A quinolinol derivative or a pesticidally acceptable salt thereof, a composition and uses thereof

Abstract

The present invention belongs to the field of pesticides, and particularly relates to a quinolinol derivative or a pesticidally acceptable salt thereof, a composition and uses thereof. The compound has the structure of formula (I): wherein the definitions of each group are as shown in the specification. The compound with a quinolinol structure of the present invention has higher biological activity than known compounds, can effectively sterilize and has sufficient safety for crops, and is not prone to generating resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of pesticides, and particularly relates to a quinolinol derivative or a pesticidally acceptable salt or composition thereof, and also relates to the use of these compounds or their pesticidally acceptable salts or compositions as fungicides. Background Art

[0002] It is known that quinoline derivatives obtained by replacing hydrogen with substituents such as allyloxy, amino, benzoyl, etc. at the 4-position of the quinoline skeleton have certain biological activities against plant pathogenic bacteria. In the patent application with the application number CN98805678.X, 4-quinolinol derivatives and their acid addition salts having specific substituents simultaneously at the 2-position, 3-position, and 5-8 positions of the quinoline skeleton exhibit good antibacterial activities against various plant pathogenic bacteria including Magnaporthe oryzae, Bipolaris oryzae, Podosphaera xanthii, Colletotrichum coccodes, etc. In the patent application with the application number 01813588.9, it is further described that 4-quinolinol derivatives and their acid addition salts having methyl substituents at the 2-position and 3-position, a tert-butyl substituent at the 6-position, and a fluorine substituent at the 8-position of the quinoline skeleton are used for the control of rice blast. However, there is still room for improvement in the control activity against control targets including rice blast, and at lower application rates, the activity is not satisfactory enough.

[0003] Technical Problem

[0004] To solve the above problems existing in the prior art, the present invention provides a quinolinol derivative or a pesticidally acceptable salt or composition thereof and its use. The applicant unexpectedly found that quinolinol derivatives, especially 2,3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline derivatives or their pesticidally acceptable salts, not only have excellent biological activities against rice blast, but also have satisfactory control activities against other control targets except rice blast, and have excellent safety for crops.

[0005] Technical Solution

[0006] The technical solution adopted by the present invention to achieve the above object is: a quinolinol derivative or a pesticidally acceptable salt thereof, and its structural formula is as follows:

[0007]

[0008] In formula (I),

[0009] R1 represents H, C1-C6 alkyl, halo C1-C6 alkyl, C1-C6 alkylthio, halo C1-C6 alkylthio, C1-C6 alkoxy, or halo C1-C6 alkoxy;

[0010] R2 represents H, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkylthio, halo-C1-C6 alkylthio, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0011] Alternatively, R1 and R2 together form a group -(CH2) t -, where t represents an integer from 2 to 8;

[0012] R3, R4, and R5 are each independently selected from H, halogen, CN, nitro, aldehyde group, carboxyl group, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C3-C6 cycloalkyl, phenyl or phenyl-substituted C1-C6 alkyl;

[0013] X represents halogen, CN, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy or C3-C6 cycloalkyl, and m represents an integer from 0 to 3.

[0014] Furthermore, in formula (I), R1 represents H, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0015] R2 represents H, C1-C6 alkyl, halo-C1-C6 alkyl, C1-C6 alkoxy or halo-C1-C6 alkoxy;

[0016] Alternatively, R1 and R2 together form a group -(CH2) t -, where t represents an integer from 2 to 7;

[0017] R3 and R4 are each independently selected from H, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C1-C6 alkoxy, halo-C1-C6 alkoxy or C3-C6 cycloalkyl;

[0018] R5 is selected from H, halogen, CN, nitro, aldehyde group, carboxyl group, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, halo-C2-C6 alkenyl, C1-C6 alkoxy, halo-C1-C6 alkoxy, C3-C6 cycloalkyl, phenyl or benzyl;

[0019] X represents halogen, CN, nitro, C1-C6 alkyl, halo-C1-C6 alkyl, C2-C6 alkenyl, C1-C6 alkoxy or C3-C6 cycloalkyl, and m represents an integer from 1 to 3;

[0020] Furthermore, both R3 and R4 are Me or Et, X is 6-t-Bu, and m is 1.

[0021] Further, in formula (I), R1 and R2 together form a group -(CH2) t -, where t represents an integer from 2 to 5.

[0022] Further, in formula (I), R3 and R4 are the same and are selected from H, C1-C6 alkyl, halogenated C1-C6 alkyl, C2-C6 alkenyl, halogenated C2-C6 alkenyl, C1-C6 alkoxy, or C3-C6 cycloalkyl; preferably, R3 and R4 are the same and are 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, CBr3, OMe, OEt, vinyl, cyclopropyl.

[0023] Further, in formula (I), R1 and R2 together form a group -(CH2) t -, where t represents an integer from 2 to 5;

[0024] R3 and R4 are each independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropyl;

[0025] R5 is selected 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, cyclopropyl, cyclopropoxy, nitro, aldehyde group, carboxyl group, hydroxyl group;

[0026] X represents H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropyl, and m is 1 or 2.

[0027] Further, in formula (I), R1 and R2 together form a group -(CH2) t -, where t represents an integer from 3 to 4;

[0028] Both R3 and R4 are Me or Et;

[0029] R5 is selected from H, F, Cl, Br, CN, Me, Et, n-Pr, i-Pr, CH2Cl, CHCl2, CCl3, CH2F, CHF2, CF3, CH2CF3, CH2CH2Cl, vinyl, OMe, OEt, nitro;

[0030] X represents tert-butyl and m is 1.

[0031] Furthermore, the compounds of formula (I) are specifically selected from:

[0032]

[0033]

[0034]

[0035] The agriculturally acceptable salts can be salts prepared by reacting the quinolinol derivatives of the present invention with chemically acceptable acids, where the chemically acceptable acids can be inorganic acids (such as hydrochloric acid, sulfuric acid, phosphoric acid, or hydrobromic acid, etc.) or organic acids (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid, or benzoic acid, etc.); the agriculturally acceptable salts can also be salts prepared by reacting the quinolinol derivatives of the present invention with chemically acceptable bases, where the chemically acceptable bases can be inorganic bases (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.).

[0036] Furthermore, the agriculturally acceptable salts can be potassium salts, sodium salts, ammonium salts, calcium salts, pyridinium salts, or choline salts.

[0037] The present invention also discloses a bactericidal composition, comprising at least one of the quinolinol derivatives or their agriculturally acceptable salts as described above in a bactericidally effective amount; furthermore, it also comprises a formulation carrier or a formulation adjuvant.

[0038] The present invention also discloses a method for controlling plant diseases, comprising applying at least one of the quinolinol derivatives or their agriculturally acceptable salts as described above in a biologically effective amount or the bactericidal composition as described above to plants.

[0039] The present invention also discloses the use of at least one of the quinolinol derivatives or their agriculturally acceptable salts as described above or the bactericidal composition as described above in controlling plant diseases; preferably, the plant diseases are bacterial diseases or fungal diseases.

[0040] In the definitions of the above compound structural formulas, the professional terms used have the following meanings:

[0041] Halogen or halide: refers to fluorine, chlorine, bromine, or iodine.

[0042] C1-C6 alkyl: a straight-chain or branched-chain alkyl group with 1-6 carbon atoms, such as methyl, ethyl, propyl, isopropyl, or tert-butyl.

[0043] Halogenated C1-C6 alkyl: a straight-chain or branched-chain alkyl group with 1-6 carbon atoms, where the hydrogen atoms on these alkyl groups can be partially or completely replaced by halogen atoms. For example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, etc.

[0044] C2-C6 alkenyl: a straight-chain or branched-chain alkenyl group with 2-6 carbon atoms. For example, vinyl, propenyl, etc.

[0045] Halogenated C2-C6 alkenyl: a straight-chain or branched-chain alkenyl group with 2-6 carbon atoms, where the hydrogen atoms on these alkenyl groups can be partially or completely replaced by halogen atoms. For example, vinyl chloride group, etc.

[0046] C1-C6 alkoxy: a straight-chain or branched-chain alkyl group with 1-6 carbon atoms, connected to the structure through an oxygen atom bond.

[0047] Halogenated C1-C6 alkoxy: a straight-chain or branched-chain alkoxy group with 1-6 carbon atoms, where the hydrogen atoms on these alkoxy groups can be partially or completely replaced by halogen atoms. For example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy, etc.

[0048] The group abbreviations appearing in the present invention are the same as those commonly used by those skilled in the art. For example, 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.

[0049] The synthesis method of the compound represented by formula I is specifically to react the compound of formula III with the compound of formula II (in the following listed chemical formulas, as long as no other definitions are made, the substituents and symbols have the same meanings as those defined in formula I) in the presence or absence of a basic reagent and in the presence or absence of a solvent to obtain the target product, the compound of formula I. The compounds represented by formula II and III can be obtained commercially or can be prepared by referring to the methods described in EP407192A:

[0050]

[0051] Furthermore, the solvent is selected from one or a mixture of solvents such as acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane, ethyl acetate;

[0052] Furthermore, the reaction can be carried out under normal pressure or high pressure, preferably under atmospheric pressure, and the post-treatment can be carried out according to conventional methods.

[0053] The compound of formula I according to the present invention, or its agriculturally acceptable salts or compositions, are respectively suitable as fungicides, and are particularly suitable as fungicides or bactericides with remarkable efficacy. Some of them are systemically effective and can be used as foliar fungicides, seed treatment fungicides and soil fungicides for crop protection. In addition, they are suitable for controlling harmful fungi occurring especially in wood or plant roots, specifically by treating fungi or bacteria, or materials, plants, soil or seeds to be protected from fungal or bacterial attack, with an effective amount of at least one compound of formula I as defined in the present invention, or its agriculturally acceptable salts or compositions.

[0054] The compounds I according to the present invention, or their agriculturally acceptable salts or compositions, are suitable for controlling plant diseases, especially fungal or bacterial diseases, in various cultivated plants such as cereals, for example wheat, rye, barley, triticale, oats or rice; sugar beet, for example sugar beet or fodder beet; fruits, such as pomaceous fruits, stone fruits or berries, for example apples, pears, plums, peaches, apricots, cherries, strawberries or blueberries; leguminous plants, for example lentils, peas, alfalfa or soybeans; oil plants, for example rape, mustard, olive, sunflower, coconut, cocoa bean, castor oil plant, oil palm, peanuts or soybeans; cucurbitaceous plants, for example pumpkins, cucumbers or melons; fiber plants, for example cotton, flax or jute; citrus fruits, for example oranges, lemons, grapefruits or tangerines; vegetables, for example spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, cucurbits or sweet peppers; laurel plants, for example avocados, cinnamon or camphor; crops of greater economic value, for example maize, soybeans, rape, sugar cane, oil palm, tobacco, nuts, coffee, tea, bananas, grapes, hops, etc.; lawns; natural rubber plants or ornamental and forest plants, for example flowers, shrubs, broad-leaved trees or evergreen trees, for example conifers, and plant propagation materials such as seeds, plant tubers, cuttings, etc.

[0055] Preferably, the compound I or its agriculturally acceptable salts or compositions are respectively used for controlling fungal or bacterial diseases in field crops, for example potatoes, sugar beets, tobacco, wheat, rye, barley, oats, rice, maize, cotton, soybeans, rape, leguminous plants, sunflowers, coffee or sugar cane; fruits; ornamental plants or vegetables such as cucumbers, tomatoes, kidney beans or pumpkins.

[0056] The present invention also provides a fungicidal composition comprising a compound of formula I. The compound of formula I can be formulated in various ways according to usual biological and / or chemical parameters and / or physical parameters. Examples of suitable formulations are: wettable powders (WP), soluble concentrates (SL), soluble powders (SP), dispersible concentrates (DC), aqueous solutions (AS), microemulsions (ME), emulsifiable concentrates (EC), emulsions in water (EW), sprayable solutions, suspensions (SC), oil-based suspensions (OD), dusts (DP), capsule suspensions (CS), water-dispersible granules (WG), water-soluble granules (SG), large granules (GG), granules for broadcasting and soil application (GR), aerosols (AE), ultra-low volume formulations (ULV), and waxes. Necessary formulation adjuvants such as inert substances, surfactants, solvents and other additives.

[0057] 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, feeding stimulants, compatibilizers, antifreeze agents, defoamers, colorants, tackifiers and binders.

[0058] Suitable solvents and liquid carriers are water and / or organic solvents such as medium to high boiling mineral oil fractions, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons such as toluene, paraffin wax, tetrahydronaphthalene, alkylated naphthalenes; alcohols such as ethanol, propanol, butanol, benzyl alcohol, cyclohexanol; diols; dimethyl sulfoxide (DMSO); ketones such as cyclohexanone; esters such as lactate, carbonate, fatty acid esters, γ-butyrolactone; fatty acids; phosphonates; amines; amides such as N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.

[0059] 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; polysaccharide substances such as cellulose, starch; fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin such as cereal flours, bark flours, wood flours and nut shell flours, and mixtures thereof.

[0060] Suitable surfactants are surface-active substances such as anionic, cationic, non-ionic 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.

[0061] Suitable adjuvants are compounds which have negligible pesticidal activity per se or even no pesticidal activity per se and which improve the biological properties of Compound I against the target; examples are surfactants, mineral oils or vegetable oils and other auxiliaries.

[0062] Suitable thickeners are polysaccharides (such as xanthan gum, carboxymethyl cellulose), inorganic clays (organo-modified or unmodified), polycarboxylates and silicates, etc.

[0063] Suitable antifreezes are ethylene glycol, propylene glycol, urea and glycerol, etc.

[0064] Suitable defoamers are polysiloxanes, long-chain alcohols and fatty acid salts, etc.

[0065] Suitable colorants (such as red, blue or green colorants) are poorly water-soluble pigments and water-soluble dyes, which can be inorganic colorants (such as iron oxide, titanium oxide, iron hexacyanoferrate) and organic colorants (such as alizarin colorants, azo colorants and phthalocyanine colorants).

[0066] In the admixed preparation or the tank mix preparation, suitable active substances that can be mixed with the active substances of the present invention are, for example, known substances in "The Complete Technology of New Varieties of World Pesticides" (China Agricultural Science and Technology Press, September 2010). For example, the following mentioned fungicide active substances can be mixed with the mixture of formula I. (Note: The name of the compound is either the common name according to the International Organization for Standardization (ISO) or the chemical name, with codes when appropriate): azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, 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-methylpropanoic acid -8-Benzyl-3-[(3-acetoxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxepan-7-yl] ester, [(3S,6S,7R,8R)-8-benzyl-3-[[3-acetoxymethoxy-4-methoxypyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxepan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[(3-isobutoxycarbonyloxy-4-methoxypyridine-2-carbonyl)amino]-6-methyl-4,9-dioxo-1,5-dioxepan-7-yl] 2-methylpropanoate, [(3S,6S,7R,8R)-8-benzyl-3-[[3-(1,3-benzodioxol-5-ylmethoxy)-4-methoxypyridine-2-carbonyl]amino]-6-methyl-4,9-dioxo-1,5-dioxepan-7-yl] 2-methylpropanoate, (3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8-(phenylmethyl)-1,5-dioxepan-7-yl 2-methylpropanoate; benodanil, bixafen, boscalid, carboxin, fenfuram, fluopyram, flutolanil, fluxapyroxad, furametpyr, isopyrazam, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, N-(4'-trifluoromethylthio-biphenyl-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-methano-naphthalen-5-yl]-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; 3-difluoromethyl-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide, 3-trifluoromethyl-1-methyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide, 1,3-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide, 3-trifluoromethyl-1,5-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide, 3-difluoromethyl-1,5-dimethyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide, 1,3,5-trimethyl-N-(1,1,3-trimethyl-2,3-dihydro-inden-4-yl)pyrazole-4-carboxamide; diflumetorim, (5,8-difluoroquinazolin-4-yl)-{2-[2-fluoro-4-(4-trifluoromethylpyridin-2-yloxy)phenyl]ethyl}amine; nitro-phenyl derivatives: binapacryl, dinobuton, dinocap, fluazinam; ferimzone; organo-metallic compounds: triphenyltin salts, such as fentin-acetate, fentinchloride or fentinhydroxide; ametoctradin and silthiofam; azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole,Prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole, imazalil, pefurazoate, prochloraz, triflumizol, fenarimol, nuarimol, 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, hymexazole, octhilinone, oxolinic acid, bupirimate, benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl, diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone, pyriofenone, cyprodinil, mepanipyrim, pyrimethanil, blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin,Streptomycin, oxytetracyclin, polyoxine, validamycin A, fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil, fludioxonil, edifenphos, iprobenfos, pyrazophos, isoprothiolane, dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole, dimethomorph, flumorph, mandipropamid, pyrimorph, benthiavalicarb, iprovalicarb, valifenalate, 4-fluorophenyl N-(1-(1-(4-cyanophenyl)ethylsulfonyl)butan-2-yl)carbamate, propamocarb, propamocarb-hydrochlorid, Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, ferbam, mancozeb, maneb, metam, metiram, propineb, thiram, zineb, ziram, anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorophenol and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitrophenyl)-N-ethyl-4-methylbenzenesulfonamide, dodine free base, guazatine,Guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine-tris(albesilate), dithianon, 2,6-dimethyl-1H,5H-[1,4]dithieno[2,3-c:5,6-c']bipyrrole-1,3,5,7(2H,6H)-tetrone, validamycin, polyoxin B; Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamid, dicyclomet, fenoxanil, acibenzolar-S-methyl, probenazole, isotianil, tiadinil, prohexadione-calcium; Phosphonates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts, bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamine, fenpyrazamine, flumetover, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper, proquinazid, tebufloquin, tetrachloroisophthalonitrile, triazoxide, etc.

[0067] Beneficial effects

[0068] In summary, due to the adoption of the above technical solutions, the beneficial effects of the present invention are as follows:

[0069] By chemically modifying the compound with the structure of 2,3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline and introducing a pyrazole structure, the obtained quinolinol derivatives or their agriculturally acceptable salts not only have excellent biological activity against rice blast, but also have satisfactory control activity against other control targets besides rice blast, and have excellent safety for crops.

[0070] Embodiments of the present invention

[0071] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with 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 scope of protection of the present invention.

[0072] By comprehensively considering the economy, diversity, and biological activity of the synthesized compounds, some compounds are preferably listed in the following table. The specific compound structures are shown in Table 1, and the specific compound physical property data are shown in Table 2. The compounds in Tables 1-2 are only for better explaining the present invention and will not limit the present invention. Those skilled in the art should not understand that the scope of the above subject matter of the present invention is limited to the following compounds.

[0073]

[0074] Table 1 Structure of Compound of Formula I

[0075]

[0076]

[0077]

[0078]

[0079] Table 2 1 H NMR data

[0080]

[0081]

[0082] The method for preparing the compounds of the present invention is illustrated in the following technical solutions and examples. The raw materials can be purchased on the market or can be prepared by methods known in the literature or as detailed. Those skilled in the art should understand that the compounds of the present invention can also be synthesized using other synthetic routes. Although specific raw materials and conditions in the synthetic route have been described below, they can be easily replaced with other similar raw materials and conditions, and various isomers of the compounds and the like resulting from such modifications or variations of the preparation method of the present invention are included within the scope of the present invention. In addition, the preparation method described below can be further modified according to the disclosure of the present invention using conventional chemical methods well-known to those skilled in the art. For example, protecting appropriate groups during the reaction, etc.

[0083] Example 1

[0084] Synthesis of Compound I-3:

[0085]

[0086] Intermediate II-3 (2.47 g, 10 mmol) and dichloromethane (30 ml) were added to a reaction flask. Intermediate III-3 (1.98 g, 10 mmol) was added under stirring at 20 °C. Triethylamine (2 eq) was added and the reaction was stirred at 20 °C. The reaction was monitored by TLC (ethyl acetate: petroleum ether = 1:1, GF254, UV visualization). After the reaction was complete, the solvent was evaporated, dried, and purified by column chromatography to obtain Compound I-3, 3.17 g, a white solid powder, melting point: 176.1 - 177.2 °C; 1H NMR (500 MHz, Chloroform-d) δ 7.43 (dd, J = 12.8, 1.8 Hz, 2H), 4.25 (t, J = 7.3 Hz, 2H), 3.24 (t, J = 7.4 Hz, 2H), 2.99 (qd, J = 7.5, 1.5 Hz, 2H), 2.77 (d, J = 1.6 Hz, 3H), 2.71 (q, J = 7.5 Hz, 2H), 2.29 (d, J = 1.7 Hz, 3H), 1.37–1.29 (m, 12H).

[0087] Example 2

[0088] Synthesis of Compound I-41:

[0089] Add intermediate II-41 (same as II-2, 2.47 g, 10 mmol) and acetonitrile (30 ml) into a reaction flask. While stirring at 20 °C, add intermediate III-41 (2.12 g, 10 mmol). Then add triethylamine (2 eq) while stirring at 20 °C. Monitor the reaction by TLC (ethyl acetate: petroleum ether = 1:1, GF254, UV visualization). After the reaction is complete, rotary evaporate the solvent, dry, and purify by column chromatography to obtain 3.12 g of compound I-41, the target compound, as a white solid powder, melting point: 158.6 - 159.2 °C; 1 H NMR (500 MHz, Chloroform-d) δ 7.47–7.40 (m, 2H), 4.24–4.17 (m, 2H), 3.16 (t, J = 6.5 Hz, 2H), 3.00 (qd, J = 7.4, 2.0 Hz, 2H), 2.77 (d, J = 3.1 Hz, 3H), 2.29 (d, J = 2.2 Hz, 3H), 2.10 (th, J = 5.7, 2.8 Hz, 2H), 1.94 (dtt, J = 8.9, 5.9, 2.6 Hz, 2H), 1.33 (s, 12H)

[0090] Example 3

[0091] Synthesis of Compound 6:

[0092] Add intermediate II-6 (same as II-2, 2.47 g, 10 mmol) and acetonitrile (30 ml) into a reaction flask. While stirring at 20 °C, add intermediate III-6 (2.40 g, 10 mmol). Then add triethylamine (2 eq) while stirring at 20 °C. Monitor the reaction by TLC (ethyl acetate: petroleum ether = 1:1, GF254, UV visualization). After the reaction is complete, rotary evaporate the solvent, dry, and purify by column chromatography to obtain the target compound I-6, 3.12 g, as an off-white solid powder, melting point: 197 - 202 °C; 1H NMR (500 MHz, Chloroform-d) δ 7.45–7.40 (m, 2H), 4.20 (s, 2H), 3.29–3.22 (m, 2H), 2.77 (d, J = 1.7 Hz, 3H), 2.31 (d, J = 1.7 Hz, 3H), 2.14–2.06 (m, 2H), 1.96 (td, J = 6.0, 3.1 Hz, 2H), 1.46 (s, 9H), 1.33 (d, J = 1.7 Hz, 9H).

[0093] Example 4

[0094] Preparation of Formulation:

[0095] 1. Dust: Weigh 20% of the compound of formula (I) and 80% of kaolin, mix them evenly, and obtain the product by grinding.

[0096] 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 add kaolin to 100%. Mix evenly and obtain the product after air-flow pulverization.

[0097] 3. Water dispersible granules: Weigh 60% of the compound of formula (I), 6% of sodium lignosulfonate, 4% of NNO (alkylnaphthalenesulfonate formaldehyde condensate), 2% of Nekal BX (sodium dibutylnaphthalenesulfonate), 3% of K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomite, 5% of glucose, and add kaolin to 100%. Mix evenly, after air-flow pulverization, weigh the powder, add water and mix, granulate in a granulator, then dry and screen to obtain the granular product.

[0098] 4. Emulsifiable concentrate: Weigh 15% of the compound of formula (I), 5% of agricultural emulsifier 700#, 5% of agricultural emulsifier 500#, 6% of agricultural emulsifier 1601#, 10% of cyclohexanone, 3% of N-methylpyrrolidone, and add solvent oil 150 to 100%. Dissolve completely and mix evenly to obtain the product.

[0099] 5. Suspension concentrate: Weigh 15% of the compound of formula (I), 4% of FS3000 (phosphate ester type anionic surfactant), 2% of NS-500LQ (nonionic hydroxy polyoxyethylene 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 organically modified silicone defoamer, and add deionized water to 100%. Make into a slurry and obtain the product after sand grinding.

[0100] All of the above are weight percentages.

[0101] Example 5

[0102] Protective control test against Pyricularia oryzae:

[0103] The host crop is rice (Ludao No. 1), and the specific operation is as follows:

[0104] Weigh a certain mass of the compound sample, dissolve it in acetone to prepare a stock solution for later use. During the test, prepare a series of concentration gradient liquid medicines of the compound sample and the control agent with 0.1% Tween 80 water for in-vivo screening. Select potted rice seedlings with three leaves and one heart and consistent growth, mark them and arrange them in order for the experiment. The type of sprayer is a spray tower, spray 30 ml of liquid medicine for each treatment, and dry naturally. After 24 h, inoculate the pathogenic bacteria, and set a blank control. In a Petri dish full of spores, rinse the surface spores with sterile water and filter with 2 - 4 layers of gauze to make a concentration of 1×10 5 -1×106 A spore suspension of 5×10 5 -6×10 5 spores / mL was prepared. Then, it was evenly sprayed onto the rice seedlings using an inoculation sprayer (pressure 0.1 MPa). After inoculation, the test materials were transferred to a humidity chamber or artificial climate chamber with a relative humidity > 95%, a temperature of 26 - 28°C, and cultured in the dark. After 24 hours, they were transferred to an incubator or greenhouse with a 12-hour light-dark cycle and a light intensity greater than 20,000 lx for high-humidity culture. After 5 - 7 days, the disease severity was investigated based on the incidence of the blank control.

[0105] Efficacy level:

[0106] A: Efficacy is above 80%;

[0107] B: Efficacy is between 50 - 79%;

[0108] C: Efficacy is less than 50%;

[0109] The results of the protective test against rice blast are shown in Table 3.

[0110] Table 3 Results of the protective test against rice blast

[0111]

[0112] Example 6

[0113] Protective control test against rice blast (Pyricularia oryzae):

[0114] The host crop was rice (Shannong 13), and the specific operation was as follows:

[0115] A certain mass of the compound sample was weighed and dissolved in acetone to prepare a stock solution for later use. During the test, the compound sample and the control agent were prepared into a series of concentration gradient solutions with 0.1% Tween 80 in water for in vivo screening. Pot-grown rice seedlings with three leaves and one heart and consistent growth were selected, marked, and arranged in order for the experiment. The type of sprayer was a spray tower, and 30 ml of the solution was sprayed for each treatment and left to dry naturally. After 24 hours, the pathogen was inoculated, and a blank control and other agent controls were set. In a Petri dish filled with spores, sterile water was added, the surface spores were scraped off, and filtered through 2 - 4 layers of gauze to prepare a spore suspension with a concentration of 5×10 5 -6×10 5 spores / mL. Then, it was evenly sprayed onto the rice seedlings using an inoculation sprayer (pressure 0.1 MPa). After inoculation, the test materials were transferred to a humidity chamber or artificial climate chamber with a relative humidity > 85% and a temperature of 26 - 28°C. After 24 hours, they were transferred to an incubator or greenhouse with a light intensity greater than 2,000 lx for high-humidity culture. After 5 - 7 days, the disease situation was investigated based on the incidence of the blank control.

[0116] Efficacy level:

[0117] ​​​​0: The control efficacy is above 95%;

[0118] 1: The control efficacy is above 90%;

[0119] 2: The control efficacy is above 80%;

[0120] 3: The control efficacy is between 50 - 79%;

[0121] 4: The control efficacy is less than 50%;

[0122] The results of the protective test against rice blast are shown in Table 4.

[0123] Table 4 Results of the protective test against rice blast at different concentrations

[0124]

[0125]

[0126] Example 7

[0127] Protective control test against powdery mildew of cucurbits (Sphaeotheca fuliginea):

[0128] The host crop is cucumber (Jinyou No. 1). The potted seedling method is adopted. The specific operation is as follows:

[0129] Weigh a certain mass of the compound sample, dissolve it in acetone, and prepare a stock solution for later use. During the test, the compound sample and the control agent are prepared into a series of concentration gradient solutions with 0.1% Tween 80 water for in - vivo screening. Select potted cucumber seedlings at the 2 - 4 leaf stage with consistent growth as the test host plants for cucumber powdery mildew. The type of the sprayer is a spray tower. Spray 30 ml of the solution for each treatment and let it dry naturally. After 24 h, inoculate the pathogenic bacteria, and set a blank control and other agent controls. Prepare a suspension of fresh spores of powdery mildew bacteria produced on the diseased cucumber leaves within 24 h (concentration: 1×10 5 spores / mL), and spray it on the inoculated leaves, and culture it under suitable conditions. After 7 - 10 d, the water control is completely diseased, and the test results are investigated.

[0130] Control efficacy level:

[0131] I: The control efficacy is above 90%;

[0132] II: The control efficacy is above 80%;

[0133] III: The control efficacy is between 50 - 79%;

[0134] IV: The control efficacy is less than 50%;

[0135] The results of the protective test against powdery mildew of cucurbits are shown in Table 5.

[0136] Table 5 Results of Protective Tests against Powdery Mildew of Cucurbitaceae

[0137]

[0138]

[0139] The above embodiments are only for illustrating the technical concept and features of the present invention, and the purpose is to enable those of ordinary skill in the art to understand the content of the present invention and implement it accordingly. It should not be used to limit the protection scope of the present invention. Any equivalent changes or modifications made according to the essence of the content of the present invention should be covered within the protection scope of the present invention.

[0140] Industrial Applicability

[0141] The compounds of the present invention can be used as fungicides for controlling plant diseases, and are particularly suitable for use in rice, wheat and / or cucurbitaceae.

Claims

1. A quinolinol derivative or a pesticidally acceptable salt thereof, having the following structural formula: In formula (I), R1 and R2 together form a group -(CH2) t -, where t represents 3, 4, 5; R3 and R4 are each independently selected from H, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropyl; R5 is selected 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, CH2CF3, CH2CH2Cl, vinyl, OMe, OEt, n-PrO, i-PrO, n-BuO, i-BuO, s-BuO, t-BuO, cyclopropyl, cyclopropoxy, nitro, aldehyde group, carboxyl group, hydroxyl group; X represents H, F, Cl, Br, Me, Et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropyl, and m is 1 or 2.

2. A quinolinol derivative or a pesticidally acceptable salt thereof as described in claim 1, wherein In formula (I), R1 and R2 together form the group -(CH2) t -, t represents an integer from 3 to 4; R3 and R4 are each independently selected from Me or Et; R5 is selected 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 tert-butyl, and m is 1.

3. A quinolinol derivative as claimed in any one of claims 1-2 or a pesticidally acceptable salt thereof, characterized in that, Selected from:

4. A bactericidal composition, characterized in that, Comprising at least one of the quinolinol derivatives or pesticidally acceptable salts thereof as described in any one of claims 1-3 in a bactericidally effective amount.

5. The bactericidal composition according to claim 4, characterized in that, Also comprising a formulation carrier or formulation adjuvant.

6. A method for controlling plant fungal diseases, characterized in that, Comprising applying a biologically effective amount of at least one of the quinolinol derivatives or pesticidally acceptable salts thereof as described in any one of claims 1-3 or a bactericidal composition as described in any one of claims 4-5 to plants.

7. Use of at least one of the quinolinol derivatives or pesticidally acceptable salts thereof as described in any one of claims 1-3 or a bactericidal composition as described in any one of claims 4-5 in controlling plant fungal diseases.

8. The use according to claim 7, wherein, The plant disease is a disease in which plants are infected with Pyricularia oryzae.

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