CN113880840B - A quinoline phenol derivative or its acceptable salt as pesticide, composition and use thereof - Google Patents
A quinoline phenol derivative or its acceptable salt as pesticide, composition and use thereof Download PDFInfo
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- CN113880840B CN113880840B CN202010621034.8A CN202010621034A CN113880840B CN 113880840 B CN113880840 B CN 113880840B CN 202010621034 A CN202010621034 A CN 202010621034A CN 113880840 B CN113880840 B CN 113880840B
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/90—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
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- 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
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- 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
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- 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
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- C07—ORGANIC CHEMISTRY
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- 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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- C07—ORGANIC CHEMISTRY
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- 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
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Abstract
本发明属于农药领域，具体涉及一种喹啉酚类衍生物或其作为农药可接受的盐、组合物及其用途，所述化合物具有式(I)结构：式中各基团定义如说明书中所示。本发明的具有喹啉酚类结构的化合物具有比已知化合物更高的生物活性，能够有效杀菌并且对作物有足够的安全性，且不易产生抗性。The present invention belongs to the field of pesticides, and specifically relates to a quinoline phenol derivative or a salt thereof acceptable as a pesticide, a composition and use thereof, wherein the compound has a structure of formula (I): The definitions of the groups in the formula are as shown in the specification. The compound having a quinoline phenol structure of the present invention has higher biological activity than known compounds, can effectively kill bacteria, has sufficient safety to crops, and is not easy to produce resistance.
Description
Technical Field
The invention belongs to the technical field of pesticides, and particularly relates to a quinoline phenol derivative or a salt and a composition thereof which are acceptable as pesticides, and application of the compounds or the salt and the composition thereof which are acceptable as pesticides as bactericides.
Background
It is known that quinoline derivatives obtained by substituting hydrogen at the 4-position of the quinoline skeleton with substituents such as allyloxy, amino, benzoyl and the like have certain biological activity on plant pathogenic bacteria. In the patent application with the application number of CN98805678.X, it is described that 4-quinolinol derivatives and acid addition salts thereof having specific substituents simultaneously at the 2-, 3-and 5-8-positions of the quinoline skeleton show good antibacterial activity against various plant pathogenic bacteria including Pyricularia oryzae, powdery mildew, potato anthracnose and the like. In the patent application 01813588.9, it is further described that 4-quinolinol derivatives having methyl substituents at the 2-and 3-positions of the quinoline skeleton, tert-butyl substituents at the 6-position and fluoro substituents at the 8-position and their acid addition salts are useful for controlling rice blast. However, there is room for improvement in the control activity against control subjects including rice blast, and at lower amounts, the activity is not sufficient.
Technical problem
In order to solve the problems in the prior art, the invention provides a quinoline phenol derivative or a salt, a composition and application thereof which are acceptable as pesticides. The applicant has unexpectedly found that quinoline phenol derivatives, particularly 2, 3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline derivatives or their pesticidally acceptable salts, have not only excellent biological activity against rice blast but also satisfactory control activity against other control subjects other than rice blast, and excellent safety against crops.
Technical solution
The technical scheme adopted by the invention for realizing the purpose is that a quinolinol derivative or a salt thereof acceptable as a pesticide has the following structural formula:
in the formula (I) of the present invention,
R 1 represents H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 1-C6 alkylthio, halogenated C 1-C6 alkylthio, C 1-C6 alkoxy or halogenated C 1-C6 alkoxy;
r 2 represents H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 1-C6 alkylthio, halogenated C 1-C6 alkylthio, C 1-C6 alkoxy or halogenated C 1-C6 alkoxy;
Or R 1 and R 2 together form a group- (CH 2)t -, t represents an integer from 2 to 8;
R 3、R4、R5 is each independently selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, halogenated C 2-C6 alkenyl, C 1-C6 alkoxy, halogenated C 1-C6 alkoxy, C 3-C6 cycloalkyl, phenyl or phenyl substituted C 1-C6 alkyl;
X represents halogen, CN, nitro, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, C 1-C6 alkoxy or C 3-C6 cycloalkyl, and m represents an integer of 0 to 3.
Further, in formula (I), R 1 represents H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 1-C6 alkoxy or halogenated C 1-C6 alkoxy;
R 2 represents H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 1-C6 alkoxy or halogenated C 1-C6 alkoxy;
Or R 1 and R 2 together form a group- (CH 2)t -, t represents an integer from 2 to 7;
R 3、R4 is independently selected from H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, halogenated C 2-C6 alkenyl, C 1-C6 alkoxy, halogenated C 1-C6 alkoxy, or C 3-C6 cycloalkyl;
R 5 is selected from H, halogen, CN, nitro, aldehyde, carboxyl, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, halogenated C 2-C6 alkenyl, C 1-C6 alkoxy, halogenated C 1-C6 alkoxy, C 3-C6 cycloalkyl, phenyl or benzyl;
X represents halogen, CN, nitro, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, C 1-C6 alkoxy or C 3-C6 cycloalkyl, m represents an integer of 1 to 3;
further, R 3、R4 is Me or Et, X is 6-t-Bu, and m is 1.
Further, in formula (I), R 1 and R 2 together form a group- (CH 2)t -, and t represents an integer of 2 to 5.
Further, in formula (I), R 3、R4 is the same and is selected from H, C 1-C6 alkyl, halogenated C 1-C6 alkyl, C 2-C6 alkenyl, halogenated C 2-C6 alkenyl, C 1-C6 alkoxy or C 3-C6 cycloalkyl, preferably R 3、R4 is the same and 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、CBr3、OMe、OEt、 vinyl and cyclopropane.
Further, in formula (I), R 1 and R 2 together form a group- (CH 2)t -, t represents an integer from 2 to 5;
R 3、R4 is independently selected from H, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane group;
R 5 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, cyclopropane-oxy, nitro, aldehyde, carboxyl, hydroxyl;
X represents H, F, cl, br, me, et, n-Pr, i-Pr, n-Bu, i-Bu, s-Bu, t-Bu, OMe, OEt, vinyl, cyclopropane, and m is 1 or 2.
Further, in formula (I), R 1 and R 2 together form a group- (CH 2)t -, t represents an integer from 3 to 4;
r 3、R4 is Me or Et;
R 5 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.
Further, the compound of formula (I) is specifically selected from:
The pesticide acceptable salt can be a salt prepared by reacting the quinolinol derivative of the present invention with a chemically acceptable acid, wherein the chemically acceptable acid can be an inorganic acid (such as hydrochloric acid, sulfuric acid, phosphoric acid or hydrobromic acid, etc.) or an organic acid (such as oxalic acid, maleic acid, fumaric acid, malic acid, tartaric acid, citric acid or benzoic acid, etc.), and the pesticide acceptable salt can also be a salt prepared by reacting the quinolinol derivative of the present invention 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, etc.) or an organic base (such as trimethylamine, triethylamine, etc.).
Further, the pesticidally acceptable salt may be a potassium salt, a sodium salt, an ammonium salt, a calcium salt, a pyridine salt or a choline salt.
The invention also discloses a sterilization composition which comprises a sterilization effective amount of at least one of the quinoline phenol derivatives or the salts thereof which are acceptable by pesticides, and further comprises a preparation carrier or a preparation auxiliary agent.
The invention also discloses a method for controlling plant diseases, which comprises the step of applying a biological effective amount of at least one of the quinolinol derivatives or the salts thereof which are acceptable by pesticides or the bactericidal composition on plants.
The invention also discloses application of the quinolinol derivative or at least one of the quinolinol derivative serving as a pesticide acceptable salt or the bactericidal composition in controlling plant diseases, and preferably, the plant diseases are bacterial diseases or fungal diseases.
In the definition of the structural formula of the above compounds, the terms used have the following meanings:
Halogen or halogen means fluorine, chlorine, bromine, iodine.
C 1-C6 alkyl, straight-chain or branched alkyl having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, isopropyl or tert-butyl.
Halogenated C 1-C6 alkyl groups, straight-chain or branched alkyl groups having 1 to 6 carbon atoms, and hydrogen atoms on these alkyl groups may be partially or completely substituted with halogen, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl and the like.
C 2-C6 alkenyl straight-chain or branched alkenyl having 2 to 6 carbon atoms, such as vinyl, propenyl, etc.
Halogen C 2-C6 alkenyl straight-chain or branched alkenyl having 2 to 6 carbon atoms, and hydrogen atoms on these alkenyl groups may be partially or entirely substituted with halogen, for example, chlorovinyl group and the like.
C 1-C6 alkoxy, a straight or branched alkyl group having 1 to 6 carbon atoms, is bonded to the structure via an oxygen atom bond.
Halogenated C1-C6 alkoxy groups, straight-chain or branched alkoxy groups having 1 to 6 carbon atoms, in which the hydrogen atoms may be partially or completely substituted by halogen, for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
The abbreviations for the radicals appearing in the present invention are consistent with those commonly used by those skilled 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.
The synthesis method of the compound shown in the formula I comprises the step of reacting a compound shown in the formula III with a compound shown in the formula II (in the chemical formulas listed below, substituents and symbols have the same meanings as those of the substituents and symbols shown in the formula I, so long as the substituents and symbols are not defined in the formula I), and the target product shown in the formula I is obtained after the reaction is carried out in the presence or absence of an alkaline reagent and in the presence or absence of a solvent. The compounds of the formulae II, III are both commercially available or can be prepared by the methods described in EP 407192A:
further, the solvent is selected from one or more solvents selected from acetonitrile, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran, dichloromethane, benzene, toluene, xylene, dichloroethane and ethyl acetate;
further, the reaction may be carried out at normal pressure or high pressure, preferably at 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 as fungicides, in particular as bactericides, have a marked efficacy as fungicides or bactericides, some of which are systemically effective and can be used in crop protection as foliar fungicides, seed dressing fungicides and soil fungicides. Furthermore, they are suitable for controlling harmful fungi which occur in particular in wood or plant roots, in particular for treating fungi or bacteria with an effective amount of at least one compound of the formula I as defined in the invention or as pesticidally acceptable salts, compositions or materials, plants, soil or seeds to be protected from fungal or bacterial attack.
The compounds I according to the invention or their pesticidally acceptable salts, compositions are suitable for use in various cultivated plants such as cereals, for example wheat, rye, barley, triticale, oats or rice; beet, for example sugar beet or fodder beet, fruits, such as pome, stone fruits or berries, for example apples, peas, plums, peaches, almonds, cherries, strawberries or blueberries, legumes, for example lentils, peas, alfalfa or soybeans, oil plants, for example oilseed rape, mustard, olives, sunflowers, coconuts, cocoa beans, castor oil plants, oil palm, peanuts or soybeans, cucurbitaceae plants, for example pumpkin, cucumber or melon, fiber plants, for example cotton, flax or jute, citrus fruits, for example oranges, lemons, grapefruits or tangerines, vegetables, for example spinach, lettuce, asparagus, cabbage, carrot, onion, tomatoes, potatoes, cucurbits or persimmon peppers, laurel plants, for example avocados, cinnamon or camphor, crops of greater economic value, for example corn, soybeans, beans, rape, oil palm, tobacco, nuts, coffee, tea, bananas, grapes, hops, turf, natural rubber plants or ornamental and forest plants, for example flowers, wood, broadleaf trees or evergreen trees, for example conifer, and plant material such as those of the plant cuttings, especially fungal material.
Preferably, the compounds I or their pesticidally acceptable salts, compositions are used for controlling fungal or bacterial diseases on field crops, such as potatoes, sugar beet, tobacco, wheat, rye, barley, oats, rice, maize, cotton, soybean, oilseed rape, legumes, sunflower, coffee or sugar cane, fruits, ornamental plants or vegetables, such as cucumber, tomato, beans or pumpkin, respectively.
The invention also provides a bactericide composition comprising the compound of the formula I. The compounds of formula I may be formulated in a variety of ways, depending on the usual biological and/or chemical parameters and/or physical parameters. Examples of suitable formulation choices are Wettable Powders (WP), wettable powders (SL), soluble Powders (SP), dispersible solutions (DC), aqueous Solutions (AS), microemulsions (ME), emulsifiable Concentrates (EC), aqueous Emulsions (EW), sprayable solutions, suspensions (SC), dispersible oil suspensions (OD), powders (DP), microencapsulated suspensions (CS), water dispersible granules (WG), water Soluble Granules (SG), macrogranules (GG), granules for broadcasting and soil application (GR), aerosols (AE), ultra low volume formulations (ULV) and wax formulations. 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, permeation enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, anti-freeze agents, anti-foam agents, colorants, tackifiers and binders.
Suitable solvents and liquid carriers are water and/or organic solvents, such as medium to high boiling mineral oil fractions, for example kerosene, diesel oil, oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes, alcohols, for example ethanol, propanol, butanol, benzyl alcohol, cyclohexanol, glycols, dimethyl sulfoxide (DMSO), ketones, for example cyclohexanone, esters, for example lactate, carbonate, fatty acid ester, gamma-butyrolactone, fatty acids, phosphonates, amines, amides, for example 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, which can be used as emulsifiers, dispersants, pro-solvents, wetting agents, penetration enhancers, protective colloids or adjuvants.
Suitable adjuvants are compounds which have a negligible or even no pesticidal activity per se and improve the biological properties of the compounds I towards the target, examples being surfactants, mineral or vegetable oils and other adjuvants.
Suitable thickeners are polysaccharides (e.g., xanthan gum, carboxymethylcellulose), inorganic clays (organically modified or unmodified), polycarboxylates and silicates, and the like.
Suitable antifreeze agents are ethylene glycol, propylene glycol, urea, and glycerin, among others.
Suitable defoamers are polysiloxanes, long chain alcohols, fatty acid salts and the like.
Suitable colorants (e.g. red, blue or green) are low water-soluble pigments and water-soluble dyes, and 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 admixed with the active substances according to the invention in the formulation or tank mix are, for example, the substances known from the world technical university of new agricultural chemicals (China agricultural science and technology Press 2010.9). For example, the fungicide active substances mentioned below can be mixed with mixtures of the formula I (remark: the names of the compounds, or of the common names according to the International organization for standardization (ISO), or of the chemical names, where appropriate by the code numbers), azoxystrobin (azoxystrobin), trifloxystrobin (coumethoxystrobin), coumoxystrobin (coumoxystrobin), dimoxystrobin (dimoxystrobin), enestrobin (enestroborin), enestrobin (fenaminstrobin), fenoxystrobin/flufenpyrad (flufenoxystrobin), fluoxastrobin (fluoxastrobin), iminobacteria (kresoxim-methyl), ethaboxam (metominostrobin), oryzamine (orysastrobin), picoxystrobin (picoxystrobin), pyraclostrobin (pyraclostrobin), pyrametostrobin, pyraclostrobin (pyraoxystrobin), trifloxystrobin (trifloxystrobin), 2- [2- (2, 5-dimethylphenoxymethyl) phenyl ] -3-methoxyacrylic acid methyl ester, 2- (2- (3, 6-dichlorophenyl) -1-methyleneoxyphenyl) -2-propyl-oxazamate (6735), 2-methamidone (3735), 2-methyl-35-2-oxazolone (3735) and (N-methyl) can be used as fungicide active substances-8-Benzyl-3- [ (3-acetoxy-4-methoxypyridine-2-carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxahept-7-yl ] ester, 2-methylpropanoic acid [ (3S, 6S,7R, 8R) -8-benzyl-3- [ [ 3-acetoxymethoxy-4-methoxypyridine-2-carbonyl ] amino ] -6-methyl-4, 9-dioxo-1, 5-dioxahept-7-yl ] ester, 2-methylpropanoic acid [ (3S, 6S,7R, 8R) -8-benzyl-3- [ (3-isobutoxycarbonyl-4-methoxypyridine-2-carbonyl) amino ] -6-methyl-4, 9-dioxo-1, 5-dioxahept-7-yl ] ester, 2-methylpropanoic acid [ (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-dioxahept-7-yl ] ester, 2-methylpropanoic acid (3S, 6S,7R, 8R) -3- [ [ (3-hydroxy-4-methoxy-2-pyridinyl) carbonyl ] amino ] -6-methyl-4, 9-dioxo-8- (phenylmethyl) -1, 5-dioxahept-7-yl ester, meflozin (benodanil), bisafen, Boscalid (boscalid), carboxin (carboxin), furbenomyl (fenfuram), fluopyram (fluopyram), fluoamide (flutolanil), fluxapyroxad (fluxapyroxad), furazolidone (furametpyr), isopyrazam, propiconazole (mepronil), carboxin oxide (oxycarboxin), penflufen, penthiopyrad (penthiopyrad), sedaxane, leaf-blight-phthalide (tecloftalam), Brionazole (thifluzamide), N- (4' -trifluoromethylthiobiphenyl-2-yl) -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide, N- (2- (1, 3-trimethylbutyl) phenyl) -1, 3-dimethyl-5-fluoro-1H-pyrazole-4-carboxamide, N- [9- (dichloromethylene) -1,2,3, 4-tetrahydro-1, 4-methylenenaphthalen-5-yl ] -3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxamide; 3-difluoromethyl-1-methyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 3-trifluoromethyl-1-methyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 1, 3-dimethyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 3-trifluoromethyl-1, 5-dimethyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 3-difluoromethyl-1, 5-dimethyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide, 1,3, 5-trimethyl-N- (1, 3-trimethyl-2, 3-indan-4-yl) pyrazole-4-carboxamide; difluoro-forest (diflumetorim), (5, 8-difluoroquinazolin-4-yl) - {2- [ 2-fluoro-4- (4-trifluoromethylpyridin-2-yloxy) phenyl ] ethyl } amine, nitrophenyl derivatives, leku Acad (binapacryl), dimite Tex (dinobuton), dimite Pr (dinocap), fluazinam (fluazinam), azohydrazone (ferimzone), organometallic compounds, triphenyltin-based salts, such as, for example, french frietin (fentin-acetate), triphenyltin chloride (fentinchloride) or Dufulin (fentinhydroxide), ametoctradin and silthiopham (silthiofam), penconazole (azaconazole), Bispyristate (bitertanol), furfuryl azole (bromuconazole), cyproconazole (cyproconazole), difenoconazole (difenoconazole), diniconazole (diniconazole), diniconazole M (diniconazole-M), oxyzodone (epoxiconazole), fenbuconazole (fenbuconazole), fluquinconazole (fluquinconazole), flusilazole (flusilazole), flutriafol (flutriafol), Hexaconazole (hexaconazole), amidazole (imibenconazole), cyclopentanol (ipconazole), metconazole, myclobutanil (myclobutanil), oxypconazole, paclobutrazol (paclobutrazole), penconazole (penconazole), propiconazole (propiconazole), prothioconazole (prothioconazole), simeconazole (simeconazole), tebuconazole (tebuconazole), Triflumizole (tetraconazole), triazolone (triadimefon), pyraclostrobin (triadimenol), triticonazole (triticonazole), uniconazole (uniconazole), imazalil (imazalil), fenoxanil (pefurazoate), prochloraz (prochloraz), triflumizole (triflumizol), isopyrazam (fenarimol), flubenamal (nuarimol), pyripyropene (pyrifenox), Oxazine (triforine), 4-dodecyl-2, 6-dimethylmorpholine (aldimorph), molinate (dodemorph), molinate acetate (dodemorph-acetate), fenpropimorph (fenpropimorph), kringle (tridemorph), fenpropidin (fenpropidin), benomyl (piperalin), spiroxamine (spiroxamine), benalaxyl (benalaxyl), benalaxyl (benalaxyl-M), kiralaxyl, metalaxyl (metalaxyl), metalaxyl-M (mefenoxam), formamide (ofurace), oxadixyl (oxadixyl), fenhexamid (fenhexamid), hymexazol (hymexazole), isohexide (octhilinone), oxaquin (oxolinicacid), sulfoxaflor (bupirimate), benomyl (benomyl), carbendazim (carbendazim), fuberidazole (fuberidazole), Thiabendazole (thiabendazole), thiophanate methyl (thiophanate-methyl), diethofencarb (diethofencarb), ethaboxam (ethaboxam), pencycuron (pencycuron), fluopicolide (fluopicolide) zoxamide (zoxamide), metrafenone (metrafenone), pyrifenone, cyprodinil (mepanipyrim), pyrimethanil (pyrimethanil), Blasticidin (blasticidin-S), kasugamycin (kasugamycin), kasugamycin hydrate (kasugamycinhydrochloride-hydrate), midomycin (mildiomycin), streptomycin (streptomycin), terramycin (oxytetracyclin), polyoxin (polyoxine), validamycin (VALIDAMYCINA), triflumuron (fluoroimid), iprodione, procymidone (procymidone), Ketene (vinclozolin), fenpiclonil (fenpiclonil), fluoxastrobin (fluoxastrobin), kewen (edifenphos), iprobenfos (iprobenfos), triazophos (pyrazophos), isoprothiolane (isoprothiolane), chloronitramine (dicloran), pentachloronitrobenzene (quintozene), tetrachloronitrobenzene (tecnazene), tolclofos-methyl (tolclofos-methyl), biphenyl, difenoconazole (chloroneb), Chlorazol (ethyldiazole), dimethomorph (dimethomorph), flumorph (flumorph), mandipropamid (mandipropamid), pyrimorph (pyrimorph), benthiavalicarb (benthiavalicarb), iprovalicarb (iprovalicarb), VALIFENALATE, N- (1- (1- (4-cyanophenyl) ethanesulfonyl) butan-2-yl) carbamic acid 4-fluorophenyl ester, bavistin (propamocarb), propamocarb hydrochloride (propamocarb-hydrochlorid), Bordeaux mixture, copper acetate, copper hydroxide, copper king (copperoxychloride), basic copper sulfate, thiram (ferbam), mancozeb (maneb), wilms (metam), metiram (metiram), methysezin (propineb), thiram (thiram), zineb (zineb), ziram (ziram), dichlormid (anilazine), chlorothalonil (chlorothalonil), Captan (captafol), captan (captan), folpet (folpet), dichlofluanid (dichlofluanid), dichlorophenol (dichlorophen), sulfenamide (flusulfamide), hexachlorobenzene (hexachlorobenzene), pentachlorophenol (pentachlorphenole) and salts thereof, tetrachlorophthalide (phthalide), tolylfluanid (tolylfluanid), N- (4-chloro-2-nitrophenyl) -N-ethyl-4-methylbenzenesulfonamide, Polyvidin free base, biguanide salt (guazatine), biguanide octylamine (guazatine-acetate), biguanide octylacetate (iminoctadine), biguanide octylamine triacetate (iminoctadine-triacylate), bis-octaguanamine salt (iminoctadine-tris (albesilate)), dithianon (dithianon), 2, 6-dimethyl-1H, 5H- [1,4] dithiadieno [2,3-c:5,6-c' ] bipyrrolidinyl-1, 3,5,7 (2H, 6H) -tetraone, validamycin (validamycin), polyoxin (polyoxinB), melanin synthesis inhibitor (pyroquinen), tricyclazole (tricyclazole), chlorocyclopropylamide (carpropamid), dicyclopentadienyl (dicyclomet), cyhalonil (fenoxanil), thiadiazolin (acibenzolar-S-methyl), thiabendazole (probenazole), isothiabendazole (isotianil), tiadinil (tiadinil), calcium (prohexadione-calcium) propisochlor, phosphonates such as chlorpyrifos (fosetyl), fosetyl-aluminum (fosetyl-aluminum), phosphorous acid and salts thereof, bronopol (bronopol), miticidal amine (chinomethionat), cyflufenamid (cyflufenamid), iprodione (cymoxanil), dazomet (dazomet), prochloraz (debacarb), pyridalyl (dichlomerizine), difenoconazole (difenzoquat), Felteon-sodium methyl sulfate (difenzoquat-methylsulfate), diphenylamine, fenpyraclostrobin (fenpyrazamine), fluorobiphenyl (flumetover), sulfenpyrad, flutianil, sulfencarb (methasulfocarb), chlordine (nitrapyrin), iprovalicarb (nitrothral-isopropyyl), copper quinolinate (oxin-coppers), propoxyquinoline (proquinazid), tebufloquin, leaf-cumyl phthalide, and the like, Zosin (triazoxide) and the like.
Advantageous effects
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
By chemically modifying a compound with a2, 3-dimethyl-6-tert-butyl-8-fluoro-4-hydroxyquinoline structure, a pyrazole structure is introduced, and the obtained quinolinol derivative or a salt thereof which is acceptable as a pesticide has excellent biological activity on rice blast, satisfactory control activity on other control objects except rice blast, and excellent safety on crops.
Embodiments of the invention
The technical solutions in the embodiments of the present invention will be clearly and completely described below in connection with the embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
By comprehensively considering the economy, diversity and bioactivity 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 of tables 1-2 are only for better illustration of the present invention and are not meant to limit the present invention, and 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.
TABLE 1 Structure of Compounds of formula I
TABLE 2 1 H NMR data
The process for preparing the compounds of the present invention is 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. Those skilled in the art will appreciate that other synthetic routes may also be used to synthesize the compounds of the present invention. Although specific starting materials and conditions in the synthetic routes have been described below, they may be readily replaced with other similar starting materials and conditions, and variations or modifications to the preparation methods of the present invention, such as various isomers of the compounds, are included within 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, protection of the appropriate groups during the reaction, and the like.
Example 1
Synthesis of Compound I-3:
Intermediate II-3 (2.47 g,10 mmol) and methylene chloride (30 ml) were added to a reaction flask, intermediate III-3 (1.98 g,10 mmol) was added under stirring at 20℃and triethylamine (2 eq) was added under stirring at 20℃followed by TLC (ethyl acetate: petroleum ether=1:1, GF254, UV development), after completion of the reaction, the solvent was spun off, dried, and purified by column chromatography to give compound I-3,3.17g as a white solid powder, melting point ：176.1-177.2℃;1H NMR(500MHz,Chloroform-d)δ7.43(dd,J＝12.8,1.8Hz,2H),4.25(t,J＝7.3Hz,2H),3.24(t,J＝7.4Hz,2H),2.99(qd,J＝7.5,1.5Hz,2H),2.77(d,J＝1.6Hz,3H),2.71(q,J＝7.5Hz,2H),2.29(d,J＝1.7Hz,3H),1.37–1.29(m,12H).
Example 2
Synthesis of Compound I-41:
adding intermediate II-41 (II-2, 2.47g,10 mmol) and acetonitrile (30 ml) into a reaction bottle, adding intermediate III-41 (2.12 g,10 mmol) under stirring at 20 ℃, adding triethylamine (2 eq) under stirring at 20 ℃, tracking by TLC (ethyl acetate: petroleum ether=1:1, GF254, UV color development), completely reacting, then spinning out the solvent, drying, purifying by column chromatography to obtain the compound I-41, namely the target compound 3.12g, 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 an intermediate II-6 (II-2, 2.47g,10 mmol) and acetonitrile (30 ml) into a reaction bottle, adding the intermediate III-6 (2.40 g,10 mmol) under stirring at 20 ℃, adding triethylamine (2 eq) under stirring at 20 ℃, tracking the reaction (ethyl acetate: petroleum ether=1:1, GF254, UV color development) by TLC, completely reacting, then unscrewing the solvent, drying, purifying by column chromatography to obtain the target compound I-6,3.12g, off-white solid powder with a melting point ：197-202℃;1H NMR(500MHz,Chloroform-d)δ7.45–7.40(m,2H),4.20(s,2H),3.29–3.22(m,2H),2.77(d,J＝1.7Hz,3H),2.31(d,J＝1.7Hz,3H),2.14–2.06(m,2H),1.96(td,J＝6.0,3.1Hz,2H),1.46(s,9H),1.33(d,J＝1.7Hz,9H).
Example 4
Preparation of the preparation:
1. The powder is prepared by weighing 20% of the compound of formula (I) and 80% of kaolin, mixing uniformly, and pulverizing.
2. The wettable powder is prepared by weighing 20% of a compound of formula (I), 8% of calcium lignosulfonate, 2% of sodium dodecyl sulfate, 3% of white carbon black and 100% of kaolin. Mixing uniformly, and obtaining the product after jet milling.
3. The water dispersible granule is prepared by weighing 60% of a compound of formula (I), 6% of sodium lignin sulfonate, 4% of NNO (alkyl naphthalene sulfonate formaldehyde condensate), 2% of nekal BX (dibutyl sodium naphthalene sulfonate), 3%K-12 (sodium dodecyl sulfate), 5% of carboxymethyl (ethyl) cellulose, 5% of diatomite, 5% of glucose and kaolin to 100%. Mixing uniformly, pulverizing by air flow, weighing powder, adding water, mixing, granulating in a granulator, drying, and sieving to obtain granular product.
4. And (3) the emulsifiable concentrate is prepared by weighing 15% of a compound shown in the formula (I), 5% of pesticide emulsion 700#, 5% of pesticide emulsion 500#, 6% of pesticide emulsion 1601#, 10% of cyclohexanone, 3% of N-methyl pyrrolidone and 150% of solvent oil to 100%, and completely dissolving and uniformly mixing the components to obtain the product.
5. 15% Of a compound shown in a formula (I), 4% of FS3000 (phosphate ester type anionic surfactant), 2% of NS-500LQ (nonionic hydroxyl 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, adding deionized water to 100%, preparing slurry, and sanding to obtain the product.
All the above are weight percentages.
Example 5
Rice blast protective control test (Pyricularia oryzae):
the host crop is rice (Lu Dao No. 1), and the specific operation is as follows:
Weighing a compound sample with a certain mass, dissolving the compound sample in acetone, and preparing a mother solution for standby. In the test, compound samples and control medicines were prepared into serial concentration gradient medicine solutions with water of 0.1% tween 80 for in vivo screening. Selecting potted rice seedlings with three leaves, one core and consistent growth vigor, and discharging the potted rice seedlings in sequence after marking for experiments. The sprayer is a spray tower, spraying 30ml of medicinal liquid per treatment, and naturally drying. After 24h, the pathogenic bacteria were inoculated and a blank control was set. Washing surface spores in a culture dish full of spores, filtering with 2-4 layers of gauze to prepare spore suspension with the concentration of 1X 10 5-1×106 spores/mL, uniformly spraying on rice seedlings with an inoculation sprayer (the pressure is 0.1 MPa), transferring the inoculated test material into a humidity preserving box (chamber) or a climatic chamber, culturing at the temperature of 26-28 ℃ and under dark conditions, transferring the test material into a culture box (chamber) or a greenhouse high-humidity culture with alternating light and darkness and illumination intensity of more than 20000lx after 24 hours, and carrying out grading investigation according to blank control morbidity conditions after 5-7 days.
Level of control effect:
A, the prevention effect is more than 80 percent;
the control efficiency is 50-79%;
c, the prevention effect is less than 50%;
The rice blast protection test results are shown in Table 3.
TABLE 3 Rice blast protective test results
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 compound sample with a certain mass, dissolving the compound sample in acetone, and preparing a mother solution for standby. In the test, compound samples and control medicines were prepared into serial concentration gradient medicine solutions with water of 0.1% tween 80 for in vivo screening. Selecting potted rice seedlings with three leaves, one core and consistent growth vigor, and discharging the potted rice seedlings in sequence after marking for experiments. The sprayer is a spray tower, spraying 30ml of medicinal liquid per treatment, and naturally drying. After 24h, the pathogens were inoculated, and blank controls and other agent controls were set. Adding sterile water into a culture dish full of spores, scraping surface spores, filtering with 2-4 layers of gauze to prepare spore suspension with the concentration of 5 multiplied by 10 5-6×105/mL, uniformly spraying on rice seedlings with an inoculation sprayer (the pressure is 0.1 MPa), transferring the inoculated test material into a humidity preserving box (chamber) or a climatic chamber, the relative humidity is more than 85%, the temperature is 26-28 ℃, transferring the test material into the culture box (chamber) with the illumination intensity of more than 2000lx or a greenhouse for high-humidity culture after 24 hours, and investigating according to the disease condition of blank control after 5-7 days.
Level of control effect:
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%;
3, the prevention effect is 50-79%;
4, the prevention effect is less than 50%;
the rice blast protection test results are shown in Table 4.
TABLE 4 Rice blast protection test results at various concentrations
Example 7
Melon powdery mildew protective control test (Sphaeotheca fuliginea):
the host crop is cucumber (jin you No. 1), and a pot seedling method is adopted, and the specific operation is as follows:
Weighing a compound sample with a certain mass, dissolving the compound sample in acetone, and preparing a mother solution for standby. In the test, compound samples and control medicines were prepared into serial concentration gradient medicine solutions with water of 0.1% tween 80 for in vivo screening. And selecting 2-4 leaf stage potted cucumber seedlings which grow neatly and consistently as test host plants of cucumber powdery mildew. The sprayer is a spray tower, spraying 30ml of medicinal liquid per treatment, and naturally drying. After 24h, the pathogens were inoculated, and blank controls and other agent controls were set. Fresh spores of powdery mildew generated in 24h on diseased cucumber leaves are prepared into suspension (the concentration is 1X 10 5 spores/mL), and the suspension is sprayed on inoculated leaves and cultured under proper conditions. And after 7-10 days, completely curing the disease by using clear water, and investigating test results.
Level of control effect:
I, the control effect is more than 90 percent;
II, the prevention effect is more than 80%;
III, the prevention effect is 50-79%;
IV, the prevention effect is less than 50%;
the protective test results of melon powdery mildew are shown in table 5.
TABLE 5 protective test results for powdery mildew of melon
The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement the same, and are not intended to limit the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be included within the scope of the present invention.
Industrial applicability
The compound of the invention can be used as a bactericide for controlling plant diseases, and is especially suitable for paddy rice, wheat and/or melons.
Claims (8)
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| 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 |
| AU782532B2 (en) * | 2000-05-30 | 2005-08-04 | Meiji Seika Pharma Co., Ltd. | Rice blast control agents |
| DE10135466A1 (en) * | 2001-07-20 | 2003-02-06 | Bayer Cropscience Ag | Biphenyl-substituted 4-hydroxy-quinolones |
| CN110452167B (en) * | 2018-04-16 | 2020-08-21 | 东莞市东阳光农药研发有限公司 | Quinoline derivatives and preparation method and use thereof |
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