is selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3OMe, OEt, vinyl, cyclopropane.
Further, in the formula (I), R1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 5;
R3、R4each independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane;
R5selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl, vinyl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopropaneoxy, nitro, aldehyde group, carboxyl and 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, and m is 1 or 2.
Further, in the formula (I), R1And R2Together form a radical- (CH)2)t-, t represents an integer of 3 to 4;
R3、R4are both Me or Et;
R5selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2CF3、CH2CH2Cl, vinyl, OMe, OEt,A nitro group;
x represents a tert-butyl group, and m is 1.
Further, the compound of formula (I) is specifically selected from:
Figure BDA0002565164940000021
Figure BDA0002565164940000031
Figure BDA0002565164940000041
the agrochemically acceptable salt can be a salt prepared by reacting the quinolyl phenol derivative 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) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid); the pesticide acceptable salt can also be a salt prepared by reacting the quinoline phenol derivative 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 an organic base (such as trimethylamine, triethylamine and the like).
Further, the pesticidally acceptable salt may be a potassium, sodium, ammonium, calcium, pyridinium or choline salt.
The invention also discloses a bactericidal composition which comprises at least one of the quinoline phenolic derivatives or the salts thereof which are acceptable as pesticides, wherein the quinoline phenolic derivatives or the salts thereof have bactericidal effective dose; further, the preparation also comprises a preparation carrier or a preparation auxiliary agent.
The invention also discloses a method for controlling plant diseases, which comprises applying a biologically effective amount of at least one of the quinolyl phenol derivatives or the salts thereof which are acceptable as pesticides or the bactericidal composition on plants.
The invention also discloses the application of the quinolyl phenol derivative or at least one of the salt thereof which is acceptable as pesticide or the bactericidal composition in controlling plant diseases; preferably, the plant disease is a bacterial disease or a fungal disease.
In the definitions of the structural formulae of the compounds mentioned above, the terms used have the following meanings:
halogen or halogen: refers to fluorine, chlorine, bromine, iodine.
C1-C6Alkyl groups: straight or branched chain alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
Halogen substituted C1-C6Alkyl groups: straight-chain or branched alkyl groups having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkyl groups may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C2-C6Alkenyl: a linear or branched alkenyl group having 2 to 6 carbon atoms, such as an ethenyl group, a propenyl group and the like.
Halogen substituted C2-C6Alkenyl: straight-chain or branched alkenyl groups having 2 to 6 carbon atoms, in which hydrogen atoms may be partially or entirely substituted with halogen, for example, chloroethenyl group and the like.
C1-C6Alkoxy groups: a linear or branched alkyl group having 1 to 6 carbon atoms bonded to the structure via an oxygen atom bond.
halo-C1-C6 alkoxy: straight or branched alkoxy having 1 to 6 carbon atoms, wherein hydrogen atoms in the alkoxy groups may be partially or wholly replaced by halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.
The radical abbreviations appearing in the present invention are in accordance with those commonly used in the art, e.g., Me represents methyl, Et represents ethyl, Pr represents propyl, Bu represents butyl, n-Bu represents n-butyl, i-Bu represents isobutyl, s-Bu represents sec-butyl, t represents tert-butyl, phenyl represents phenyl, OMe represents methoxy, etc.
A method for synthesizing a compound represented by the formula I comprises the step of reacting a compound represented by the formula III with a compound represented by the formula II (in the chemical formula shown below, the substituents and symbols have the same meanings as those defined in the formula I as long as the substituents and symbols are not defined in any other way) in the presence or absence of an alkaline reagent and in the presence or absence of a solvent to obtain a target compound represented by the formula I. The compounds represented by formulae II and III are commercially available or can be prepared by methods described in EP 407192A:
Figure BDA0002565164940000051
further, the solvent is selected from one or more of acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane and ethyl acetate;
further, the reaction may be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and the post-treatment may be carried out according to a conventional method.
The compounds of the formula I according to the invention or their salts, respectively compositions, which are acceptable as pesticides are suitable with outstanding efficacy as fungicides, in particular as fungicides or bactericides, some of which are systemically effective and can be used in crop protection as foliar fungicides, fungicides for seed dressing and soil fungicides. Furthermore, they are suitable for controlling harmful fungi, which occur in particular in wood or in the roots of plants, in particular for treating fungi or bacteria, or materials, plants, soils or seeds to be protected against fungal or bacterial attack, with an effective amount of at least one compound of the formula I as defined according to the invention or as a pesticidally acceptable salt, composition.
The compounds I according to the invention or their salts and compositions as pesticides are suitable for use in various cultivated plants, such as cereals, for example wheat, rye, barley, triticale, oats or rice; sugar beets, such as sugar or fodder beets; fruits such as pomes, stone fruits or berries, e.g. apples, pears, plums, peaches, almonds, cherries, strawberries or blueberries; leguminous plants, such as lentils, peas, alfalfa or soybeans; oil plants, such as rape, mustard, olives, sunflowers, coconut, cocoa beans, castor oil plants, oil palm, peanuts or soybeans; cucurbits, such as squash, cucumber or melon; fibrous plants, such as cotton, flax or jute; citrus fruits such as oranges, lemons, grapefruits or tangerines; vegetables, such as spinach, lettuce, asparagus, cabbage, carrots, onions, tomatoes, potatoes, cucurbits or bell peppers; laurel plants, such as avocado, cinnamon or camphor; crops of greater economic value, such as corn, soybean, oilseed rape, sugar cane, oil palm, tobacco, nuts, coffee, tea, bananas, grapes, hops, and the like; lawn; natural rubber plants or ornamental and forest plants, for example flowers, shrubs, broad-leaved trees or evergreens, for example conifers, and plant propagation material, for example seeds, tubers, cuttings and the like, for controlling plant diseases, in particular fungal diseases or bacterial diseases.
Preferably, the compounds I or their salts, compositions, respectively, are used in field crops, for example potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, maize, cotton, soybeans, oilseed rape, leguminous plants, sunflowers, coffee or sugar cane; fruits; preventing and treating fungal or bacterial diseases on ornamental plants or vegetables such as cucumber, tomato, kidney bean or pumpkin.
The invention also provides a bactericide composition comprising a compound of formula I. The compounds of formula I can be formulated in a variety of ways depending on the general biological and/or chemical and/or physical parameters. Examples of suitable formulation choices are: wettable Powders (WP), wettable liquids (SL), Soluble Powders (SP), dispersible liquids (DC), Aqueous Solutions (AS), Microemulsions (ME), Emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, Suspensions (SC), dispersible oil suspensions (OD), powders (DP), microcapsule suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules for spreading and soil application (GR), Aerosols (AE), ultra low volume agents (ULV) and wax products. Necessary formulation auxiliaries, such as inert substances, surfactants, solvents and other additives.
Examples of suitable additives are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetting agents, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, anti-freezing agents, anti-foaming agents, colorants, tackifiers, and binders.
Suitable solvents and liquid carriers are water and/or organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, such as toluene, paraffins, tetrahydronaphthalene, alkylated naphthalenes; alcohols, such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; glycols; dimethylsulfoxide (DMSO); ketones, such as cyclohexanone; esters, such as lactate, carbonate, fatty acid ester, γ -butyrolactone; a fatty acid; a phosphonate ester; amines; amides, such as N-methylpyrrolidone, fatty acid dimethylamide; and mixtures thereof.
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 oxide; polysaccharides such as cellulose, starch; fertilizers, such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, such as cereal flour, bark flour, wood flour and nut shell flour, and mixtures thereof.
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, dissolution promoters, wetting agents, penetration enhancers, protective colloids or adjuvants.
Suitable adjuvants are compounds which have negligible or even no pesticidal activity per se and which improve the biological properties of the compounds I on the target; examples are surfactants, mineral or vegetable oils and other auxiliaries.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethyl cellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates, and the like.
Suitable anti-freeze agents are ethylene glycol, propylene glycol, urea, glycerol, and the like.
Suitable antifoams are polysiloxanes, long-chain alcohols and fatty acid salts, and the like.
Suitable colorants (e.g. colored in red, blue or green) are pigments and dyes of low water solubility, which may be inorganic colorants (e.g. iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (e.g. alizarin colorants, azo colorants and phthalocyanine colorants).
Suitable active substances which can be mixed with the active substances according to the invention in a mixed or tank-mixed formulation are, for example, the substances known from the "national institute of New agricultural chemical technology" (national agricultural science and technology, published under the name 2010.9). For example, the fungicide active substances mentioned below may be mixed with the compounds of formula I (remarks: name of the compound, either by common name according to the International organization for standardization (ISO), or by chemical name, where appropriate with a code number): azoxystrobin (azoxystrobin), strobilurin (coumoxystrobin), coumoxystrobin (coumoxystrobin), dimoxystrobin (dimoxystrobin), enestroburin (enestrobin), enestroburin (fenaminstrobin), fenoxystrobin/fluxastrobin (flufenoxystrobin), fluoxastrobin (fluoxastrobin), kresoxim-methyl (kresoxim-methyl), metominostrobin (metominobin), orysastrobin (orysastrobin), picoxystrobin (picoxystrobin), pyraclostrobin (pyraclostrobin), pyraclostrobin (pyraoxystrobin), pyraoxystrobin (pyraoxystrobin), 2- [2- (2, 5-dimethylphenoxymethyl) phenyl]-methyl 3-methoxyacrylate, 2- (2- (3- (2, 6-dichlorophenyl) -1-methallyloxyaminomethyl) phenyl) -2-methoxyimino-N-methylacetamide, pyribencarb, triclopyr/chlorodincarb, oxazolinone (famoxadone), fenamidone (fenamidone); cyazofamid (cyazofamid), amisulbrom, 2-methylpropionic acid [ sic ], [ solution of cyazofamid (cyazofamid) ], and [ solution of cyazofamid ], [ solution of amisulbrom ], [ solution of 2-methylpropionic acid ], [ solution of cyazofamid (cyazofamid ], [ solution of amisulbrom ], [ solution of cyazofamid ], [ solution of amisulbrom ], [ solution of cyazofamid ], [ solution of 2-methyl-2-methylpropionic acid ] and [ solution of a
Figure BDA0002565164940000071
-8-benzyl-3- [ (3-acetoxy-4-methoxypyridine-2-carbonyl) amino]-6-methyl-4, 9-dioxo-1, 5-dioxepin-7-yl]Ester, 2-methylpropanoic acid [ (3S,6S,7R,8R) -8-benzyl-3- [ [ 3-acetoxymethoxy-4-methoxypyridine-2-carbonyl]Amino group]-6-methyl-4, 9-dioxo-1, 5-dioxepin-7-yl]Ester, 2-methylpropanoic acid [ (3S,6S,7R,8R) -8-benzyl-3- [ (3-isobutoxycarbonyloxy-4-methoxypyridine-2-carbonyl) amino]-6-methyl-4, 9-dioxo-1, 5-dioxepin-7-yl]Ester, 2-methylpropionic acid [ (3S,6S,7R,8R) -8-benzyl-3- [ [3- (1, 3-benzodioxol-5-ylmethoxy) -4-methoxypyridine-2-carbonyl]Amino group]-6-methyl-4, 9-dioxo-1, 5-dioxepin-7-yl]Ester, 2-methylpropanoic acid (3S,6S,7R,8R) -3- [ [ (3-hydroxy-4-methoxy-2-pyridinyl) carbonyl]Amino group]-6-methyl-4, 9-dioxo-8- (phenylmethyl) -1, 5-dioxepin-7-yl ester; benoxanil, bixafen, boscalid (boscalid), carboxin (carboxin), furamex (fenfuram), fluopyram (flupyram), flutolanil (flutolanil), flutolanil (fluxapyroxad), furametpyr (furametpyr), isopyrazam, mepronil (mepronil), oxycarboxin (oxarboxin), penflufen, penthiopyrad (penthiopyrad), sedaxane, phylloquat (tecloftalam), fludioxonil (thifluzamide), N- (4' -trifluoromethylsulfanyl-biphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- (2- (1,3, 3-trimethylbutyl) phenyl) -1, 3-dimethyl-5-fluoro-1H-4-carboxamide, N- [9- (methylene) pyrazole-carbonyl ] -1-methyl-4-carboxamide, 2,3, 4-tetrahydro-1, 4-methanonaphthalen-5-yl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; 3-difluoromethyl-1-methyl-N- (1,1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 3-trifluoromethyl-1-methyl-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-2, 3-indan-4-yl) pyrazole-4-carboxamide, 1,3, 5-trimethyl-N- (1,1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide; difluoro (F)Forest (diflumetorim), (5, 8-difluoroquinazolin-4-yl) - {2- [ 2-fluoro-4- (4-trifluoromethylpyridin-2-yloxy) phenyl]Ethyl } amine; nitrophenyl derivatives: binacryl, dinotefuran, dinocap, fluazinam; pyriminobac (ferimzone); an organometallic compound: triphenyltin-based salts, such as fentin-acetate, fentinchloride or fentinhydroxide; ametocradin and silthiopham (silthiofam); azaconazole (azaconazole), bitertanol (bitertanol), bromuconazole (broconazol), cyproconazole (cyproconazole), difenoconazole (difenoconazole), diniconazole (diniconazole), diniconazole M (diniconazole-M), epoxiconazole (epoxyconazole), fenbuconazole (fenbuconazole), fluquinconazole (fluquinconazole), flusilazole (flusilazole), flutriafol (flutriafol), hexaconazole (hexaconazole), amidazole (imaconazol), ipconazole (ipconazol), cyclopentconazole (metconazole), myclobutanil (epoxyconazole), epoxyconazole (paclobutrazol), paclobutrazol (paclobutrazol), pyriconazole (bithiozol), pyriconazole (bithionol), pyriconazole (bitazonol), pyriconazole (diniconazole), pyriconazole (diniconazole), pyriproxyfen (propiconazole), pyrimethanazole (tetraconazole), pyriproxyfen (tetraconazole), pyrimethanazole (tetraconazole), pyriproxyfen (tetraconazole), pyrimethanil (tetraconazole), pyriproxyfen (tetraconazole), pyrimethanil), pyrimethanzol (tetraconazole), pyriproxyfen (tetraconazole), pyrim (tetraconazole), pyrimethanil), pyrim (tetraconazole), pyrimethanil), pyrimethanazole (tetraconazole), pyrim (tetraconazole), pyrimethanazole (tetraconazole), pyrim (tetraconazole), pyrim-ethyl (tetraconazole), pyrim (tetraconazole), pyrim-ethyl (tetraconazole), pyrim (tetraconazole), pyrim-ethyl (tetraconazole), pyrim-ethyl (tetraconazole), pyrim (tetraconazole), pyrim-ethyl (tetraconazole), pyrim-ethyl (tetraconazole, Pyribenzoxim (pyrifenox), triforine (triforine), 4-dodecyl-2, 6-dimethylmorpholine (aldimorph), dodemorph (dodemorph), dodemorph acetate (dodemorph-acetate), fenpropimorph (fenpropimorph), tridemorph (tridemorph), fenpropidin (fenpropidin), flutriafol (piperalin), spiroxamine (spiroxamine), benalaxyl (benalaxyl-M), miraxyl (metalaxyl-M), metalaxyl (metalaxyl), mefenoxamine (furoamide), oxadixyl (oxadixyl), fenhexamide (fenoxamine), hymexazol (benoxazamide), benazol (benazol-M), isothiazolinone (fenazaquin), carbendazim (fenflurazole), carbendazim (benazolin), carbendazim (fenbutazine), carbendazim (benazol), carbendazim (benazolin), carbendazim (fenpyrad (benazolin), benazolidone (benazolidone) (benazol), benazolidone (benazol), benazolidone (benazol), benazolidone (benazol), benazolidone (benazol), benazolidone (benazol), benazolidone (benazol), benazolidone (benazol), benazolil), benazol), benazolil), benazol), benazolone (benazol, benazol-M), benazolil), benazolone, benazolil), benazol, benazolil, benazolone, benazolidone (benazolil, benazolone, benazolil, benazolone, benazol,Thiophanate-methyl, diethofencarb (diethofencarb), ethaboxam (ethaboxam), pencycuron (pencycuron), fluopicolide (fluopicolide), zoxamide (zoxamide), metrafenone (metrafenone), pyriofenone, cyprodinil (cyclopropyridine), mepanipyrim (mepanipyrim), pyrimethanil (pyrimethanil), blasticidin (bleticidin-S), kasugamycin (kasugamycin), kasugamycin hydrate (kasugamycin), milomycin (milomycin), streptomycin (streromycin), oxytetracycline (oxytetracycline), polyoxin (polyoxine), validamycin (valacyclina), fluocinolone (fenacin), iprodione (iprodione), pyrimethanil (fenthiobac (fenpyrane), pyrimethanil (fenpyraflufen), pyrimethanil (fenpropidin (fenpropidium), pyrimethanil (fenpropidin (pyrimethanil), pyrimethanil (pyricularia), pyricularia (pyricularia), pyricularia (pyricularia) and pyricularia (pyricularia) a (pyricularia), pyricularia (pyricularia) a (pyricularia) and pyricularia (pyricularia), pyricularia (pyricularia), pyricularia) a (pyribena), pyricularia (pyribena), pyriben) a (pyricularia (pyribena (pyricularia) a), pyriben (pyriben) a (pyriben), pyriben) a (pyribena (pyribenazolum), pyribenazolum (pyribena (pyribenazoles (pyribena (pyribenazolum (pyribena (pyriben) a (pyriben), pyriben) a (pyribena), pyribena (pyriben), pyriben (pyribena (pyriben) a (pyriben), pyribena (pyriben), pyriben) a), pyribena), pyriben (pyribena (pyribenazolum), pyriben (pyriben) a (pyribena (pyriben (pyribenazolum), pyribenazolum (pyriben (pyribenazolum), pyriben (pyribenazolum), pyribenazolum (pyriben (pyribenazolum), pyriben (pyribenazolum), pyriben (pyribenazolum), pyriben, Biphenyl, dicyclopentadienyl (chloroneb), chlordiazepoxide (etridiazole), dimethomorph (dimethomorph), flumorph (flumorph), mandipropamid (manipropamid), pyrimorph (pyrimorph), benthiavalicarb (benthiavalicarb), iprovalicarb, valifenalate, N- (1- (4-cyanophenyl) ethanesulfonyl) but-2-yl) carbamic acid 4-fluorophenyl ester, oryzanol (propamocarb), propamocarb hydrochloride (propamocarb-hydrochloride), Bordeaux mixture (Bordeaux), copper acetate, copper hydroxide, copper oxychloride (copperoxochloride), copper sulfate hydroxide, ferrous acetate (ferbam), mancozeb (cozeb), manmanmaneb (manebneb), metiram (metiram), propiram (propiram), zinc (propiram), propiram (propiram), zinc (propiram), propineb (propiram), propiram (propiram), propiram (propineb), propineb (propiram), propiram (propiram), propiram (propineb), propiram (propiram), propiram (propineb), propiram (propiram), propiram (propiram), propineb), propiram (propiram), propiram (propiram), propiram (propiram), propiram (propiram), propiram), propiram (propiram ), propiram (propiram), propiram), propiram (propiram), propiram (propiram), propiram (propiram ), propiram), propiram), propiram, captan (captan), folpet (folpet), dichlofluanid (dichlorphenad), dichlorophen (dichlorphen), flusulfamide (fluulmamide), hexachlorobenzene (hexachlorobenzene), pentachlorophenol (pentachlorophenol) and its salts, tetrachlorophthalide (phthalide), tolyfluoride (tolyfluoride), N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methylbenzenesulfonamide, dodine free base, biguanide salts (guazatine), iminoctadine (guazatine-acetate),Iminoctadine acetate, iminoctadine triacetate, bis-octaguanidine (octoguanidine) acetate, dithianon (dithianon), 2, 6-dimethyl-1H, 5H- [1,4]Dithiadieno [2,3-c:5,6-c']Dipyrrole-1, 3,5,7(2H,6H) -tetrone, validamycin (validamycin), polyoxin (polyoxin B); a melanin synthesis inhibitor: pyroquilon (pyroquilon), tricyclazole (tricyclazole), chlorocyclopropylamide (carpropamid), dicloromethride (diclomet), fenpyrad (fenoxanil), acibenzolar-S-methyl, thiabendazole (probenazole), isotianil (isotianil), tiadinil (tiadinil), calcium prohexadione-calcium; phosphonic acid esters: phycophytate (foseyl), fosetyl-aluminum (foseyl-aluminum), phosphorous acid and its salts, bronopol (bronopol), ametrytis (chinomethionat), cyflufenamid (cyflufenamid), cymoxanil (cymoxanil), dazomet (dazomet), prochloraz (debarb), diclomezine (diclomezine), difenzoquat (difenzoquat), difenzoquat-methyl sulfate (difenzoquat-methyl sulfate), diphenylamine, fenpyrazamide (fenpyrazamine), flurbiprofen (fluetover), flusulfamide, flutianil, methiocarb (methasulfocarb), chlordine (nitropyrin), isopropyl-isoprox (nitropyrol), oxine-copper (oxine-copter), proquindoxe (prothioconazole), cumquat (flufenpyrad, flufenpyrazoxazide (flufenpyrad), trifloxystrobin (flufenpyrazone), etc.
Advantageous effects
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
by chemically modifying a compound with a 2, 3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline structure and introducing a pyrazole structure, the obtained quinolol derivative or the salt thereof which is acceptable as a pesticide has excellent biological activity on rice blast, has satisfactory control activity on other control objects except for the rice blast, and has excellent safety on crops.
Modes for carrying out the invention
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. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
By taking into account the economics, diversity and biological activity of the synthesized compounds, it is preferred that some of the compounds are listed in the following table. Specific compound structures are shown in table 1, and specific compound physical property data are shown in table 2. The compounds in tables 1-2 are only for better illustration of the invention and are not intended to be limiting, and those skilled in the art will not understand that the scope of the above subject matter of the invention is limited to the following compounds.
Figure BDA0002565164940000091
TABLE 1 Structure of Compounds of formula I
Figure BDA0002565164940000092
Figure BDA0002565164940000101
Figure BDA0002565164940000111
Figure BDA0002565164940000121
TABLE 21H NMR data
Figure BDA0002565164940000122
Figure BDA0002565164940000131
The methods for preparing the compounds of the present invention are illustrated in the following schemes and examples. The starting materials are commercially available or can be prepared by methods known in the literature or as shown in detail. It will be appreciated by those skilled in the art that other synthetic routes may also be utilized to synthesize the compounds of the present invention. Although specific starting materials and conditions for the synthetic routes are described below, they can be readily substituted with other similar starting materials and conditions, and variations or modifications of the preparation process of the present invention, such as various isomers of the compounds, are included in the scope of the present invention. In addition, the preparation methods described below may be further modified in accordance with the present disclosure using conventional chemical methods well known to those skilled in the art. For example, protecting the appropriate groups during the reaction, and the like.
Example 1
Synthesis of Compound I-3:
Figure BDA0002565164940000141
adding the intermediate II-3(2.47g, 10mmol) and dichloromethane (30ml) into a reaction bottle, adding the intermediate III-3(1.98g, 10mmol) at 20 ℃ under stirring, adding triethylamine (2eq) at 20 ℃ under stirring for reaction, tracking the reaction by TLC (ethyl acetate: petroleum ether 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning, drying, and purifying by column chromatography to obtain the compound I-3, 3.17g, white solid powder, melting point: 176.1-177.2 ℃; 1H NMR (500MHz, Chloroform-d) δ 7.43(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).
Example 2
Synthesis of Compound I-41:
adding intermediate II-41 (same as II-2, 2.47g, 10mmol) and acetonitrile (30ml) into a reaction flask, adding intermediate III-41(2.12g, 10mmol) under stirring at 20 deg.C, adding triethylamine (2eq) under stirring at 20 deg.C, and tracking reaction by TLC(ethyl acetate: petroleum ether: 1, GF254, UV color development), after completion of the reaction, the solvent was spun off, dried, and purified by column chromatography to obtain compound I-41, i.e., the target compound 3.12g, a white solid powder, melting point: 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)
example 3
Synthesis of Compound 6:
adding the intermediate II-6 (same as II-2, 2.47g and 10mmol) and acetonitrile (30ml) into a reaction bottle, adding the intermediate III-6(2.40g and 10mmol) under stirring at 20 ℃, adding triethylamine (2eq) under stirring at 20 ℃, tracking the reaction by TLC (ethyl acetate: petroleum ether is 1:1, GF254, UV color development), after the reaction is completed, removing the solvent by spinning, drying, and purifying by column chromatography to obtain the target compound I-6, 3.12g, white-like solid powder with a melting point: 197 ℃ and 202 ℃; 1H NMR (500MHz, Chloroform-d) δ 7.45-7.40 (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).
Example 4
Preparation of the preparation:
1. powder preparation: weighing 20% of the compound of the formula (I) and 80% of kaolin, uniformly mixing, and crushing to obtain the product.
2. Wettable powder: weighing 20% of the compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium lauryl sulfate, 3% of white carbon black and kaolin to 100%. Mixing uniformly, and performing jet milling to obtain the product.
3. Water dispersible granules: 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% of nekal BX (sodium dibutylnaphthalene sulfonate), 3% of K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomaceous earth, 5% of glucose and kaolin are weighed to 100%. Uniformly mixing, after jet milling, weighing the powder, adding water for mixing, granulating in a granulator, and then drying and screening to obtain granular products.
4. And (3) missible oil: weighing 15% of the compound of the formula (I), 5% of Nongru 700#, 5% of Nongru 500#, 6% of Nongru 1601#, 10% of cyclohexanone, 3% of N-methylpyrrolidone and solvent oil 150, adding to 100%, dissolving completely and mixing uniformly to obtain the product.
5. Suspending agent: weighing 15% of a compound shown in the formula (I), 4% of FS3000 (phosphate type anionic surfactant), 2% of NS-500LQ (nonionic hydroxy polyethylene oxide block copolymer), 0.2% of xanthan gum, 1% of magnesium aluminum silicate, 5% of ethylene glycol, 0.1% of BIT (1, 2-benzisothiazolin-3-one), 0.3% of organic modified siloxane defoamer and adding deionized water to 100%, preparing slurry, and sanding to obtain the product.
The above are all weight percentages.
Example 5
Rice blast protective control test (Pyricularia oryzae):
the host crop is rice (Lu rice No. 1), and the specific operation is as follows:
weighing a certain mass of compound sample, dissolving in acetone, and preparing into mother liquor for later use. In the test, compound samples and control agents were prepared into serial concentration gradient solutions with 0.1% tween 80 in water for in vivo screening. Potted rice seedlings with three leaves, one heart and consistent growth are selected, marked and then discharged in sequence for experiments. The sprayer is a spray tower, and 30ml of liquid medicine is sprayed for each treatment and naturally dried. After 24h, the pathogenic bacteria are inoculated, and a blank control is set. Washing surface spores with sterile water in a culture dish full of spores, filtering with 2-4 layers of gauze to obtain a filtrate with a concentration of 1 × 105-1×106Spraying spore suspension (one/mL) on rice seedling with inoculating sprayer (pressure 0.1MPa), transferring inoculated test material into moisture-keeping box (chamber) or artificial climate chamber, and keeping relative humidity>95 percent, culturing at 26-28 ℃ under a dark condition, transferring into an incubator (room) with 12h light-dark alternation and illumination intensity more than 20000lx or culturing in a greenhouse at high humidity after 24h, and carrying out grading investigation according to blank control disease occurrence after 5-7 d.
The control effect grade is as follows:
a: the control effect is more than 80 percent;
b: the control effect is between 50 and 79 percent;
c: the control effect is less than 50 percent;
the results of the rice blast protection test are shown in Table 3.
TABLE 3 protective test results for rice blast
Figure BDA0002565164940000161
Example 6
Rice blast protective control test (Pyricularia oryzae):
the host crop is rice (Shannong 13), and the specific operation is as follows:
weighing a certain mass of compound sample, dissolving in acetone, and preparing into mother liquor for later use. In the test, compound samples and control agents were prepared into serial concentration gradient solutions with 0.1% tween 80 in water for in vivo screening. Potted rice seedlings with three leaves, one heart and consistent growth are selected, marked and then discharged in sequence for experiments. The sprayer is a spray tower, and 30ml of liquid medicine is sprayed for each treatment and naturally dried. After 24h, the pathogens are inoculated, and blank control and other medicament control are set. Adding sterile water into a culture dish full of spores, scraping surface spores, filtering with 2-4 layers of gauze to obtain the product with the concentration of 5 multiplied by 105-6×105Spraying spore suspension (one/mL) on rice seedling with inoculating sprayer (pressure 0.1MPa), transferring inoculated test material into moisture-keeping box (chamber) or artificial climate chamber, and keeping relative humidity>85 percent, the temperature is 26-28 ℃, the culture is moved into an incubator (room) with the illumination intensity of more than 2000lx or a greenhouse for high-humidity culture after 24 hours, and the disease occurrence condition is investigated after 5-7 days according to blank control.
The control effect grade is as follows:
0: the control effect is more than 95 percent;
1: the control effect is more than 90 percent;
2: the control effect is more than 80 percent;
3: the control effect is between 50 and 79 percent;
4: the control effect is less than 50 percent;
the results of the rice blast protection test are shown in Table 4.
TABLE 4 results of the rice blast protection test at different concentrations
Figure BDA0002565164940000171
Figure BDA0002565164940000181
Example 7
Melon powdery mildew protective control test (Sphaeotheca fuliginea):
the host crop is cucumber (Jinyou No. 1), and the method adopts a potted seedling method and comprises the following specific operations:
weighing a certain mass of compound sample, dissolving in acetone, and preparing into mother liquor for later use. In the test, compound samples and control agents were prepared into serial concentration gradient solutions with 0.1% tween 80 in water for in vivo screening. Selecting potted cucumber seedlings with 2-4 leaf stage and regular and consistent growth as test host plants of cucumber powdery mildew. The sprayer is a spray tower, and 30ml of liquid medicine is sprayed for each treatment and naturally dried. After 24h, the pathogens are inoculated, and blank control and other medicament control are set. The fresh spores of powdery mildew generated in 24h on the leaves of the cucumber with disease are prepared into suspension (the concentration is 1 multiplied by 10)5spores/mL), sprayed onto inoculated leaves, and cultured under appropriate conditions. After 7-10 days, the disease is completely developed by clear water contrast, and the test result is investigated.
The control effect grade is as follows:
i: the control effect is more than 90 percent;
II: the control effect is more than 80 percent;
III: the control effect is between 50 and 79 percent;
IV: the control effect is less than 50 percent;
the melon powdery mildew protective test results are shown in table 5.
TABLE 5 melon powdery mildew protective test results
Figure BDA0002565164940000182
Figure BDA0002565164940000191
The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose thereof is to enable those skilled in the art to understand the contents of the present invention and implement the present invention accordingly, and not to limit the protection scope of the present invention accordingly. All equivalent changes or modifications made in accordance with the spirit of the present disclosure are intended to be covered by the scope of the present disclosure.
Industrial applicability
The compound of the invention can be used as a bactericide for controlling plant diseases, and is particularly suitable for rice, wheat and/or melons.

Claims (10)

1. A quinolyl phenol derivative or a pesticidally acceptable salt thereof, having the formula:
Figure FDA0002565164930000011
in the formula (I), the compound is shown in the specification,
R1representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R2representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkylthio, halo C1-C6Alkylthio radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or, R1And R2Are formed togetherGroup- (CH)2)t-, t represents an integer of 2 to 8;
R3、R4、R5each independently selected from H, halogen, CN, nitro, aldehyde group, carboxyl and C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl or phenyl substituted C1-C6An alkyl group;
x represents halogen, CN, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6Cycloalkyl, and m represents an integer of 0 to 3.
2. A quinolylphenol derivative according to claim 1, wherein in the formula (I),
R1representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
R2representation H, C1-C6Alkyl, halo C1-C6Alkyl radical, C1-C6Alkoxy or halo C1-C6An alkoxy group;
or, R1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 7;
R3、R4each independently selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy or C3-C6A cycloalkyl group;
R5selected from H, halogen, CN,Nitro, aldehyde, carboxyl, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy, halo C1-C6Alkoxy radical, C3-C6Cycloalkyl, phenyl or benzyl;
x represents halogen, CN, nitro, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6Cycloalkyl, m represents an integer of 1 to 3;
preferably, R3、R4All are Me or Et, X is 6-t-Bu, and m is 1.
3. The quinolenol derivative according to claim 2, wherein R in the formula (I) is represented by the formula1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 5.
4. The quinolenol derivative according to claim 3, wherein R in the formula (I) is represented by the formula3、R4Same, selected from H, C1-C6Alkyl, halo C1-C6Alkyl radical, C2-C6Alkenyl, halo C2-C6Alkenyl radical, C1-C6Alkoxy or C3-C6A cycloalkyl group; preferably, R3、R4The same is selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3OMe, OEt, vinyl, cyclopropane.
5. The quinolenol derivative according to claim 1, wherein R in the formula (I) is represented by the formula1And R2Together form a radical- (CH)2)t-, t represents an integer of 2 to 5;
R3、R4each independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane;
R5selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2Br、CHBr2、CBr3、CH2CF3、CH2CH2Cl, vinyl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropane, cyclopropaneoxy, nitro, aldehyde group, carboxyl and 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, and m is 1 or 2.
6. The quinolenol derivative according to claim 5, wherein R in the formula (I) is represented by the formula1And R2Together form a radical- (CH)2)t-, t represents an integer of 3 to 4;
R3、R4are both Me or Et;
R5selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH2Cl、CHCl2、CCl3、CH2F、CHF2、CF3、CH2CF3、CH2CH2Cl, vinyl, OMe, OEt, nitro;
x represents a tert-butyl group, and m is 1.
7. A quinolylphenol derivative according to any one of claims 1 to 6, or a pesticidally acceptable salt thereof, selected from the group consisting of:
Figure FDA0002565164930000021
Figure FDA0002565164930000031
8. a fungicidal composition comprising a fungicidally effective amount of at least one of the quinolyl phenol derivatives of any one of claims 1 to 7 or a pesticidally acceptable salt thereof; preferably, the composition also comprises a preparation carrier or a preparation auxiliary agent.
9. A method for controlling plant diseases, which comprises applying a biologically effective amount of at least one of the quinolyl phenol derivatives or the salts thereof as a pesticidal salt as claimed in any one of claims 1 to 7 or the fungicidal composition as claimed in claim 8 to plants.
10. Use of at least one of the quinolyl phenol derivatives or the salts thereof as a pesticidal acceptable according to any one of claims 1 to 7 or the fungicidal composition according to claim 8 for controlling plant diseases; preferably, the plant disease is a bacterial disease or a fungal disease; more preferably, the plant disease is a disease of infection of a plant with Pyricularia oryzae.
CN202010621034.8A 2020-07-01 2020-07-01 Quinolinophenol derivative or salt thereof acceptable as pesticide, composition and application thereof Pending CN113880840A (en)

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EP0669321B1 (en) * 1989-07-07 2000-09-27 Meiji Seika Kabushiki Kaisha Use of 4-acyloxyquinoline derivatives as insecticides or acaricides
TW521072B (en) * 1997-06-02 2003-02-21 Meiji Seika Kaisha 4-quinolinol derivatives and fungicides containing the same as an active ingredient used for agriculture and horticulture
CN1193017C (en) * 2000-05-30 2005-03-16 明治制果株式会社 Rice blast control agents
DE10135466A1 (en) * 2001-07-20 2003-02-06 Bayer Cropscience Ag Biphenyl-substituted 4-hydroxy-quinolones
CN109320452B (en) * 2017-07-31 2019-10-18 东莞东阳光科研发有限公司 Quinoline derivatives and its preparation method and application
CN108863889B (en) * 2018-08-09 2020-06-26 西北农林科技大学 L-pyroglutamic acid derivative and preparation method and application thereof

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CN115872999A (en) * 2022-06-20 2023-03-31 江苏吉贝尔药业股份有限公司 Thiazolidine acid derivative or pharmaceutically acceptable salt, composition and application thereof

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