CN113045561A - Diarylamine derivatives as fungicides - Google Patents
Diarylamine derivatives as fungicides Download PDFInfo
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- CN113045561A CN113045561A CN202010629681.3A CN202010629681A CN113045561A CN 113045561 A CN113045561 A CN 113045561A CN 202010629681 A CN202010629681 A CN 202010629681A CN 113045561 A CN113045561 A CN 113045561A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/76—1,3-Oxazoles; Hydrogenated 1,3-oxazoles
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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
- A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
- A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
- A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
- C07D413/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings
- C07D413/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links
Abstract
The invention discloses a diarylamine derivative used as a fungicide, which has a structural general formula as follows:
Description
Technical Field
The invention relates to the technical field of sterilization, in particular to a diarylamine derivative used as a fungicide.
Background
The germs cause great damage to crops, especially to agricultural products such as grains, fibers and the like, such as cotton, rice, corn, wheat, soybean and the like, which can meet the basic requirements of human beings. Killing or inhibiting the growth of pathogens while avoiding or reducing damage to the crop is an effective way to improve agricultural production. There is therefore a continuing need to develop more effective novel fungicides. Although chinese patent CN109923111A reports an antibiotic compound, its chemical formula is shown as follows:
however, the structure of the compound is greatly different from that of the compound in the patent, and the structure is only used for bacterial control.
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
In order to meet the requirement of agriculture, the invention provides a diarylamine derivative used as a fungicide, and the compound can be used as a bactericide for effectively controlling diseases caused by downy mildew, epidemic disease, anthracnose, rust disease and the like.
The technical scheme of the invention is as follows:
the invention provides a diarylamine derivative used as a fungicide, which has a structural general formula as follows:
in the formula:
R1、R2can be the same or different and is respectively selected from hydrogen, halogen, cyano, C1-C12 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 alkylthio and C1-C4 alkylsulfonyl;
R3selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkylcarbonyl, halogenated C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl and halogenated C1-C4 alkylsulfonyl;
x is selected from O, S or NR5；
R4Is one or more substituents, each independently selected from halogen, cyano, NO2, carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
R5selected from hydrogen, C1-C4 alkyl;
the diarylamine derivative does not include a compound A, and the structural formula of the compound A is shown as follows:
preferred diarylamine derivatives of the present invention are:
R1、R2can be the same or different and is respectively selected from hydrogen, halogen and cyano;
R3selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl;
x is selected from O or NR5；
R4Is one or more substituents, each independently selected from halogen, cyano, NO2, carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
R5selected from hydrogen.
Further preferred diarylamine derivatives of the present invention are:
R1、R2can be the same or different and is respectively selected from H, F, Cl, Br and I;
R3selected from hydrogen, potassium, sodium;
x is selected from O or NR5；
R4Is one or more substituents, each independently selected from fluoro, chloro, bromo or iodo, hydroxy, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methylsulfonyl;
R5selected from hydrogen.
Further preferred diarylamine derivatives of the present invention are:
R1、R2can be the same or different and is respectively selected from H, F, Cl and Br;
R3selected from hydrogen, potassium, sodium;
x is selected from O or NR5；
R4Is one or more substituents, each independently selected from fluoro, chloro, bromo, hydroxy, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methylsulfonyl;
R5selected from hydrogen.
Still further preferred diarylamine derivatives of the present invention are:
R1、R2can be the same or different and is respectively selected from H, F, Cl and Br;
R3selected from hydrogen, potassium, sodium;
x is selected from O or NR5；
R4Is one or more substituents, each independently selected from fluoro, chloro, bromo, hydroxy, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl;
R5selected from hydrogen.
In the diarylamine derivatives of the present invention, stereoisomers (different configurations are represented by R and S, respectively) may be formed due to the attachment of different groups or substituents to the chiral carbon or nitrogen. The invention includes the R-isomer and the S-isomer and mixtures thereof in any proportion.
In the diarylamine derivatives given above, the terms used in the compilation are generally defined as follows:
unsubstituted means that all substituents are hydrogen.
Halogen: refers to fluorine, chlorine, bromine or iodine.
Alkyl groups: straight-chain, branched or cyclic alkyl, such as methyl, ethyl, propyl, isopropyl, tert-butyl or cyclopropyl.
Halogenated alkyl groups: straight-chain or branched haloalkyl groups in which the hydrogen atoms may be partially or wholly replaced by halogen atoms, for example, haloalkyl groups such as chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl or trifluoromethyl.
Alkoxy groups: straight-chain, branched-chain or cyclic alkoxy, for example methoxy, ethoxy, propoxy, isopropoxy, tert-butoxy or cyclopropoxy.
Haloalkoxy groups: straight-chain or branched haloalkoxy groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms, for example, haloalkyl groups such as chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy or trifluoromethoxy groups.
Alkylthio group: straight or branched chain alkyl groups attached to the structure via a sulfur atom.
Haloalkylthio: straight-chain or branched alkylthio groups in which the hydrogen atoms may be partially or fully substituted by halogen atoms. For example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.
Acids which can form salts with the diarylamine derivatives of the present invention include carboxylic acids such as acetic acid, propionic acid, butyric acid, oxalic acid, adipic acid, dodecanedioic acid, lauric acid, stearic acid, trifluoroacetic acid, fumaric acid, maleic acid, benzoic acid or phthalic acid, sulfonic acids such as methanesulfonic acid, 1, 3-propanedisulfonic acid, p-toluenesulfonic acid or dodecylbenzenesulfonic acid; and inorganic acids such as hydrochloric acid, sulfuric acid, nitric acid or carbonic acid.
Bases which can form salts with the diarylamine derivatives of the present invention include sodium hydroxide, potassium hydroxide, calcium hydroxide, lithium hydroxide, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, metallic sodium, sodium hydride, sodium amide, butyl lithium, and the like.
The partially diarylamine derivatives of the present invention can be illustrated by specific compounds listed in table 1, but do not limit the present invention.
Table 1 examples of partial diarylamine derivatives of the invention
The synthesis method comprises the following steps:
the diarylamine derivatives of the present invention can be prepared according to the following method:
a first route,
L is easy leaving group such as F, Cl, Br, etc.
According to the above reaction equation, (formula a) and substituted pyridazinamines (formula b) are reacted in the presence or absence of a base, preferably using a solvent. The reaction temperature is preferably 0 to 150 ℃, and the reaction time is 30 minutes to 20 hours, preferably 0.5 to 10 hours. The solvent is any inert solvent which does not directly affect the reaction, including aromatic hydrocarbons such as benzene, toluene and xylene; ketones, such as acetone methyl ethyl ketone and methyl isobutyl ketone; halogenated hydrocarbons such as dichloromethane, chloroform and dichloroethane; lipids, such as methyl acetate and ethyl acetate; and polar solvents such as tetrahydrofuran, acetonitrile, dioxane, N-dimethylformamide, N-methylpyrrolidone, dimethylsulfoxide and pyridine.
The base includes metal hydrides such as sodium hydride; alkali metal hydroxides such as sodium hydroxide and potassium hydroxide; alkali metal carbonates such as sodium carbonate and potassium carbonate; sodium amide; organic amines such as pyridine and triethylamine.
In order to isolate the diarylamine derivative after the reaction, in the case of using a solvent soluble in water, the solvent is distilled off under reduced pressure, water is added to the resulting residue, and a water-insoluble aromatic hydrocarbon such as benzene, toluene and xylene is used; halogenated alkanes such as chloroform and dichloromethane; and esters such as ethyl acetate, and washing the extract with saturated aqueous sodium chloride solution, drying the obtained extract with a drying agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate, and then removing the solvent under reduced pressure. When a water-insoluble solvent is used, water is added to the reaction mixture, separation is carried out with shaking, the resulting organic layer is washed with a saturated aqueous sodium chloride solution, dried over a drying agent such as anhydrous magnesium sulfate or anhydrous sodium sulfate, and then the solvent is removed under reduced pressure. The residue obtained is purified by recrystallization, suspension and washing and column chromatography to give the diarylamine derivative.
The diarylamine derivatives (formula a) and (formula b) were commercially available as intermediates for synthesizing the diarylamine derivatives.
Pest control agents:
the diarylamine derivative of the present invention shows excellent activity against various diseases in the agricultural field. The examples of diseases mentioned below are intended only to illustrate the invention, but in no way limit it.
The diarylamine derivatives of the present invention can be used for preventing and treating the following diseases: oomycete diseases such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, beet downy mildew, sugarcane downy mildew, tobacco downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, Chinese cabbage downy mildew, spinach downy mildew, radish downy mildew, grape downy mildew, onion downy mildew), white rust (rape white rust, Chinese cabbage white rust), damping-off (rape damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber damping-off, cotton seedling damping-off), cotton rot (hot pepper rot, loofah sponge rot, wax gourd blight), epidemic diseases (broad bean blight, cucumber blight, pumpkin blight, melon blight, hot pepper, leek blight, garlic blight, cotton blight, tomato blight, etc.; fungi imperfecti diseases such as wilt (sweet potato wilt, cotton wilt, sesame wilt, castor wilt, tomato wilt, bean wilt, cucumber wilt, pumpkin wilt, winter melon wilt, watermelon wilt, sweet melon wilt, hot pepper wilt, broad bean wilt, rape wilt, soybean wilt), root rot (hot pepper root rot, eggplant root rot, bean rot, cucumber root rot, bitter gourd root rot, cotton black root rot, broad bean root rot), damping off (seedling blight of cotton, sesame seedling blight, hot pepper seedling blight, cucumber damping off, cabbage stalk rot), anthracnose (sorghum anthracnose, cotton anthracnose, kenaf anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, mulberry leaf, hot pepper, bean disease, cucumber anthracnose, red sesame anthracnose, jute anthracnose, flax anthracnose, tobacco anthracnose, eggplant disease, hot pepper anthracnose, vegetable bean disease, and cucumber blight, Balsam pear anthracnose, pumpkin anthracnose, wax gourd anthracnose, watermelon anthracnose, melon anthracnose, litchi anthracnose), verticillium wilt (cotton verticillium wilt, sunflower verticillium wilt, tomato verticillium wilt, hot pepper verticillium wilt, eggplant verticillium wilt), scab (pumpkin scab, wax gourd scab, melon scab), gray mold (boll gray mold, red ramie gray mold, tomato gray mold, hot pepper gray mold, bean gray mold, celery gray mold, spinach gray mold, kiwi gray mold), brown spot (cotton brown spot, jute brown spot, beet brown spot, peanut brown spot, pepper brown spot, wax gourd brown spot, soybean brown spot, sunflower brown spot, pea brown spot, broad bean brown spot), black spot (flax brown spot, rape black spot, sesame black spot, sunflower black spot, castor black spot, tomato black spot, pepper black spot, eggplant black spot, bean black spot, cucumber black spot, celery black spot, carrot black rot, carrot black spot, apple black spot, peanut black spot), spot blight (tomato spot blight, pepper spot blight, celery spot blight), early blight (tomato early blight, pepper early blight, eggplant early blight, potato early blight, celery early blight), ring spot (soybean ring spot, sesame ring spot, bean ring spot), leaf blight (sesame leaf blight, sunflower leaf blight, watermelon leaf blight, melon leaf blight), stem base rot (tomato stem base rot, bean stem base rot), and others (corn round spot, kenaf waist fold, rice blast, black sheath disease, sugarcane eye spot, cotton boll aspergillosis, peanut crown rot, soybean stem blight, soybean black spot, melon northern leaf blotch, tea leaf spot, black spot, peanut net spot, red leaf spot, tomato black spot, potato black spot, tomato spot, Pepper white spot disease, white gourd leaf spot disease, celery black rot disease, spinach heart rot disease, kenaf leaf mold disease, kenaf spot disease, jute stem spot disease, soybean purple spot disease, sesame leaf spot disease, castor gray spot disease, tea brown leaf spot disease, eggplant brown orbicular spot disease, kidney bean red spot disease, bitter gourd leukoderma, watermelon spot disease, jute bottom rot disease, sunflower root stem rot disease, kidney bean carbon rot disease, soybean target spot disease, eggplant rod spore leaf spot disease, cucumber target spot disease, tomato leaf mold, eggplant leaf mold, broad bean red spot disease and the like); basidiomycete diseases such as rust (wheat stripe rust, wheat stalk rust, wheat leaf rust, peanut rust, sunflower rust, sugarcane rust, leek rust, onion rust, chestnut rust, soybean rust), smut (maize head smut, maize smut, sorghum head smut, sorghum loose smut, sorghum stalk smut, chestnut kernel smut, sugarcane head smut, kidney bean rust) and others (such as wheat sharp eyespot, rice sheath blight, etc.); ascomycetous diseases, such as powdery mildew (wheat powdery mildew, rape powdery mildew, sesame powdery mildew, sunflower powdery mildew, beet powdery mildew, eggplant powdery mildew, pea powdery mildew, towel gourd powdery mildew, pumpkin powdery mildew, wax gourd powdery mildew, melon powdery mildew, grape powdery mildew, broad bean powdery mildew), sclerotinia rot (flax sclerotinia rot, rape sclerotinia rot, soybean sclerotinia rot, peanut sclerotinia rot, tobacco sclerotinia rot, pepper sclerotinia rot, eggplant sclerotinia rot, kidney bean sclerotinia rot, pea sclerotinia rot, cucumber sclerotinia rot, bitter gourd sclerotinia rot, wax gourd sclerotinia rot, watermelon sclerotinia rot, celery sclerotinia rot), scab (apple scab, pear scab) and the like.
The diarylamine derivatives of the present invention have excellent fungicidal activity and can be advantageously used for protecting crops, livestock and livestock animals important in agriculture and horticulture, and the environment where humans are usually exposed from harmful bacteria.
Further, the diarylamine derivative is used for preparing a bactericide for preventing and treating fungal diseases.
The fungal diseases are downy mildew, white rust, damping-off, cotton rot, epidemic disease, late blight, fusarium wilt, root rot, damping off, anthracnose, verticillium wilt, scab, gray mold, brown spot, black spot, spot blight, early blight, ring spot, rice blast, rust disease, smut, powdery mildew or sclerotinia rot.
The amount of the compound used to achieve the desired effect will vary depending on factors such as the compound used, the crop being protected, the type of pest, the extent of infection, the climatic conditions, the method of application, and the dosage form employed.
A dosage of 10 g to 1000 g of diarylamine derivative per hectare provides adequate control.
A further object of the present invention relates to diarylamine derivatives, a method for controlling phytopathogenic fungi in crops of agricultural and horticultural importance and/or in livestock and breeding animals and/or in the environment frequented by humans. In particular, the amount of compound used varies from 10 grams per hectare to 1000 grams per hectare.
For practical application in agriculture, it is often beneficial to use a composition comprising one or more of the diarylamine derivatives of the present invention.
Therefore, another object of the present invention relates to a bactericidal composition containing one or more diarylamine derivatives as active ingredients, wherein the weight percentage of the active ingredients in the composition is 0.1-99%.
The compositions may be used in the form of dry powders, wettable powders, emulsifiable concentrates, microemulsions, pastes, granules, solutions, suspensions, etc., the type of composition being selected depending on the particular application.
The compositions are prepared in a known manner, for example by diluting or dissolving the active substance with a solvent medium and/or a solid diluent, optionally in the presence of a surfactant.
Useful solid diluents or carriers are for example: silica, kaolin, bentonite, talc, diatomaceous earth, dolomite, calcium carbonate, magnesium oxide, chalk, clay, synthetic silicates, attapulgite, sepiolite and the like.
Besides water, usable liquid diluents also include, for example, aromatic organic solvents (xylene or a mixture of alkylbenzenes, chlorobenzene, etc.), paraffins (petroleum fractions), alcohols (methanol, propanol, butanol, octanol, glycerol), esters (ethyl acetate, isobutyl acetate, etc.), ketones (cyclohexanone, acetone, acetophenone, isophorone, ethyl amyl ketone, etc.), amides (N, N-dimethylformamide, N-methylpyrrolidone, etc.).
Useful surfactants include sodium, calcium, triethylamine or triethanolamine salts of alkyl sulfonates, alkylaryl sulfonates, polyoxyethylene alkylphenols, polyoxyethylene esters of sorbitol, lignosulfonates, and the like.
The composition may further contain specific additives for specific purposes, for example, binders such as gum arabic, polyvinyl alcohol, polyvinyl pyrrolidone, etc.
The concentration of the active ingredient in the above composition may vary within wide limits depending on the active ingredient, the purpose of use, the environmental conditions and the type of formulation employed. The concentration of the active ingredient is generally in the range from 0.1 to 99%, preferably from 5 to 60%.
If desired, further active ingredients compatible with the diarylamine derivatives of the invention, such as further acaricides/insecticides, fungicides, plant growth regulators, antibiotics, herbicides, fertilizers, can be added to the compositions.
However, the form of the composition is not limited thereto, and one or two or more compounds in combination may be mixed as an active ingredient.
Several common formulation methods are exemplified below:
preparation of a suspending agent: the content of active components in the common formula is 5-35%. Adding water as medium, raw medicine, dispersant, suspending agent and anti-freezing agent into a sand mill, grinding, and making into suspension.
Preparing the aqueous emulsion: the raw medicine, the solvent and the emulsifier are added together to be dissolved into a uniform oil phase. Mixing water and antifreeze agent to obtain uniform water phase. And adding the water phase into the oil phase or adding the oil phase into the water phase under high-speed stirring to form the aqueous emulsion with good dispersibility. The content of the active component of the aqueous emulsion is generally 5 to 15 percent. To prepare concentrated emulsions, the diarylamine derivatives of the invention can be dissolved in one or more solvents mixtures and emulsifiers added to enhance the dispersion of the compounds in water.
Preparing wettable powder: according to the formula requirement, the original medicine, various surfactants, solid diluents and the like are fully mixed and crushed by an ultrafine crusher to obtain a wettable powder product with a preset content (for example, 10-60%). To prepare wettable powders suitable for spraying, the diarylamine derivatives of the invention can be mixed with finely divided solid powders such as clays, inorganic silicates, carbonates and wetting agents, binders and/or dispersants.
Preparing water dispersible granules: mixing and crushing the original medicine, the powdery solid diluent, the wetting and spreading agent, the adhesive and the like, adding water, kneading, adding into a granulator with a certain specification of sieve for granulation, and then drying and sieving (according to the range of the sieve). Or adding the raw medicine, dispersant, disintegrant, wetting agent and solid diluent into a sand mill, grinding with water as a medium to prepare a suspending agent, and then carrying out spray drying granulation to prepare a granular product with the content of 20-30 percent.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to embodiments and examples, but those skilled in the art will understand that the following embodiments and examples are only illustrative of the present invention and should not be construed as limiting the scope 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. Those who do not specify the conditions are performed according to the conventional conditions or the conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
The present invention is further illustrated by specific examples and comparative examples, but it should be understood that these examples are for illustrative purposes only and are not to be construed as limiting the invention in any way.
Example 1: preparation of Compound 23
16.4g (0.1mol) of 3, 6-dichloro-4-aminopyridazine and 27g of potassium carbonate were added to a 150mL acetonitrile solution containing 18.8g (00.1mol) of 2, 6-dichlorobenzoxazole with stirring at room temperature, the mixture was stirred under reflux at elevated temperature for 2 to 3 hours, after completion of the reaction by TLC, the solvent was distilled off under reduced pressure, and the residue was added to an excess of water, stirred, filtered and washed with water and petroleum ether in this order to obtain 26.2g of a white solid with a yield of 83.2%. (1HNMR, 400MHz, internal standard TMS, solvent CDCl3)δppm 8.83(1H,s)，7.82(1H,s)，7.56(1H,d)，7.48(1H,d)，7.35(1H,d)。
Example 2: preparation of Compound 75
16.4g (0.1mol) of 3, 6-dichloro-4-aminopyridazine and 26g of potassium carbonate were added to 150mL of acetonitrile solution containing 18.7g (0.1mol) of 2, 6-dichlorobenzimidazole with stirring at room temperature, the mixture was heated under reflux with stirring for 2 to 3 hours, after completion of the reaction monitored by TLC, the solvent was distilled off under reduced pressure, and the residue was added to an excess of water, stirred, filtered and washed with water and petroleum ether in this order to obtain 26.8g of a white solid with a yield of 86.4%. (1HNMR, 400MHz, internal standard TMS, solvent (CDCl)3)δppm 8.80(1H,s)，7.78(1H,s)，7.50(1H,d)，7.45(1H,d)，7.32(1H,d)。
EXAMPLE 3 preparation of sodium salt of Compound 23
To 100mL of a methanol solution containing 31.6g (0.1mol) of Compound 23 was added 4g (0.1mol) of sodium hydroxide with stirring at room temperature, and the mixture was reacted with stirring at room temperature for 2 to 3 hours, and the solvent was distilled off under reduced pressure to obtain 36.1g of a white solid in 99% yield. (1HNMR, 400MHz, internal standard TMS, solvent D2O)δppm 8.90(1H,s)，7.65(1H,d)，7.52(1H,s)，7.38(1H,d)。
Table 2 characterization of the Compounds of the invention partially shown in formula I
Example 4: 30% wettable powder
And (3) fully mixing the compound 2 and other components, and crushing by using an ultrafine crusher to obtain a 30% wettable powder product.
Example 5: 40% thick suspending agent
Compound 1 and other ingredients are thoroughly mixed to give a suspension concentrate, and the suspension concentrate is diluted with water to give a dilution of any desired concentration.
Example 6: 60% water dispersible granule
Mixing and crushing the compound 23 and other components, adding water, kneading, adding into a granulator with a 10-100 mesh screen for granulation, drying, and sieving (according to the range of the screen).
Test examples measurement of fungicidal Activity
The diarylamine derivative provided by the invention shows good activity to various germs in the agricultural field, and an activity test method and partial test results are as follows.
In vivo protective activity assay: the living potted plant assay method is adopted. The test compound was dissolved in a small amount of acetone (the volume ratio of acetone to the amount of sprayed solution was equal to 0.05), and diluted to the desired concentration with water containing 0.1% tween 80. Spraying the pesticide on plant test materials, and inoculating diseases after 24 hours. After inoculation, the plants were cultivated in a climatic chamber and after 24 hours the plant specimens were transferred to a greenhouse for cultivation. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week).
The results of the antibacterial activity test of the diarylamine derivative are as follows:
when the concentration of the liquid medicine is 400ppm, the control effect of the compounds 3, 23, 6, 40, 41, 58, 75, 78 and 114 in the list on cucumber downy mildew and tomato late blight reaches 100 percent.
When the concentration of the liquid medicine is 25ppm, the prevention effect of the compounds 23 and 114 in the list on cucumber downy mildew and tomato late blight reaches more than 90 percent; the control effect of the compound 75 on cucumber anthracnose is 100 percent.
The compound has good control effect on important diseases harmful to agricultural production and has wide application prospect.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A diarylamine derivative for use as a fungicide, characterized in that the diarylamine derivative has the following structural formula:
wherein R is1、R2Can be the same or different and is respectively selected from hydrogen, halogen, cyano, C1-C12 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkylamino, C1-C4 alkylthio and C1-C4 alkylsulfonyl;
R3selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkylcarbonyl, halogenated C1-C4 alkylcarbonyl, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl and halogenated C1-C4 alkylsulfonyl;
x is selected from O, S or NR5；
R4Is one or more substituent groups, and is selected from halogen, cyano, NO2Carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
R5selected from hydrogen, C1-C4 alkyl;
the diarylamine derivative does not include a compound A, and the structural formula of the compound A is shown as follows:
2. a diarylamine derivative according to claim 1, wherein R is represented by formula1、R2Can be the same or different and is respectively selected from hydrogen, halogen and cyano;
the R is3Selected from hydrogen, potassium, sodium, calcium, C1-C4 alkyl;
the X is selected from O or NR5；
The R is4Is one or more substituent groups, each independently selected from halogen, cyano, NO2Carboxyl, hydroxyl, C1-C4 alkyl, halogenated C1-C4 alkyl, C1-C4 alkoxy, halogenated C1-C4 alkoxy, C1-C4 alkyl C1-C4 alkoxy, C1-C4 alkoxy C1-C4 alkoxy, C1-C4 alkoxycarbonyl, halogenated C1-C4 alkoxycarbonyl, C1-C4 alkylaminocarbonyl, halogenated C1-C4 alkylaminocarbonyl, C1-C4 alkylsulfonyl, halogenated C1-C4 alkylsulfonyl;
R5selected from hydrogen.
3. A diarylamine derivative according to claim 1, wherein R is represented by formula1、R2Can be the same or different and is respectively selected from H, F, Cl, Br and I;
the R is3Selected from hydrogen, potassium, sodium;
the X is selected from O or NR5；
The R is4Is one or more substituents, each independently selected from fluoro, chloro, bromo or iodo, hydroxy, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methylsulfonyl;
the R is5Selected from hydrogen.
4. A diarylamine derivative according to claim 1, wherein R is represented by formula1、R2Can be the same or different and is respectively selected from H, F, Cl and Br;
the R is3Selected from hydrogen, potassium, sodium;
the X is selected from O or NR5；
The R is4Is one or more substituents, each independentlySelected from the group consisting of fluoro, chloro, bromo, hydroxy, cyano, methyl, ethyl, n-propyl, isopropyl, sec-butyl, tert-butyl, trifluoromethyl, difluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl, methylsulfonyl;
the R is5Selected from hydrogen.
5. A diarylamine derivative according to claim 1, wherein R is represented by formula1、R2Can be the same or different and is respectively selected from H, F, Cl and Br;
the R is3Selected from hydrogen, potassium, sodium;
the X is selected from O or NR5；
The R is4Is one or more substituents each independently selected from fluoro, chloro, bromo, hydroxy, cyano, methyl, ethyl, trifluoromethyl, methoxy, ethoxy, isopropoxy, trifluoromethoxy, carboxy, methoxycarbonyl, ethoxycarbonyl, methylaminocarbonyl;
the R is5Selected from hydrogen.
6. A salt obtained by reacting the diarylamine derivative described in any one of claims 1 to 5 with an acid or a base.
7. Use of a diarylamine derivative according to any one of claims 1 to 5 or a salt according to claim 6 for controlling fungal diseases.
8. Use of a diarylamine derivative according to claim 7 for controlling fungal diseases, characterized in that the fungal diseases include downy mildew, white rust, damping off, pythium rot, epidemic disease, late blight, root rot, damping off, anthracnose, yellow wilt, scab, gray mold, brown spot, black spot, spot blight, early blight, ring spot, rice blast, rust, smut, powdery mildew or sclerotinia.
9. A fungicidal composition containing the diarylamine derivative according to any one of claims 1 to 6 as an active ingredient.
10. The germicidal composition of claim 9, wherein the active ingredients are present in the germicidal composition in an amount ranging from about 0.1% to about 99% by weight.
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| CN202010629681.3A CN113045561B (en) | 2020-07-01 | 2020-07-01 | Diarylamine derivatives as fungicides |
| PCT/CN2021/102896 WO2022001998A1 (en) | 2020-07-01 | 2021-06-29 | Diarylamine derivative used as fungicide |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH610183A5 (en) * | 1971-12-24 | 1979-04-12 | Marktredwitz Chem Fab Ag | Fungicidal composition |
| CN109053693A (en) * | 2018-09-20 | 2018-12-21 | 周银平 | The preparation and its application of pyridazine aminated compounds |
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| DE3614595A1 (en) * | 1986-04-30 | 1987-11-05 | Hoechst Ag | BENZOXAZOLYL AND BENTHIAZOLYLANILINE, METHOD FOR THE PRODUCTION THEREOF AND THEIR USE AS A FUNGICIDE AGENT |
| CZ20011466A3 (en) * | 1998-11-17 | 2001-09-12 | Kumiai Chemical Industry Co., Ltd. | Derivatives of pyrimidinyl benzimidazole, triazinyl benzimidazole, aniline pyrimidine or aniline triazine and agricultural and horticultural fungicidal agents containing thereof |
| EP2398791A1 (en) * | 2009-02-18 | 2011-12-28 | Amgen, Inc | INDOLE/BENZIMIDAZOLE COMPOUNDS AS mTOR KINASE INHIBITORS |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CH610183A5 (en) * | 1971-12-24 | 1979-04-12 | Marktredwitz Chem Fab Ag | Fungicidal composition |
| CN109053693A (en) * | 2018-09-20 | 2018-12-21 | 周银平 | The preparation and its application of pyridazine aminated compounds |
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