CN115925681A - Pyrazole amide compounds, preparation thereof and application thereof as pesticides and bactericides - Google Patents
Pyrazole amide compounds, preparation thereof and application thereof as pesticides and bactericides Download PDFInfo
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- CN115925681A CN115925681A CN202210425135.7A CN202210425135A CN115925681A CN 115925681 A CN115925681 A CN 115925681A CN 202210425135 A CN202210425135 A CN 202210425135A CN 115925681 A CN115925681 A CN 115925681A
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- -1 Pyrazole amide compounds Chemical class 0.000 title claims abstract description 29
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 21
- 239000003899 bactericide agent Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims description 32
- 239000000575 pesticide Substances 0.000 title claims description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 69
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- 239000000126 substance Substances 0.000 claims abstract description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 33
- 238000006243 chemical reaction Methods 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 29
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
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- CTSLXHKWHWQRSH-UHFFFAOYSA-N oxalyl chloride Chemical compound ClC(=O)C(Cl)=O CTSLXHKWHWQRSH-UHFFFAOYSA-N 0.000 claims description 16
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- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
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- 239000011734 sodium Substances 0.000 description 1
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- PYODKQIVQIVELM-UHFFFAOYSA-M sodium;2,3-bis(2-methylpropyl)naphthalene-1-sulfonate Chemical compound [Na+].C1=CC=C2C(S([O-])(=O)=O)=C(CC(C)C)C(CC(C)C)=CC2=C1 PYODKQIVQIVELM-UHFFFAOYSA-M 0.000 description 1
- JHYCSFCFGILRSJ-UHFFFAOYSA-M sodium;benzenesulfonate;formaldehyde Chemical compound [Na+].O=C.[O-]S(=O)(=O)C1=CC=CC=C1 JHYCSFCFGILRSJ-UHFFFAOYSA-M 0.000 description 1
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Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/55—Design of synthesis routes, e.g. reducing the use of auxiliary or protecting groups
Abstract
A pyrazole amide compound of phenoxypyridine ethylamine has a chemical structural formula shown in formula I and formula II:
Description
Technical Field
The invention belongs to the technical field of agricultural chemistry, and relates to an N- (1- (6-phenoxypyridine-3-yl) ethyl) pyrazole amide compound, a preparation method thereof and application thereof as a pesticide and a bactericide.
Background
The pyrazole amide compound shows excellent biological performance of pesticides and plays an important role in pesticides. For example, tolfenpyrad has good control effect on diamond back moth and eggplant thrips on cruciferous vegetables. Fluxapyroxad is used for preventing and treating main diseases of grains, soybeans, corns, rapes, fruit trees, vegetables, sugar beets, peanuts, cotton, lawns, special crops and the like, such as diseases of the grains, the soybeans, the fruit trees and the vegetables caused by septoria, botrytis cinerea, powdery mildew, cercospora, puccinia, rhizoctonia, sclerotinia and the like, gray mold, rust disease and powdery mildew of leguminous plants, cotton rhizoctonia solani, diseases of sunflowers and oilseed rape caused by alternaria and the like. However, the compounds still have the problems of narrow activity spectrum, high toxicity and the like, such as little effectiveness of tolfenpyrad on homoptera and hemiptera main pests, but high toxicity on aquatic organisms. Therefore, the expansion of the activity spectrum of the compounds and the reduction of the toxicity risk have important significance for the expansion of the application range of the compounds.
Disclosure of Invention
In order to overcome the problems of narrow activity spectrum, high toxicity and the like of the existing pyrazole amide compounds, the invention discloses a class of pyrazole amide compounds of phenoxypyridylethylamine based on the principle of biological isostere and in view of the same importance of pyridine heterocycles in pesticides, and the pyrazole amide compounds have excellent insecticidal or bactericidal activity and can be used as agricultural insecticides or bactericides.
The invention provides a first aspect of N- (1- (6-phenoxypyridine-3-yl) ethyl) pyrazole amide compound, which has a structural general formula shown in formulas I and II:
in the formulas I and II, R = H, halogen, C1-C4 alkyl, methoxy, trifluoromethyl, trifluoromethoxy and methylthio;
in the formulas I and II, the halogen represented by R is F, cl or Br;
in the formulas I and II, the C1-C4 alkyl represented by R is methyl, ethyl, isopropyl or tert-butyl;
the binding site of m =0-5,R is at least one of the remaining 5 binding sites.
The compounds of formulae I and II according to the present invention may in particular be selected from the following numbered compounds:
the invention of the 2 nd aspect provides a preparation method of the above N- (1- (6-phenoxypyridin-3-yl) ethyl) pyrazole amide compound (compounds represented by formulas I and II), comprising the following steps: reacting the compound shown in the formula III or the formula IV with the compound shown in the formula V to obtain the compound shown in the formula I and the compound shown in the formula II respectively.
In the formula V, R is defined as formula I and formula II, and in the preparation method, the molar ratio of formula III or formula IV to formula V is 1.2:1; the reaction temperature is-5 to 30 ℃, and the reaction time is 2 to 36 hours; the acid-binding agent is triethylamine or pyridine; the organic solvent is dichloromethane.
The reaction is carried out according to the following steps: dissolving the compound shown in the formula V in an organic solvent, adding an acid binding agent, stirring, dropwise adding a diluted solution shown in the formula III or IV, reacting for 3-18h at-5-50 ℃, adding water after the reaction is completely monitored by a point plate, extracting for multiple times by using a dichloromethane solution, combining dichloromethane layers of organic layers, washing the organic layers by using saturated sodium chloride, drying the organic layers by using anhydrous sodium sulfate, carrying out suction filtration, removing the solvent by pressure reduction, and carrying out chromatography purification on residues by using a 100-200-mesh silica gel column to obtain the compound shown in the formula V.
In the preparation method, the compounds shown in the formulas III and IV are prepared according to the following method: dissolving the formula VI or the formula VII in an organic solvent, carrying out ice bath, slowly dropwise adding oxalyl chloride, adding a catalyst, and reacting to obtain the formula III or the formula IV.
In the above preparation method, the molar ratio of formula VI or formula VII to oxalyl chloride is 1:1.1-2; the reaction temperature is-10-5 ℃, and the reaction time is 1-12h; the catalyst is N, N-dimethylformamide; the organic solvent is dichloromethane.
The formulas VI and VII are all commercially available.
The reaction is carried out according to the following steps: dissolving the formula VI or the formula VII in dichloromethane, carrying out ice-water bath, reducing the temperature to zero, dripping 2 drops of N, N-Dimethylformamide (DMF), slowly dripping oxalyl chloride solution, slowly heating to room temperature after dripping is finished, and stirring at room temperature for 2 hours; after the reaction is completely monitored by a dot plate, the reaction solution is firstly concentrated under reduced pressure, and redundant oxalyl chloride solution and dichloromethane are removed to obtain the compound shown in the formula III or the formula IV.
In the preparation method, the compound shown in the formula V is prepared by the following method: dissolving the formula VIII in an organic solvent, adding a reducing agent and concentrated hydrochloric acid, stirring, and reacting completely to obtain a compound of a formula V.
In the formula VIII, R is defined as the formula I and the formula II, and in the preparation method, the molar ratio of the formula VIII to the reducing agent is 1:2; the reaction temperature is-5-30 ℃, and the reaction time is 2-36h; the organic solvent is a mixed solvent of ethanol or methanol and water.
The reaction is carried out according to the following steps: adding the formula VIII into a mixed solvent of ethanol and water, stirring, sequentially adding zinc powder and concentrated hydrochloric acid, reacting at room temperature, monitoring the reaction by a point plate, adjusting the pH value to be more than 7, filtering, extracting by ethyl acetate, and concentrating to obtain the compound shown in the formula V.
In the preparation method, the compound shown as the formula VIII is prepared according to the following method: dissolving the compound in the formula IX in an organic solvent, adding hydroxylamine hydrochloride while stirring, carrying out reflux reaction, and carrying out treatment after the reaction is finished to obtain the compound in the formula VIII.
In the formula VIIII, R is defined as formula I and formula II, and in the preparation method, the molar ratio of the compound in the formula IX to the hydroxylamine hydrochloride is 1:1.05; the reaction temperature is 20-100 ℃, and the reaction time is 2-36h; the organic solvent is a mixed solvent of ethanol or methanol and water.
The reaction is carried out according to the following steps: adding the compound shown in the formula VIII into a mixed solvent of ethanol and water, stirring, adding hydroxylamine hydrochloride, carrying out reflux reaction, pouring a reaction solution into ice water after the reaction is completely monitored by a point plate, standing, precipitating a white solid, and carrying out suction filtration to obtain the compound shown in the formula VIII.
The invention provides a bactericide and/or insecticide composition and a preparation method thereof, wherein the composition comprises an N- (1- (6-phenoxypyridin-3-yl) ethyl) pyrazole amide compound (a compound shown in a formula I or a formula II) and an agriculturally acceptable carrier, wherein the weight percentage content of the N- (1- (6-phenoxypyridin-3-yl) ethyl) pyrazole amide compound (an active ingredient) in the composition is 0.1-99%, and specifically 30-60%.
The preparation method of the bactericide and/or insecticide composition provided by the invention comprises the following steps: the N- (1- (6-phenoxypyridine-3-yl) ethyl) pyrazole amide compound (a compound shown in a formula I or a formula II) is mixed with an agriculturally acceptable carrier to prepare the compound.
The N- (1- (6-phenoxypyridine-3-yl) ethyl) pyrazole amide compound can be a single compound or a mixture of several compounds.
The agriculturally acceptable carrier has the following characteristics: 1) Formulated with the active ingredient to facilitate application to the site to be treated, for example: plants, seeds or soil; 2) Is favorable for storage, transportation or operation; 3) And may be a solid or liquid, including a substance that is normally a gas but has been compressed into a liquid. In general, carriers commonly used in formulating pesticidal and fungicidal compositions for agricultural use may be used.
Preferably, the agriculturally acceptable carrier may be selected in particular from a solid carrier and/or a liquid carrier.
The solid carrier is selected from at least one of natural or synthetic silicate, ammonium sulfate, calcium sulfate, aluminum oxide silicate, natural or synthetic resin, polychloroprene, starch, bentonite and wax, wherein the natural or synthetic silicate can be selected from at least one of attapulgite, talc, aluminum silicate, diatomite, mica, montmorillonite and calcium silicate, and the natural or synthetic resin can be selected from at least one of benzofuran resin, styrene polymer (molecular weight is 5-20 ten thousand) and styrene copolymer (such as styrene-butadiene copolymer); the wax may be chosen in particular from beeswax and/or paraffin wax.
The liquid carrier is at least one selected from water, C1-C4 alcohol, C3-C8 ketone, aromatic hydrocarbon, petroleum fraction and C6-C12 chlorinated hydrocarbon, wherein the alcohol can be ethanol and/or ethylene glycol, the ketone can be at least one selected from acetophenone, acetone, methyl ethyl ketone and cyclohexanone, the aromatic hydrocarbon can be at least one selected from benzene, toluene and xylene, the petroleum fraction can be kerosene and/or mineral oil, and the chlorinated hydrocarbon can be at least one selected from carbon tetrachloride, dichloromethane and trichloroethane.
Typically, the fungicide and/or insecticide composition will be processed into a concentrate form and used for shipping, which is diluted by the user prior to application.
Preferably, to facilitate dilution, the fungicide and/or insecticide compositions provided by the present invention may further comprise a surfactant.
The surfactant may be added in an amount acceptable for agricultural fungicides and/or insecticides.
The surfactant is selected from at least one of an emulsifier, a dispersant, a wetting agent and a penetrant.
The emulsifier can be at least one selected from agricultural cream 500# (calcium alkylbenzene sulfonate), agricultural cream 600# phosphate (phenyl phenol polyoxyethylene ether), agricultural cream 700# (alkylphenol formaldehyde resin polyoxyethylene ether), agricultural cream 1600# (phenyl phenol polyoxyethylene polypropylene ether), polyoxyalkylene alkyl aryl ether and ethylene oxide-propylene oxide block copolymer.
The dispersant may be at least one selected from the group consisting of polycarboxylate, lignosulfonate, alkylphenol polyoxyethylene formaldehyde condensate sulfate, calcium alkylbenzene sulfonate, sodium benzene sulfonate formaldehyde condensate, sodium lauryl sulfate, sulfonated castor oil sodium salt, sodium alkylaryl sulfonate, alkylphenol polyoxyethylene pyrimidine, fatty acid polyoxyethylene ester and ester polyoxyethylene pyrimidine.
The wetting agent is selected from at least one of sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, nekal BX, fructus Gleditsiae Abnormalis powder, faeces Bombycis and fructus Sapindi Mukouossi powder.
The penetrating agent can be selected from at least one of siloxane polyoxyethylene ether, alkyl aryl sulfonate, alcohol ether succinate and phenol ether succinate.
Preferably, other adjuvants may be added to the fungicide and/or insecticide composition of the present invention as appropriate.
The addition amount of the other auxiliary agents is acceptable in the agricultural bactericide and/or pesticide.
The other auxiliary agent may be at least one selected from a disintegrant, a defoamer, an antifreeze and a thickener.
The disintegrant is at least one selected from bentonite, urea, ammonium sulfate, aluminum chloride and glucose.
The defoaming agent is at least one selected from silicone oil, silicone compounds, C10-C20 saturated fatty acid compounds and C8-C10 fatty alcohol compounds.
The antifreeze is at least one selected from ethylene glycol, propylene glycol, glycerol and polyethylene glycol.
The thickening agent is selected from at least one of xanthan gum, polyvinyl alcohol and polyethylene glycol.
The bactericide and/or insecticide composition prepared by the invention can be prepared into various dosage forms such as wettable powder, granules, concentrated emulsion, missible oil, suspending agent, aerosol or aerosol by adding corresponding components according to the method known by the technicians in the field.
Meanwhile, the fungicide and/or insecticide composition of the present invention can be applied in an effective amount according to various crops and diseases, and can be applied by foliar spray, seed treatment or soil treatment.
In certain aspects, one or more additional fungicides may be added to the fungicide and/or insecticide compositions of the present invention to provide additional advantages and effects; the compounds of formula I or II may also be used in combination with other fungicides and/or insecticides.
In addition, the application of the compound shown in the formula I or the formula II and the composition thereof in the preparation of plant bactericides and/or insecticides also belongs to the protection scope of the invention.
The compound shown in the formula I or the formula II has broad-spectrum and excellent bactericidal activity, and can be used for preventing and controlling four fungi on various crops: diseases caused by diseases of ascomycetes, basidiomycetes, deuteromycetes and oomycetes. Can obtain good control effect at very low dosage. Meanwhile, the compounds shown in the formula I or the formula II have certain systemic property and can be used as leaf surface and soil bactericides for preventing and treating diseases on various crops. The following diseases can be prevented specifically: pepper phytophthora blight, tomato early blight, tomato late blight, rice blast, wheat leaf spot, apple ring rot, rice sheath blight, rice blast, rice false smut, rice bakanae disease, wheat powdery mildew, rape sclerotinia rot, cucumber downy mildew, cucumber fusarium wilt, cotton rhizoctonia rot, cucumber gray mold, cucumber powdery mildew or apple powdery mildew.
In addition, the compound shown in the formula I or the formula II has better insecticidal and acaricidal activity, and can be used for controlling pests and mites on various crops, such as thysanoptera, homoptera, hemiptera, lepidoptera and the like.
The N- (1- (6-phenoxypyrid-3-yl) ethyl) pyrazole amide compound and the composition containing the same can prevent and control harmful fungi and pests (such as frankliniella occidentalis, plutella xylostella, alfalfa aphid and the like) of plants (such as crops: hot pepper, tomato, rice, wheat, apple, rape, cucumber and the like) under small dose, and have broad-spectrum and excellent sterilization and insecticidal effects.
Detailed Description
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto.
The experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents and materials are commercially available, unless otherwise specified.
The scheme for preparing the compounds shown in formula I and formula II is as follows:
1. the compound of formula I was prepared as follows:
EXAMPLE 1 preparation of Compound III (3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbonyl chloride)
Adding formula VI (3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carboxylic acid) into a 100ml single-neck round-bottom flask, adding 30ml dichloromethane solution, carrying out ice-water bath, cooling to zero, adding N, N-dimethylformamide into the flask by two drops, slowly adding oxalyl chloride solution (6 mmol) dropwise, slowly heating to room temperature after the addition is finished, and stirring for 2 hours at room temperature; after the reaction was monitored by spotting plates to completion, it was concentrated under reduced pressure to remove excess oxalyl chloride solution and dichloromethane to afford formula III.
Example 2 preparation of the Compound of formula VIII
A100 ml round bottom flask was charged with Compound IX (1 mmol), dissolved in ethanol and water (2:1 by volume), stirred and charged with hydroxylamine hydrochloride (1.1 mmol), and the reaction was refluxed and checked by TLC. And pouring the reaction liquid into ice water, standing, precipitating white solid, and performing suction filtration to obtain the compound of the formula VIII.
EXAMPLE 3 preparation of Compound formula V
Adding the compound 2 (1 mmol) into a 100ml round-bottom flask, adding ethanol (20 ml)/water (10 ml) for dissolving, sequentially adding zinc powder (2 mmol) and HCl (5 mmol), reacting at room temperature, and detecting the completion of the reaction by TLC. Adjusting Ph to be more than 7 by using sodium hydroxide solution, and filtering; extraction with ethyl acetate and combination of the organic phases. Drying over anhydrous sodium sulfate, filtering, and concentrating to obtain compound formula V as pale yellow oil.
EXAMPLE 4 preparation of Compound I-3
A100 mL round bottom flask was charged with the compound 1- (6- (p-tolyloxy) pyridin-3-yl) ethyl-1-amine (1 mmol), CH 2 Cl 2 And triethylamine (3 mmol), and the solution is dissolved in CH under the ice bath condition 2 Cl 2 The 3- (difluoromethyl) -1-methyl-1H-pyrazole-4-carbonyl chloride (1.2 mmol) was slowly added dropwise to the reaction mixture, and after the addition, the mixture was stirred at room temperature for 4 hours. TLC detection reaction is finished; 15mL of water, CH 2 Cl 2 Extraction (3X 15 mL). The organic layers were combined. Washing with saturated sodium chloride solution, and drying with anhydrous sodium sulfate; vacuum filtering, concentrating and removing solvent. And (3) carrying out column chromatography separation by using petroleum ether and ethyl acetate as eluent to obtain the target compound I-3.
2. Examples of compositions comprising compounds of formula I or formula II are as follows: (the following components are calculated according to the weight percentage, and the active components are added after being folded in hundred percent)
Example 5 a wettable powder containing 50% of a compound of formula I or formula II was prepared:
the wettable powder comprises the following components: 50% of a compound shown in formula I or formula II, 5% of a dispersant polycarboxylate, 3% of wetting agent lauryl sodium sulfate and 42% of a solid carrier or disintegrant bentonite; the components are mixed according to the proportion to obtain a mixture, and the mixture is subjected to airflow pulverization to obtain the 50% wettable powder.
Example 6 preparation of an emulsifiable concentrate containing 30% of a compound of formula I or formula II:
the missible oil comprises the following components: 30% of a compound shown in formula I or formula II, 12% of an emulsifier polyoxyalkylene alkyl aryl ether, 10% of a penetrant alkyl aryl sulfonate and 48% of liquid carrier cyclohexanone; the components were mixed in the proportions described to give a clear solution of 30% compound.
Example 7 preparation of water dispersible granules containing 60% of a compound of formula I or II:
the water dispersible granule comprises the following components: 70% of a compound shown in formula I or formula II, 3% of a dispersant calcium alkylbenzene sulfonate salt, 3% of a dispersant lignosulfonate, 4% of a wetting agent sodium dodecyl sulfate and 20% of a solid carrier or filler starch; the components are mixed according to the proportion to prepare the water dispersible granule of 70 percent of the compound shown in the formula I or the formula II.
3. And (3) biological activity determination:
example 8 insecticidal Activity assay
A certain mass of the original drug is weighed by a balance (0.001 g), DMF is used for preparing a 1% solution, and then distilled water containing 0.1% Tween-80 is used for diluting to the test concentration for later use.
(1) And (3) measuring the activity of the alfalfa aphids: placing about 30 heads of alfalfa aphid nymphs on broad bean leaf disks, spraying by using a Potter spraying tower, wherein the spraying liquid amount is 2.5ml, placing the treated alfalfa aphid nymphs in an observation room at 20-22 ℃ for culture, investigating the result after 24h, touching the nymph body by using tweezers, and regarding the nymph as a dead aphid without reaction. A blank control without the addition of the drug was also set.
(2) Brown planthopper activity assay: selecting rice seedlings with two cores of leaves, placing the rice seedlings in a culture dish of 6cm for fixation, inoculating 3-year-old primary brown planthopper nymphs, inoculating about 15 nymphs to each dish, performing spray treatment by using a Potter spray tower, wherein the spray liquid amount is 2.5ml, placing the treated rice seedlings in an observation room at 26-28 ℃ for culture, investigating the result after 48 hours, touching the insect body by using tweezers, determining no reaction as dead insects, and additionally arranging a blank control without adding a medicament.
(3) And (3) measuring the activity of the plutella xylostella: soaking folium Raphani in the solution for 10s by soaking method, drying in the shade in a plastic culture dish filled with filter paper, inoculating 10 heads of 2-year diamondback moth larvae in each dish, and placing in an observation room at 22 + -2 deg.C under illumination (16/8 h). Observing 48h after the drug is applied, touching the insect body with a writing brush, regarding no reaction as dead insect, repeating for 3 times, and setting a blank control without adding the drug.
(4) Assay of frankliniella occidentalis activity: by adopting a dipping method, filling 1.5ml of centrifugal tube with each concentration liquid medicine respectively, placing for 4h, then pouring out the liquid medicine, and placing the centrifugal tube on a laboratory bench for drying. Clean cabbage leaves were punched into a leaf dish with a diameter of 1.5cm by a punch, and the dish was immersed in each concentration of the drug solution for 10 seconds. Naturally drying the treated leaf disk stems at room temperature, clamping into centrifuge tubes with corresponding concentration of medicinal liquid by using small forceps, inoculating thrips into each tube for 1 piece, and investigating the result 48h after the medicine is taken. Each tube was repeated 3 times for one repeat, and a blank control without drug was set.
The test results are shown in table 2 below:
TABLE 2 pesticidal Activity of object Compounds I and II (%)
Example 9 measurement of fungicidal Activity
25mg of the new compound was dissolved in 1ml of dimethyl sulfoxide (DMSO) to prepare a mother liquor of 25000 mg/L. Tolfenpyrad and fluxapyroxad (98%) were used as positive controls.
Test targets: sclerotium napellus (sclerotiorum), gibberella zeae (Fusarium graminearum), botrytis cinerea (Botrytis cinerea), pythium aphanidermatum (Pythium aphanidermatum), cotton Rhizoctonia solani (Rhizoctonia solani), rice blast (Pyricularia grisea), cotton wilt (Fusarium oxysporum), phytophthora capsici (Phytophthora capsici), grape Anthracnose (Grape Anthracnose), and rice bakanae (Fusarium fujikururi).
Preparing a culture medium: peeling potato, cutting into small pieces, weighing 200g, wrapping with gauze, adding into 1000mL of boiling deionized water, boiling, decocting with slow fire for 30min, and adding water to 1000mL. Adding agar 20g, stirring with glass rod to dissolve, adding glucose 20g, stirring, adding water 1000mL, packaging in triangular flask, sealing with sterile sealing film, and sterilizing. Placing the triangular flask into an autoclave, adjusting to 121 deg.C, and maintaining for 30min.
Preparation of a culture medium with medicine: and operation in a sterile operating table is required. 50mL of dissolved PDA culture medium is taken out of a triangular flask, 0.1mL of test mother solution is added, the mixture is uniformly shaken and poured into 3 culture dishes, and the medicine carrying plate is obtained after cooling. DMSO solvent was used as a blank control. EC (EC) 50 For the assay, 5 series of gradient concentrations were set and plates were prepared separately.
In-vitro antibacterial activity determination: measuring general sieve and EC by hyphal growth rate method 50 . Sterilizing the sterile operating table for 30min, and sterilizing the puncher and the mushroom cake picking device by using an alcohol lamp. After cooling, the activated pathogens were beaten into 5mm cakes using a punch. Inoculating the prepared fungus cake to the middle of a flat plate with medicine by using a fungus cake picker, and contacting the hyphae with a culture medium. The inoculated plates were incubated in a 25 ℃ incubator and kept dark.
And (4) result investigation: the colony diameter was determined by the cross method. The bacteriostatic activity was calculated by the following formula.
Hypha growth inhibition rate = (control colony growth diameter-treated colony growth diameter)/(control colony growth diameter-0.5) × 100%
The test results are shown in table 3 below:
TABLE 3 fungicidal Activity of Compounds I and II against various pathogenic fungi at a concentration of 50. Mu.g/mL
Industrial applications
The compounds shown in the formulas I and II have broad-spectrum and excellent insecticidal and bactericidal activity, can be used for preventing and controlling agricultural pests such as aphids, plutella xylostella, thrips and the like, and can be used for preventing and controlling diseases caused by ascomycetes, basidiomycetes, deuteromycetes and oomycetes diseases in various crops. The compounds have good control effect under low dosage, and have wide application in the aspects of disinsection and bactericide.
Claims (11)
1. A pyrazole amide compound of phenoxypyridine ethylamine has a chemical structural formula shown in formula I and formula II:
in the formulas I and II, R = H, halogen, C1-C4 alkyl, methoxy, trifluoromethyl, trifluoromethoxy and methylthio;
wherein the halogen is F, cl or Br;
the C1-C4 alkyl is methyl, ethyl, isopropyl or tert-butyl;
the binding site of m =0-5,R is at least one of the remaining 5 binding sites.
2. The synthesis of compounds of formulae I and II according to claim 1, according to the following scheme:
the substituents are defined as in claim 1.
3. The synthesis of compounds of formulae I and II according to claim 2, comprising the following steps:
step 1, preparation of intermediate VIII
Dissolving the intermediate VIIII in an organic solvent, adding hydroxylamine hydrochloride while stirring, carrying out reflux reaction, and obtaining a compound VIII after the reaction is finished; the molar ratio of VIIII to hydroxylamine hydrochloride is 1:1.05; the reaction temperature is 20-100 ℃, and the reaction time is 2-36h; the organic solvent is a mixed solvent of ethanol or methanol and water.
Step 2, preparation of intermediate V
Dissolving the intermediate VIII in an organic solvent, adding a reducing agent and concentrated hydrochloric acid, stirring, and reacting completely to obtain a compound V; the molar ratio of the intermediate VIII to the reducing agent is 1:2; the reaction temperature is-5-30 ℃, and the reaction time is 2-36h; the organic solvent is a mixed solvent of ethanol or methanol and water.
Step 3, preparation of intermediates III and IV
Dissolving a compound VI or VII in an organic solvent, carrying out ice bath, slowly dropwise adding oxalyl chloride, adding a catalyst, and reacting to obtain an intermediate III or IV; the molar ratio of compound VI or VII to oxalyl chloride is 1:1.1-2; the reaction temperature is-10-5 ℃, and the reaction time is 1-12h; the catalyst is N, N-dimethylformamide; the organic solvent is dichloromethane.
Step 4, preparation of target objects I and II
And reacting the intermediate III or IV with the intermediate V to obtain a target object I and a target object II respectively. The molar ratio of the intermediate III or IV to the intermediate V is 1.2:1; the reaction temperature is-5-30 ℃, and the reaction time is 2-36h; the acid-binding agent is triethylamine or pyridine; the organic solvent is dichloromethane.
4. Use of the compounds of formulae I and II according to claim 1 or 2 for the preparation of an agricultural fungicide.
5. Use of a compound according to claim 1 or a pharmaceutical composition containing said compound for the preparation of: 1) A botanical insecticide; 2) A plant fungicide; 3) A plant disease inhibitor.
6. The use according to claim 4, the botanical insecticide is an insecticide that kills homoptera pests and/or lepidoptera pests, the homoptera pests being pests of at least one of the following six families: aphididae, whitefly families, planthopper families, psyllidae families, cicadae families and toriidae families; the lepidoptera pests are noctuidae and/or plutella xylostella;
the target bacteria of the plant bactericide are fungi in ascomycetes, basidiomycetes, oomycetes, deuteromycetes, phycomycetes and/or hyphomycetes;
the diseases are sclerotinia rot of colza, scab of wheat, gray mold of tomato, pythium aphanidermatum of melon and fruit, cotton rhizoctonia solani, rice blast, cotton wilt, phytophthora capsici leonian, grape anthracnose and rice bakanae disease.
7. A botanical pesticide or preparation, the active ingredients of which are compounds shown in formulas I and II in claim 1, wherein the mass percentage of the active ingredients in the botanical pesticide or preparation is 0.01% -99.99%.
8. A plant bactericidal medicine or preparation, the active ingredients of which are compounds shown in formulas I and II in claim 1, wherein the mass percentage of the active ingredients in the plant bactericidal medicine or preparation is 0.01-99.99%.
9. A plant disease inhibitor, the active ingredients of which are compounds shown in formulas I and II in claim 1, wherein the mass percentage of the active ingredients in the plant insecticide drug or preparation is 0.01-99.99%.
10. The method according to claim 9, wherein the concentration of the active ingredient of the plant pesticide, plant bactericide, or plant disease inhibitor applied is 1 to 1000mg/L.
11. A method for controlling plant pests, germs or diseases, which comprises applying the plant pesticide according to claim 6, the plant bactericide according to claim 7 or the plant disease inhibitor according to claim 8 to leaves and/or fruits and/or seeds of a plant.
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|---|---|---|---|---|
| EP0329020A1 (en) * | 1988-02-16 | 1989-08-23 | Mitsubishi Kasei Corporation | Pyrazole derivatives, processes for their manufacture and insecticidal, miticidal and fungicidal compositions containg the derivatives as active ingredients |
| EP0394043A1 (en) * | 1989-04-19 | 1990-10-24 | Sumitomo Chemical Company, Limited | An amide compound and its production and use |
| JPH0421671A (en) * | 1990-05-16 | 1992-01-24 | Mitsubishi Kasei Corp | 4-pyrazolecarboxamides and insecticide and acaricide containing the same as active ingredient |
| EP0891975A1 (en) * | 1996-04-05 | 1999-01-20 | Mitsubishi Chemical Corporation | Pyrazoles and agricultural chemicals containing them as active ingredients |
| WO1999046247A1 (en) * | 1998-03-11 | 1999-09-16 | Mitsubishi Chemical Corporation | Pyrazole compounds and agricultural chemicals containing the same as active ingredient |
| WO2009024342A2 (en) * | 2007-08-23 | 2009-02-26 | Syngenta Participations Ag | Novel microbiocides |
| CN103313973A (en) * | 2010-10-21 | 2013-09-18 | 拜耳知识产权有限责任公司 | N-benzyl heterocyclic carboxamides |
| CN110467599A (en) * | 2019-08-23 | 2019-11-19 | 南通大学 | The preparation and application of the pyrazole amide of the unit containing substituted pyridines |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0329020A1 (en) * | 1988-02-16 | 1989-08-23 | Mitsubishi Kasei Corporation | Pyrazole derivatives, processes for their manufacture and insecticidal, miticidal and fungicidal compositions containg the derivatives as active ingredients |
| EP0394043A1 (en) * | 1989-04-19 | 1990-10-24 | Sumitomo Chemical Company, Limited | An amide compound and its production and use |
| JPH0421671A (en) * | 1990-05-16 | 1992-01-24 | Mitsubishi Kasei Corp | 4-pyrazolecarboxamides and insecticide and acaricide containing the same as active ingredient |
| EP0891975A1 (en) * | 1996-04-05 | 1999-01-20 | Mitsubishi Chemical Corporation | Pyrazoles and agricultural chemicals containing them as active ingredients |
| WO1999046247A1 (en) * | 1998-03-11 | 1999-09-16 | Mitsubishi Chemical Corporation | Pyrazole compounds and agricultural chemicals containing the same as active ingredient |
| WO2009024342A2 (en) * | 2007-08-23 | 2009-02-26 | Syngenta Participations Ag | Novel microbiocides |
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| CN110467599A (en) * | 2019-08-23 | 2019-11-19 | 南通大学 | The preparation and application of the pyrazole amide of the unit containing substituted pyridines |
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