CN110804019A - Amide compound and preparation method and application thereof - Google Patents
Amide compound and preparation method and application thereof Download PDFInfo
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- CN110804019A CN110804019A CN201810884462.2A CN201810884462A CN110804019A CN 110804019 A CN110804019 A CN 110804019A CN 201810884462 A CN201810884462 A CN 201810884462A CN 110804019 A CN110804019 A CN 110804019A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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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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Abstract
The amide compound has a structure shown in formula I, has a remarkable effect on preventing and treating diseases in agriculture and forestry, particularly has a good prevention and treatment effect on cucumber powdery mildew, cucumber downy mildew and soybean rust, and has the prevention and treatment effect on the cucumber powdery mildew which is more than or equal to 90% when the concentration of the amide compound is 400ppm and the prevention and treatment effect on the cucumber downy mildew which is more than or equal to 90%; the prevention and treatment effect on soybean rust is more than or equal to 90% when the concentration of the amide compound is 100ppm, and the preparation method is simple, efficient, easy for large-scale production and wide in application prospect.
Description
Technical Field
The invention belongs to the field of agricultural bactericides and relates to an amide compound as well as a preparation method and application thereof.
Background
The growth of plants is seriously affected by plant diseases, which results in the yield reduction of crops and economic loss, so that the development of an effective antibacterial agent against the plant diseases is of great significance.
Amide fungicides are a commonly used class of fungicides, in which the amount of the fungicide is a considerable proportion, which is of interest for their high biological activity, but which are resistant to diseases after a period of use, and there is a continuing need for new and improved compounds and compositions having fungicidal activity.
Alkyl-substituted diphenyl ether pyrazole amides have been reported in the prior art, for example CN103391925A discloses compounds KC1 (i.e. compound 160 in CN 103391925A) and KC2 (i.e. compound 161 in CN 103391925A). These disclosed compounds have bactericidal activity, however, the effect is not good at low doses.
Therefore, in the art, it is desired to develop a more efficient bactericide to meet the needs of agriculture as well as forestry.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide an amide compound and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the present invention provides an amide compound having a structure represented by formula I:
wherein:
r is selected from C1-C6 alkyl or C1-C6 haloalkyl; hal is selected from halogen;
x is selected from C2-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 haloalkoxy, C2-C12 alkenyl, C2-C12 haloalkenyl, C2-C12 alkynyl, C2-C12 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C1-C12 alkylsulfinyl, C1-C12 haloalkylsulfinyl, C1-C12 alkylsulfonyl or C1-C12 haloalkylsulfonyl;
y is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;
w represents an oxygen atom or a sulfur atom.
In the present invention, the halogen is fluorine, chlorine, bromine or iodine.
As a preferred technical scheme of the invention, the amide compound is any one or a combination of at least two of the compounds shown in the following table 1 with the general formula I:
TABLE 1
Wherein F is fluorine atom, Cl is chlorine atom, and Me is methyl.
Preferably, in formula I, R is selected from methyl, ethyl, isopropyl, difluoromethyl, trifluoromethyl or 2-fluoroethyl; x is selected from C2-C12 alkyl; y is selected from C1-C6 alkyl; w represents an oxygen atom; hal is selected from fluorine or chlorine;
further preferably, in formula I, R is selected from difluoromethyl or trifluoromethyl; x is selected from C3-C6 alkyl; y is selected from C1-C3 alkyl; w represents an oxygen atom; hal is selected from fluorine or chlorine.
Most preferably, the amide-based compound is any one or a combination of at least two of the following compounds:
alkyl as used herein refers to straight or branched chain alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like. Haloalkyl refers to a group in which the alkyl group is substituted with one or more halogen atoms. Alkoxy means a group having an oxygen atom attached to the terminal of an alkyl group, such as methoxy, ethoxy, n-propoxy, isopropoxy, t-butoxy, and the like. Haloalkoxy refers to a group in which an alkoxy group is substituted with one or more halogen atoms. Halogen is F, Cl, Br or I.
In the present invention, the term "C1-C6 alkyl" refers to a straight or branched chain alkyl group having 1 to 6 carbon atoms, including, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl, and the like. The term "C1-C6 alkoxy" refers to a straight or branched chain alkoxy group having 1 to 6 carbon atoms, including without limitation methoxy, ethoxy, n-propoxy, isopropoxy, and tert-butoxy groups, and the like. The term "C1-C12 alkyl" has a similar meaning.
In the present invention, the term "C3-C8 cycloalkyl" refers to a cyclic alkyl group having 3 to 8 carbon atoms in the ring, including, without limitation, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
In the present invention, C2-C12, C1-C6, C3-C8 and the like before the specific group indicate the number of carbon atoms contained in the group, for example, C2-C12 indicates a group whose number of carbon atoms may be 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12, C1-C6 indicates a group whose number of carbon atoms may be 1, 2, 3, 4, 5 or 6, C3-C8 indicates a group whose number of carbon atoms may be 3, 4, 5, 6, 7 or 8, C2-C4 indicates a group whose number of carbon atoms may be 2, 3 or 4, and the like.
In another aspect, the present invention provides a method for preparing an amide compound as described above, the method comprising:
reacting a compound shown in a formula II with a compound shown in a formula III to obtain an amide compound shown in a formula I, wherein the reaction formula is as follows:
wherein LG represents a readily leaving group, preferably a chlorine atom, a bromine atom, an alkoxy group or an acyloxy group; hal, R, X, Y and W are as defined above and will not be described in detail herein.
Preferably, the molar ratio of the compound of formula II to the compound of formula III is 0.5-2:1, such as 0.5:1, 0.8:1, 1:1, 1.2:1, 1.5:1, 1.8:1 or 2: 1.
Preferably, the reaction is carried out in the presence of a basic substance, which is an organic base and/or an inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride or a combination of at least two of them.
In the present invention, the basic substance is used in a catalytic amount or a stoichiometric amount or an excess amount with respect to the reaction raw material represented by formula III.
Preferably, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N-dimethylformamide, or dimethyl sulfoxide.
Preferably, the reaction temperature is not less than room temperature and not more than the boiling point of the reaction solvent, such as 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or in the solvent boiling point, i.e. the reflux state reaction.
Preferably, the time of the reaction is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
Preferably, the compound shown in the formula III is prepared by the following method: reducing the compound shown in the formula IV in the presence of a reducing agent to obtain a compound shown in a formula III, wherein the reaction formula is as follows:
wherein X, Y is defined as above and will not be described herein.
Preferably, in the preparation of the compound shown in the formula III, the reducing agent is any one of hydrogen, hydrazine hydrate, iron powder, zinc powder, stannous chloride or sodium hydrosulfite or a combination of at least two of the hydrogen, the hydrazine hydrate, the iron powder, the zinc powder, the stannous chloride or the sodium hydrosulfite.
Preferably, in the preparation of the compound represented by formula III, the reaction is carried out in the presence of a catalyst, preferably any one of palladium carbon, palladium dioxide, raney nickel, ferric chloride or basic iron oxide or a combination of at least two of them.
Preferably, in the preparation of the compound represented by formula III, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N-dimethylformamide acetic acid, hydrochloric acid, water, or dimethyl sulfoxide.
Preferably, in the preparation of the compound represented by formula III, the reaction temperature is greater than or equal to 0 ℃ and less than or equal to the boiling point of the reaction solvent, such as 0 ℃, 3 ℃, 5 ℃, 8 ℃, 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃, or the like, or the reaction is performed under the reflux state of the boiling point of the solvent.
Preferably, in the preparation of the compound of formula III, the reaction time is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
Preferably, the compound shown in the formula IV is prepared by the following method: reacting the compound shown in the formula V with the compound shown in the formula VI to obtain the compound shown in the formula IV, wherein the reaction formula is as follows:
wherein L is a group susceptible to nucleophilic substitution, preferably fluorine or chlorine, and further wherein X, Y is defined as above and will not be described herein in detail.
Preferably, the molar ratio of compound of formula V to compound of formula VI is 1-3:1, such as 1:1, 1.2:1, 1.5:1, 1.8:1, 2:1, 2.2:1, 2.5:1, 2.8:1 or 3: 1.
Preferably, in the preparation of the compound represented by formula IV, the reaction is carried out in the presence of a basic substance, which is an organic base or an inorganic base.
Preferably, the organic base is any one or a combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide.
Preferably, the inorganic base is any one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride or a combination of at least two of them.
Preferably, in the preparation of the compound represented by formula IV, the solvent for the reaction is any one of dichloromethane, chloroform, acetone, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, N-dimethylformamide, dimethyl sulfoxide, or hexamethylphosphoric triamide, or a combination of at least two of them.
Preferably, in the preparation of the compound represented by formula IV, the reaction is carried out at a temperature of not less than the boiling point of the reaction solvent at room temperature, for example, 20 ℃, 25 ℃, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 60 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or the like, or under reflux at the boiling point of the solvent.
Preferably, in the preparation of the compound of formula IV, the reaction time is 0.5 to 48 hours, such as 0.5 hour, 1 hour, 3 hours, 5 hours, 8 hours, 10 hours, 12 hours, 15 hours, 18 hours, 20 hours, 23 hours, 25 hours, 28 hours, 30 hours, 33 hours, 35 hours, 38 hours, 40 hours, 44 hours, or 48 hours.
In the present invention, some of the compounds of formula VI used as starting materials are commercially available reagents, and some of the compounds can be synthesized according to literature, such as j.am. chem. soc.2006,128, 1840-1846.
In another aspect, the invention provides the application of the amide compound in controlling plant diseases.
The amide compound provided by the invention has unexpected high bactericidal activity and good control effect on plant diseases.
In the present invention, the plant diseases include Oomycetes (oomyces), Ascomycetes (Ascomycetes), Basidiomycetes (Basidiomycetes) or Deuteromycetes (deuteromyces) diseases.
Preferably, the plant diseases include, but are not limited to: wheat rust, wheat powdery mildew, wheat scab, wheat root rot, wheat sharp eyespot, wheat take all, wheat glume blight, cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, cucumber fusarium wilt, cucumber gray mold, grape downy mildew, tomato early blight, tomato late blight, rice sheath blight, rice blast, watermelon gummy stem blight, peanut scab, peanut black spot, citrus scab, pepper root rot, cotton verticillium wilt, cotton fusarium wilt, rape black stem disease, rape sclerotinia rot, pear scab, ginseng rust, corn curvularia, corn leaf rot, corn northern leaf blight, mango stem rot, apple ring rot, apple rot, banana leaf spot, soybean rust or potato late blight.
Preferably, the plant disease comprises wheat rust, wheat powdery mildew, wheat scab, wheat sharp eyespot, rice sheath blight, cucumber powdery mildew, cucumber downy mildew, banana leaf spot or soybean rust.
In another aspect, the invention provides a bactericide composition, which comprises an active ingredient and an agriculturally pharmaceutically acceptable carrier, wherein the active ingredient is the amide compound described above.
The bactericide composition can be used in the fields of agriculture, forestry, sanitation and the like.
Preferably, the active ingredient is present in the fungicide composition in an amount of 1 to 99% by weight, such as 1%, 3%, 5%, 8%, 10%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65%, 70%, 75%, 80%, 85%, 90%, 95% or 99%.
Preferably, the agriculturally pharmaceutically acceptable carrier includes a surfactant.
In the present invention, the surfactant is an ionic surfactant or a nonionic surfactant.
The surfactant includes an emulsifier, dispersant or wetting agent. The emulsifier can be polyoxyethylene fatty acid ester, polyoxyethylene fatty alcohol ether, polyoxyethylene fatty ammonia and commercially available emulsifier (Nongru 2201B, Nongru 0203B, Nongru 100#, Nongru 500#, Nongru 600-2#, Nongru 1601, Nongru 2201, Nongru NP-10, Nongru NP-15, Nongru 507#, Nongru OX-635, Nongru OX-622, Nongru OX-653, Nongru OX-667, Ningru 36 #). The dispersant comprises sodium lignosulfonate, nekal, calcium lignosulfonate, methyl naphthalene sulfonic acid formaldehyde condensate and the like. The wetting agent includes sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, etc.
Preferably, the agriculturally pharmaceutically acceptable carrier includes a solid carrier and/or a liquid carrier.
Preferably, the solid support comprises natural or synthetic clays and silicates, such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, montmorillonite and mica; white carbon black, calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine. Liquid carriers include water and organic solvents, which can also be used as adjuvants or antifreeze additives when water is used as a solvent or diluent. Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, and the like; chlorinated hydrocarbons such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, and the like; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light mineral oil; alcohols such as isopropyl alcohol, butyl alcohol, ethylene glycol, glycerin, cyclohexanol, and the like; and ethers and esters thereof; and also ketones, such as acetone, cyclohexanone, and dimethylformamide and N-methyl-pyrrolidone.
The active ingredient may be mixed with a liquid carrier and/or a solid carrier during the formulation of the fungicide composition, with the addition of surfactants (e.g. emulsifiers, dispersants, stabilizers, wetting agents) and with the addition of other adjuvants (e.g. binders, defoamers, oxidizers, etc.).
In another aspect, the present invention provides a method for controlling plant diseases, the method comprising: applying an effective dose of the fungicide composition as described above to a medium in which a plant disease or its growth is to be controlled.
Preferably, the effective dose is from 10 to 1000g per hectare, for example 10g, 20g, 50g, 80g, 100g, 120g, 150g, 180g, 200g, 250g, 300g, 350g, 400g, 450g, 500g, 600g, 700g, 800g, 900g or 1000g, preferably from 20 to 500g per hectare.
The composition of the present invention may be applied in the form of a formulation on the disease or its growth medium. The compound of formula I as an active ingredient is dissolved or dispersed in a carrier or formulated so as to be more easily dispersed when used as a bactericide. For example: the chemical preparation can be prepared into various liquid preparations, missible oil, suspending agents, water suspending agents, micro-emulsions, aqueous emulsions, powders, wettable powders, soluble powders, granules, water dispersible granules or capsules.
For certain applications, for example in agriculture, one or more other fungicides, insecticides, herbicides, plant growth regulators or fertilizers and the like may be added to the fungicidal compositions of the present invention, thereby providing additional advantages and effects.
Compared with the prior art, the invention has the following beneficial effects:
the amide compound with the structure shown in the formula I has a remarkable effect on preventing and treating diseases in agriculture and forestry, particularly has a good effect on preventing and treating powdery mildew of cucumber, cucumber downy mildew, soybean rust, rice sheath blight and potato late blight, and has the effect of preventing and treating the powdery mildew of cucumber of more than or equal to 90% and the effect of preventing and treating the downy mildew of cucumber of more than or equal to 90% when the concentration of the amide compound is 400 ppm; the control effect on soybean rust is more than or equal to 90 percent when the concentration of the amide compound is 100 ppm; and the preparation method is simple and efficient, is easy for large-scale production and has wide application prospect.
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
Preparation of N- (2- (2-isopropyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide (compound 1):
step 1: synthesis of 1-isopropyl-4-methyl-2- (2-nitrophenoxy) benzene:
taking a reaction bottle, adding o-fluoronitrobenzene (commercially available, 70.87mmol, 1.0eq) and potassium carbonate (commercially available, 70.87mmol, 1.0eq) into 60mL of DMF, adding 2-isopropyl-5-methylphenol (commercially available, 77.96mmol, 1.1eq) under reflux, keeping the temperature for reaction for 2-3h, after the reaction is finished, adding 200mL of water, extracting with ethyl acetate, washing an organic layer with saturated saline solution, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain a light yellow oily crude product, namely 1-isopropyl-4-methyl-2- (2-nitrophenoxy) benzene (11.9g, yield of 62 percent), wherein the crude product is directly subjected to the next reaction without separation.
Step 2: synthesis of 2- (2-isopropyl-5-methylphenoxy) aniline:
1-isopropyl-4-methyl-2- (2-nitrophenoxy) benzene (43.86mmol, 1.0eq), ethanol (60mL) and 5% palladium carbon (1.19g) are sequentially added into a reaction bottle, hydrazine hydrate (175.44mmol, 4eq) is slowly added into the system dropwise, reaction is carried out at room temperature for 4 hours, after the reaction is finished, palladium carbon is removed by filtration, water is added into filtrate, ethyl acetate is extracted, an organic layer is washed by saturated saline solution and dried by anhydrous sodium sulfate, concentration is carried out under reduced pressure, and residue is purified by column chromatography (eluent is petroleum ether: ethyl acetate: 25: 1) to obtain a light yellow oily product, namely 2- (2-isopropyl-5-methylphenoxy) aniline (6.03g, yield 57%).
And step 3: synthesis of N- (2- (2-isopropyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide:
to a reaction flask were added 2- (2-isopropyl-5-methylphenoxy) aniline (1.0mmol, 1.0eq), dichloromethane (20mL) and triethylamine (1.20mmol, 1.2eq) in this order, and 1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carbonyl chloride (1.1mmol, 1.1eq) was slowly added dropwise. After reacting at room temperature for 2 hours, the reaction mixture was quenched with water, extracted with dichloromethane, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate 4: 1) to give a yellow oily product (320mg, yield 76.7%).
Process for preparation of Compound 11H NMR(400MHz,CDCl3) The data are as follows (delta ppm])：8.53(dd,J＝8.1,1.6Hz,1H),7.27-7.21(m,2H),7.09(t,JH-F＝56.0Hz,1H),7.08(td,J＝7.8,1.4Hz,1H),6.99(td,J＝7.8,1.7Hz,2H),6.69(d,J＝0.8Hz,1H),6.66(dd,J＝8.1,1.4Hz,1H),3.82(s,3H),3.28-3.13(m,1H),2.27(s,3H),1.23(s,3H),1.21(s,3H)。
Synthesis example 2
Preparation of N- (2- (2-isopropyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-chloro-1H-pyrazole-4-carboxamide (compound 37):
to a reaction flask were added 2- (2-isopropyl-5-methylphenoxy) aniline (1.0mmol, 1.0eq), dichloromethane (20mL) and triethylamine (1.20mmol, 1.2eq) in this order, and 1-methyl-3-difluoromethyl-5-chloro-1H-pyrazole-4-carbonyl chloride (1.1mmol, 1.1eq) was slowly added dropwise. After reacting at room temperature for 2 hours, the reaction mixture was quenched with water, extracted with dichloromethane, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate 4: 1) to give a yellow oily product (300mg, yield 69.3%).
Process for preparation of compound 371H NMR(500MHz,CDCl3) The data are as follows (delta ppm])：8.94(s,1H),8.59(dd,J＝8.1,1.4Hz,1H),7.29(s,1H),7.22(t,JH-F＝54.1Hz,1H),7.15-7.08(m,1H),7.05-6.99(m,2H),6.75-6.66(m,2H),3.95(s,3H),3.29-3.19(m,1H),2.29(s,3H),1.24(s,3H),1.23(s,3H)。
Example 3
Preparation of N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide (compound 2):
step 1: synthesis of 1-tert-butyl-4-methyl-2- (2-nitrophenoxy) benzene:
a reaction flask was taken, o-fluoronitrobenzene (commercially available, 70.87mmol, 1.0eq) and potassium carbonate (commercially available, 70.87mmol, 1.0eq) were dissolved in 60mL of DMF, 2- (tert-butyl) -5-methylphenol (commercially available, 77.96mmol, 1.1eq) were added under reflux, the temperature was maintained for reaction for 2-3h, after completion of the reaction, 200mL of water was added, extraction was performed with ethyl acetate, and the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and concentrated under reduced pressure to give a crude product, 1-tert-butyl-4-methyl-2- (2-nitrophenoxy) benzene, as a brown oil (18.2g, yield 90%).
Step 2: synthesis of 2- (2-tert-butyl-5-methylphenoxy) aniline:
1-tert-butyl-4-methyl-2- (2-nitrophenoxy) benzene (63.78mmol, 1.0eq), ethanol (60mL), and 5% palladium on carbon (1.82g) were sequentially added to a reaction flask, hydrazine hydrate (255.14mmol, 4eq) was slowly added dropwise to the system, the reaction was carried out at room temperature for 4 hours, after completion of the reaction, palladium on carbon was removed by filtration, the reaction was quenched with water, ethyl acetate was extracted, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent was petroleum ether: ethyl acetate 10: 1) to give 2- (2- (tert-butyl) -5-methylphenoxy) aniline as a pale brown oily product (13.03g, yield 80%).
And step 3: synthesis of N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carboxamide:
2- (2-tert-butyl-5-methylphenoxy) aniline (1.96mmol, 1.0eq), dichloromethane (20mL), triethylamine (2.08mmol, 1.06eq) were added to a reaction flask in this order, and 1-methyl-3-difluoromethyl-5-fluoro-1H-pyrazole-4-carbonyl chloride (2.06mmol, 1.05eq) was slowly added dropwise. After reacting at room temperature for 2 hours, the reaction mixture was quenched with water, extracted with dichloromethane, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate 4: 1) to give N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-trifluoromethyl-1H-pyrazole-4-carboxamide (625mg, yield 73.9%) as an off-white solid.
Process for preparation of Compound 21H NMR (400MHz, DMSO) data are as follows (. delta. [ ppm. [ DMSO ]])：9.16(s,1H),8.11(s,1H),7.28(d,J＝7.1Hz,1H),7.17(t,JH-F＝53.44Hz,1H),7.12(s,2H),6.92(d,J＝7.2Hz,1H),6.71(s,1H),6.58(s,1H),3.78(s,3H),2.18(s,3H),1.35(s,9H)。
Examples4
Preparation of N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-chloro-1H-pyrazole-4-carboxamide (compound 38):
2- (2-tert-butyl-5-methylphenoxy) aniline (1.96mmol, 1.0eq), dichloromethane (20mL), triethylamine (2.08mmol, 1.06eq) were added to a reaction flask in this order, and 1-methyl-3-difluoromethyl-5-chloro-1H-pyrazole-4-carbonyl chloride (2.06mmol, 1.05eq) was slowly added dropwise. After reacting at room temperature for 2 hours, the reaction mixture was quenched with water, extracted with dichloromethane, the organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and the residue was purified by column chromatography (eluent: petroleum ether: ethyl acetate 4: 1) to give N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-difluoromethyl-5-chloro-1H-pyrazole-4-carboxamide as an off-white solid (600mg, yield 68.3%).
Process for preparation of Compound 381H NMR (400MHz, DMSO) data are as follows (. delta. [ ppm. [ DMSO ]])：9.43(s,1H),8.15-8.07(m,1H),7.27(d,J＝8.0Hz,1H),7.20(t,JH-F＝54.0Hz,1H),7.16-7.12(m,2H),6.91(dd,J＝8.0,1.1Hz,1H),6.74-6.69(m,1H),6.56(s,1H),3.89(s,3H),2.17(s,3H),1.35(s,9H)。
Example 5
Preparation of N- (2- (2-tert-butyl-5-methylphenoxy) phenyl) -1-methyl-3-ethyl-5-chloro-1H-pyrazole-4-carboxamide (compound 60):
compound 60 was synthesized according to the procedure of example 1.
Process for preparation of Compound 601H NMR(400MHz,CDCl3) The data are as follows (delta ppm])：8.74(s,1H),8.61(dd,J＝8.2,1.6Hz,1H),7.24(d,J＝7.9Hz,1H),7.09(td,J＝8.0,1.3Hz,1H),7.04-6.91(m,2H),6.69(d,J＝1.4Hz,1H),6.67(d,J＝1.2Hz,1H),3.81(s,3H),3.30-3.17(m,1H),2.97(q,J＝7.5Hz,2H),2.26(s,3H),1.28(t,J＝7.5Hz,3H),1.23(s,3H),1.21(s,3H)。
Other compounds can be prepared by similar methods by selecting different starting materials.
Example 6
In this example, a bactericide composition was prepared from the prepared amide-based compound, and a suspension concentrate having a concentration of compound 1 of 30%, an aqueous suspension concentrate having a concentration of compound 2 of 30%, and an emulsifiable concentrate having a concentration of compound 38 of 30% were prepared in the following mass ratio, the formula of the bactericide composition of compound 1 is shown in table 1 below, the formula of the bactericide composition of compound 2 is shown in table 3 below, and the formula of the bactericide composition of compound 38 is shown in table 4 below.
TABLE 2
| Compound 1 | 30％ |
| Ethylene glycol | 10％ |
| Polyoxyethylene nonyl phenol ethers | 6％ |
| Lignosulfonic acid sodium salt | 10％ |
| Carboxymethyl cellulose | 1％ |
| 37% aqueous formaldehyde solution | 0.2％ |
| 75% silicon oil aqueous solution | 0.8％ |
| Water (W) | Make up to 100% |
The preparation method comprises the following steps: compound 1 and other components were mixed thoroughly, thus obtaining a 30% suspension. And diluting the resulting suspension with water to give a dilution of any desired concentration.
TABLE 3
| Compound 2 | 30％ |
| Sodium dodecyl naphthalene sulfonate | 4％ |
| Hemicellulose | 3％ |
| Propylene oxide | 8％ |
| Water (W) | Make up to 100% |
The preparation method comprises the following steps: firstly, compound 2, 80 percent of the added water and sodium dodecyl sulfate are crushed in a ball mill, then hemicellulose and propylene oxide are dissolved in the rest 20 percent of water, and finally the crushed substances are stirred and added to obtain 30 percent aqueous suspension.
A 30% strength emulsifiable concentrate of compound 38 was prepared according to the formulation shown in table 4.
TABLE 4
| Compound 38 | 30％ |
| Phosphorous acid | 10％ |
| Ethoxylated triglycerides | 15％ |
| Toluene | Make up to 100% |
The preparation method comprises the following steps: dissolving the phosphorous acid in toluene, adding the compound 38 and the ethoxylated triglyceride to obtain a transparent solution, namely the 30% missible oil.
Example 7
In this example, the effect of the prepared amide compound on controlling cucumber powdery mildew (erysiphe cichororaceae) was measured by the following method:
the screening adopts a living potted plant determination method, i.e. a compound sample to be detected is dissolved by a small amount of solvent (the types of the solvent such as acetone, methanol, DMF, and the like are selected according to the dissolving capacity of the solvent on the sample, the volume ratio of the solvent amount to the liquid spraying amount is equal to or less than 0.05), and the solution to be detected with the required concentration is prepared by diluting the solution with water containing 0.1 percent of Tween 80. Greenhouse-cultured two-leaf-stage cucumber seedlings were used as test host plants for cucumber powdery mildew (Erysiphe cichororaceae). Foliar spray treatments were carried out with the compounds of the present invention at the designed concentrations. Additionally arranging a blank control sprayed with clear water, repeating for 3 times, and performing germ inoculation after 24h after treatment. After inoculation, the plants are placed in a climatic chamber for humid cultivation (temperature: 25 ℃ day, 20 ℃ night, relative humidity: 95-99%). After the test material was cultured for 24 hours, the greenhouse culture was transferred. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week). The results were examined with reference to the American society for plant diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
The control effect (namely the inhibition rate on the cucumber powdery mildew) of the compound 2 on the cucumber powdery mildew is more than or equal to 90 percent when the concentration of the compound is 400 ppm.
Example 8
In this example, the effect of the prepared amide-based compound on controlling cucumber downy mildew (Pseudoperonospora cubensis) was measured as follows:
the screening adopts a living potted plant determination method, i.e. a compound sample to be detected is dissolved by a small amount of solvent (the types of the solvent such as acetone, methanol, DMF, and the like are selected according to the dissolving capacity of the solvent on the sample, the volume ratio of the solvent amount to the liquid spraying amount is equal to or less than 0.05), and the solution to be detected with the required concentration is prepared by diluting the solution with water containing 0.1 percent of Tween 80. Two-leaf-stage cucumber seedlings cultivated in a greenhouse were used as test host plants for cucumber downy mildew (Pseudoperonospora cubensis). Foliar spray treatments were carried out with the compounds of the present invention at the designed concentrations. Additionally arranging a blank control sprayed with clear water, repeating for 3 times, and performing germ inoculation after 24h after treatment. After inoculation, the plants are placed in a climatic chamber for humid cultivation (temperature: 25 ℃ day, 20 ℃ night, relative humidity: 95-99%). After the test material was cultured for 24 hours, the greenhouse culture was transferred. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week). The results were examined with reference to the American society for plant Diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
The control effect (namely the inhibition rate on cucumber downy mildew) of the compound 1 on cucumber downy mildew is more than or equal to 90 percent when the concentration is 400 ppm.
Example 9
In this example, the effect of the prepared amide compound on controlling soybean rust (phakopsorappaphyrizi) is determined as follows:
the screening adopts a living potted plant determination method, i.e. a compound sample to be detected is dissolved by a small amount of solvent (the types of the solvent such as acetone, methanol, DMF, and the like are selected according to the dissolving capacity of the solvent on the sample, the volume ratio of the solvent amount to the liquid spraying amount is equal to or less than 0.05), and the solution to be detected with the required concentration is prepared by diluting the solution with water containing 0.1 percent of Tween 80. Two-leaf stage soybeans were greenhouse-cultured as test host plants for soybean rust (Phakopsora pachyrhizi). Foliar spray treatments were carried out with the compounds of the present invention at the designed concentrations. Additionally arranging a blank control sprayed with clear water, repeating for 3 times, and performing germ inoculation after 24h after treatment. After inoculation, the plants are placed in a climatic chamber for humid cultivation (temperature: 25 ℃ day, 20 ℃ night, relative humidity: 95-99%). After the test material was cultured for 24 hours, the greenhouse culture was transferred. The compound disease control effect evaluation is carried out after the control is sufficiently ill (usually, one week). The results were examined with reference to the American society for plant diseases, A Manual of Association, expressed as 100-0, with "100" representing no disease and "0" representing the most severe degree of disease.
The control effect (namely the inhibition rate on soybean rust) of the compounds 1, 2, 37 and 38 on soybean rust is more than or equal to 90 percent when the concentration is 100 ppm.
According to the method, a part of the compound is selected to be subjected to parallel measurement of the soybean rust prevention activity with the existing compounds KC1 and KC 2. The test results are shown in Table 5.
Table 5: comparison of the Effect of some of the Compounds of the invention against Soybean Rust control with control Compounds
The activity comparison data in table 5 shows that the activity of the compound of the invention is obviously superior to the compounds KC1 and KC2, and the compound has excellent plant disease control effect.
The present invention is illustrated by the above examples, but the present invention is not limited to the above examples, i.e., it is not intended that the present invention be implemented by relying on the above examples. It should be understood by those skilled in the art that any modification of the present invention, equivalent substitutions of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An amide compound, wherein the amide compound has a structure represented by formula I:
wherein:
r is selected from C1-C6 alkyl or C1-C6 haloalkyl; hal is selected from halogen;
x is selected from C2-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 haloalkoxy, C2-C12 alkenyl, C2-C12 haloalkenyl, C2-C12 alkynyl, C2-C12 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C1-C12 alkylsulfinyl, C1-C12 haloalkylsulfinyl, C1-C12 alkylsulfonyl or C1-C12 haloalkylsulfonyl;
y is selected from C1-C6 alkyl, C1-C6 haloalkyl, C1-C6 alkoxy, C1-C6 haloalkoxy, C2-C4 alkenyl, C2-C4 haloalkenyl, C2-C4 alkynyl, C2-C4 haloalkynyl, C3-C8 cycloalkyl, C3-C8 halocycloalkyl, C1-C6 alkylsulfinyl, C1-C6 haloalkylsulfinyl, C1-C6 alkylsulfonyl or C1-C6 haloalkylsulfonyl;
w represents an oxygen atom or a sulfur atom.
2. The amide-based compound according to claim 1, wherein in formula I, R is selected from methyl, ethyl, isopropyl, difluoromethyl, trifluoromethyl or 2-fluoroethyl; x is selected from C2-C12 alkyl; y is selected from C1-C6 alkyl; w represents an oxygen atom; hal is selected from fluorine or chlorine;
preferably, in formula I, R is selected from difluoromethyl or trifluoromethyl; x is selected from C3-C6 alkyl; y is selected from C1-C6 alkyl; w represents an oxygen atom; hal is selected from fluorine or chlorine.
3. The amide-based compound according to claim 1 or 2, wherein the amide-based compound is any one of or a combination of at least two of the following compounds:
4. the method for preparing amide compounds according to any one of claims 1 to 3, characterized in that the method comprises:
reacting a compound shown in a formula II with a compound shown in a formula III to obtain an amide compound shown in a formula I, wherein the reaction formula is as follows:
wherein LG represents a readily leaving group, preferably a chlorine atom, a bromine atom, an alkoxy group or an acyloxy group.
5. The preparation method according to claim 4, wherein the molar ratio of the compound represented by the formula II to the compound represented by the formula III is 0.5-2: 1;
preferably, the reaction is carried out in the presence of a basic substance, which is an organic base and/or an inorganic base;
preferably, the organic base is any one or a combination of at least two of triethylamine, N-diisopropylethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide;
preferably, the inorganic base is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride;
preferably, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N-dimethylformamide, dimethyl sulfoxide and the like;
preferably, the temperature of the reaction is equal to or higher than room temperature and equal to or lower than the boiling point of the reaction solvent;
preferably, the reaction time is 0.5 to 48 hours.
6. The preparation method according to claim 4 or 5, wherein the compound represented by the formula III is prepared by the following method: reducing the compound shown in the formula IV in the presence of a reducing agent to obtain a compound shown in a formula III, wherein the reaction formula is as follows:
preferably, in the preparation of the compound shown in the formula III, the reducing agent is any one or a combination of at least two of hydrogen, hydrazine hydrate, iron powder, zinc powder, stannous chloride or sodium hydrosulfite;
preferably, in the preparation of the compound shown in the formula III, the reaction is carried out in the presence of a catalyst, wherein the catalyst is preferably any one or a combination of at least two of palladium carbon, palladium dioxide, Raney nickel, ferric trichloride or basic ferric oxide;
preferably, in the preparation of the compound represented by the formula III, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, ethyl acetate, toluene, acetonitrile, tetrahydrofuran, dioxane, ethanol, methanol, N-dimethylformamide acetic acid, hydrochloric acid, water or dimethyl sulfoxide;
preferably, in the preparation of the compound shown in the formula III, the reaction temperature is greater than or equal to 0 ℃ and less than or equal to the boiling point of a reaction solvent;
preferably, in the preparation of the compound represented by formula III, the reaction time is 0.5 to 48 hours.
7. The preparation method according to any one of claims 4 to 6, wherein the compound represented by formula IV is prepared by the following method: reacting the compound shown in the formula V with the compound shown in the formula VI to obtain the compound shown in the formula IV, wherein the reaction formula is as follows:
wherein L is a group susceptible to nucleophilic substitution, preferably fluorine or chlorine;
preferably, the molar ratio of the compound shown as the formula V to the compound shown as the formula VI is 1-3: 1;
preferably, in the preparation of the compound represented by formula IV, the reaction is carried out in the presence of a basic substance, which is an organic base or an inorganic base;
preferably, the organic base is any one or combination of at least two of triethylamine, N-dimethylaniline, pyridine, sodium methoxide, sodium ethoxide, sodium tert-butoxide or potassium tert-butoxide;
preferably, the inorganic base is any one or a combination of at least two of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate or sodium hydride;
preferably, in the preparation of the compound represented by formula IV, the solvent for the reaction is any one or a combination of at least two of dichloromethane, chloroform, acetone, toluene, acetonitrile, tetrahydrofuran, dioxane, methanol, ethanol, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoric triamide;
preferably, in the preparation of the compound shown in the formula IV, the reaction temperature is equal to or higher than room temperature and equal to or lower than the boiling point of a reaction solvent;
preferably, in the preparation of the compound represented by formula IV, the reaction time is 0.5 to 48 hours.
8. Use of the amide-based compound according to any one of claims 1 to 3 for controlling plant diseases;
preferably, the plant disease comprises an oomycete, ascomycete, basidiomycete or deuteromycete disease.
Preferably, the plant diseases include wheat rust, wheat powdery mildew, wheat scab, wheat root rot, wheat sharp eyespot, wheat take-all, wheat glume blight, cucumber downy mildew, cucumber powdery mildew, cucumber anthracnose, cucumber fusarium wilt, cucumber gray mold, grape downy mildew, tomato early blight, tomato late blight, rice sheath blight, rice blast, watermelon vine blight, peanut scab, peanut black spot, citrus scab, pepper root rot, cotton verticillium wilt, cotton fusarium wilt, rape black stem disease, rape sclerotinia rot, pear scab, ginseng rust disease, corn campylobacter, corn northern leaf blight, mango rot, apple ring rot, apple rot, banana leaf spot, soybean rust or potato late blight, further preferably wheat rust, wheat powdery mildew, wheat scab, wheat sharp eyespot, wheat scab, grape powdery mildew, tomato blight, tomato late blight, tomato rot, tomato late blight, tomato rot, tomato brown spot, orange rot, grape powdery mildew, grape, Rice sheath blight disease, cucumber powdery mildew, cucumber downy mildew, banana leaf spot or soybean rust.
9. A bactericide composition which comprises an active ingredient which is the amide-based compound as claimed in any one of claims 1 to 3 and an agriculturally pharmaceutically acceptable carrier;
preferably, in the bactericide composition, the weight percentage of the active ingredients is 1-99%.
10. A method for controlling plant diseases, characterized in that the method comprises: applying an effective amount of the fungicidal composition of claim 9 to a medium in which control of plant diseases or their growth is desired;
preferably, the effective dose is from 10 to 1000g per hectare, preferably from 20 to 500g per hectare.
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| CN103391925A (en) * | 2010-11-15 | 2013-11-13 | 拜耳知识产权有限责任公司 | 5-halogenopyrazolecarboxamides |
| CN104557709A (en) * | 2013-10-23 | 2015-04-29 | 华中师范大学 | Pyrazole amide compound containing diphenyl ether, and application and pesticide composition of pyrazole amide compound |
| CN106336380A (en) * | 2015-07-07 | 2017-01-18 | 浙江省化工研究院有限公司 | Diphenyl ether structure-containing pyrazolecarboxamide compound and its preparation method and use |
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| CN1226244A (en) * | 1996-07-24 | 1999-08-18 | 拜尔公司 | Carbanilides used as pesticides |
| CN103391925A (en) * | 2010-11-15 | 2013-11-13 | 拜耳知识产权有限责任公司 | 5-halogenopyrazolecarboxamides |
| CN104557709A (en) * | 2013-10-23 | 2015-04-29 | 华中师范大学 | Pyrazole amide compound containing diphenyl ether, and application and pesticide composition of pyrazole amide compound |
| CN106336380A (en) * | 2015-07-07 | 2017-01-18 | 浙江省化工研究院有限公司 | Diphenyl ether structure-containing pyrazolecarboxamide compound and its preparation method and use |
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| CN116003322A (en) * | 2021-07-13 | 2023-04-25 | 南通泰禾化工股份有限公司 | Pyrazole ether compound as well as preparation method and application thereof |
| CN116003322B (en) * | 2021-07-13 | 2024-05-31 | 南通泰禾化工股份有限公司 | Pyrazole ether compound as well as preparation method and application thereof |
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