CN106946770B - High-activity imido phenylacetate compound and preparation method and application thereof - Google Patents
High-activity imido phenylacetate compound and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
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- C07D213/64—One oxygen atom attached in position 2 or 6
- C07D213/643—2-Phenoxypyridines; Derivatives thereof
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/02—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests containing liquids as carriers, diluents or solvents
- A01N25/04—Dispersions, emulsions, suspoemulsions, suspension concentrates or gels
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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
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/12—Powders or granules
- A01N25/14—Powders or granules wettable
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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
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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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
- A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
- A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
- A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
- A01N47/24—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing the groups, or; Thio analogues thereof
Abstract
The invention belongs to the field of pesticides, and particularly relates to a high-activity imido phenylacetate compound, and a preparation method and application thereof. The invention aims at the research of novel methoxy acrylate compounds, introduces a pyridine aryl ether structure in the structure, widens the research on the structure of the novel compounds, and discovers the high-activity imido phenylacetate compounds. The compound shows biological activity equivalent to that of azoxystrobin and trifloxystrobin, has better effect on most pathogenic bacteria, has outstanding effect on preventing and treating sclerotinia sclerotiorum, and still has effect under low dosage.
Description
Technical Field
The invention belongs to the field of pesticides, and particularly relates to a high-activity imido phenylacetate compound, and a preparation method and application thereof.
Background
The Strobilurin fungicide is an important fungicide successfully developed by taking a natural product Strobilurin A as a lead compound, has the characteristics of high efficiency, low toxicity, broad spectrum and systemic property, and has the functions of protection, treatment and eradication. The strobilurin fungicide has good activity on almost all fungal diseases such as basidiomycetes, ascomycetes, deuteromycetes and oomycetes, and can prevent and treat rust disease, powdery mildew, downy mildew, rice blast and other diseases of various crops. The strobilurin fungicide is a mitochondrial respiratory chain inhibitor, and is used for inhibiting cytochrome b and c1The electron transfer between the two can prevent the synthesis of cell energy, and further inhibit the mitochondrial respiration, thereby achieving the bacteriostatic action. The characteristics of unique action mechanism, high efficiency, broad spectrum and environmental friendliness make the strobilurin fungicide become an agricultural fungicide variety with high market activity and development potential and also become a research hotspot in the pesticide field.
Almost all large pesticide companies are involved in the development of such compounds. The new compounds with high activity are mainly developed by Shenyang chemical research institute, Zhejiang chemical research institute and other organizations in China, the research of other organizations mainly aims at the compounding of commercialized products, the research of compound compositions tends to be mature, but the research and development of the compounds are still deficient in China, and the development of innovative compounds with high activity is much less and less. In addition, the long-term large-scale unreasonable use of the methoxy acrylic ester bactericide is easy to cause drug resistance of pathogenic bacteria, and the pathogenic bacteria are not sensitive to the bactericide to cause the loss of the drug effect.
Disclosure of Invention
The invention aims to provide a high-activity imido phenylacetate compound and a preparation method and application thereof, and the specific technical scheme is as follows:
the high-activity imido phenylacetic acid ester compound is a compound shown in a formula I,
in the formula I, R1、R2、R3、R4And R5Respectively hydrogen, halogen, nitro, cyano, hydroxyl, amino, substituted amino, acetamido, methyl ketone, substituted oxime benzyl ether and C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy radical, C1-C12Alkylthio radical, C1-C12Alkanesulfonyl group, C1-C12Alkylcarbonyl, benzyloxy, or aryloxy.
The aryloxy group is phenoxy and pyridyloxy.
The preparation method of the high-activity imido phenylacetic acid ester compound comprises the following steps:
1) diethyl malonate reacts with magnesium chloride to obtain diethyl carboxylic acid methyl magnesium chloride, chloronicotinic acid reacts with thionyl chloride to obtain chloronicotinoyl chloride, the diethyl carboxylic acid methyl magnesium chloride reacts with the chloronicotinoyl chloride to obtain a compound shown in a structural formula 1, the compound shown in the structural formula 1 is decomposed by a ketone formula to obtain a compound shown in a structural formula 2, and then the compound is reacted with polysubstituted phenol to obtain a compound shown in an intermediate 1;
2) preparing a compound shown in a structural formula 4 by taking N-hydroxyphthalimide and a compound shown in a structural formula 3 as raw materials, and then reacting the compound with hydrazine hydrate to obtain a compound shown in an intermediate 2;
3) and reacting the intermediate 1 with the intermediate 2 to obtain the compound shown in the formula I.
The application of the high-activity imino phenylacetic acid ester compound in preparing a bactericide.
The active component of the bactericide is the high-activity imino phenylacetic ester compound.
The wettable bactericide powder consists of the following substances in percentage by mass: 40% of the high-activity imino phenylacetic acid ester compound in claim 1, 2% of sodium dodecyl sulfate, 3% of sodium lignosulfonate, 5% of naphthalene sulfonic acid formaldehyde condensate and 50% of light calcium carbonate.
A bactericide suspending agent comprises the following substances in percentage by mass: 50% of the high-activity imido phenylacetic acid ester compound disclosed in claim 1, 10% of ethylene glycol, 6% of nonylphenol polyethylene glycol ether, 10% of sodium lignosulfonate, 1% of carboxymethyl cellulose, 0.2% of aqueous formaldehyde solution with the mass fraction of 37%, 0.8% of aqueous silicone oil emulsion with the mass fraction of 75% and 22% of water.
The bactericide water dispersible granule consists of the following substances in percentage by mass: 45% of the high-activity imino phenylacetic acid ester compound in claim 1, 12% of naphthalene sulfonic acid formaldehyde condensate, 8% of N-methyl-N-oleoyl-sodium taurate, 2% of polyvinylpyrrolidone and 3% of kaolin.
The bactericide composition consists of the following substances in percentage by mass: 20% of the high-activity imino phenylacetic acid ester compound of claim 1, 20% of pyraclostrobin, 20% of dispersant, 0-1% of organic bentonite, 1-5% of polyethylene glycol PEG2000 and 34% -39% of water.
The invention has the beneficial effects that:
the invention aims at the research of novel methoxy acrylate compounds, introduces a pyridine aryl ether structure in the structure, widens the research of the structure of the novel compounds, and discovers a novel methoxy acrylate compound with high activity: imido phenylacetic acid ester compounds. The compound shows biological activity equivalent to that of azoxystrobin and trifloxystrobin, has better effect on most pathogenic bacteria, has outstanding effect on preventing and treating sclerotinia sclerotiorum, and still has effect under low dosage.
Detailed Description
The invention provides a high-activity imido phenylacetate compound, a preparation method and application thereof, and the invention is further described by combining with an embodiment.
In the compounds of the formula I according to the invention R1、R2、R3、R4And R5The substituents are exemplified by, but not limited to, table 1.
In the compound of formula I R1、R2、R3、R4And R5Substituent group
The synthesis route of the imido phenylacetic acid ester compound containing the aryloxypicoline oxime ether structural unit provided by the invention is as follows:
the reaction is carried out in a suitable solvent, such as tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone, methanol, and the like.
Suitable acids may be selected from acetic acid, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, p-toluenesulfonic acid, formic acid, phosphoric acid, and the like.
The reaction temperature is between ice bath and room temperature, typically 0-25 ℃.
The reaction time is from 0.5h to 24h, usually 20 h.
The synthetic route of the intermediate 1 is as follows:
the reaction is carried out in a suitable solvent, such as tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, dimethylsulfoxide, acetone, and the like.
Suitable bases may be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, cesium carbonate, and the like.
Each reaction temperature is between the temperature of ice bath and the boiling point temperature of the solvent, and is usually 0-100 ℃; the reaction times are in the range from 0.5h to 20h, usually from 4 to 8 h.
The synthetic route of intermediate 2 is as follows:
the reaction is carried out in a suitable solvent, such as tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N-dimethylformamide, dimethyl sulfoxide, acetone, methanol, and the like.
Suitable bases may be selected from sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, triethylamine, pyridine, sodium methoxide, sodium ethoxide, potassium tert-butoxide, sodium tert-butoxide, and the like.
Each reaction temperature is between the temperature of ice bath and the boiling point temperature of the solvent, and is usually 0-100 ℃; the reaction times are in the range from 0.5h to 20h, usually from 4 to 8 h.
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.
Example 1: synthesis of Compound Ia
(1) Preparation of pyridine aryl ether methyl ketone (P1)
a) Triethylamine (183.2g, 1.8mol) and diethyl malonate (119g, 0.9mol) were charged in a 2L three-necked flask, and dried toluene (700ml) was added thereto, followed by addition of magnesium chloride (51g, 0.53mol) with stirring. The reaction was stirred at room temperature (25 ℃ C.) for 1.5 h.
b) 6-Chloronicotinic acid (120g, 0.75mol), thionyl chloride (300ml) and dry toluene (200ml) were added to a 1L three-necked flask, and two drops of DMF were added dropwise thereto, followed by heating and refluxing for 2 hours. After cooling slightly, the reflux apparatus was changed to a distillation apparatus, and excess thionyl chloride and the solvent toluene were distilled off. Immediately after completion, heating was stopped, and after cooling, the remaining toluene was evaporated by using a rotary evaporator.
c) Adding a proper amount of dry toluene into the product obtained after distillation in the step b) for dilution, and slowly adding the diluted product into the reaction liquid stirred at room temperature in the step a). Stirring was continued for 40min and then acidified with concentrated HCl solution (261g, 2.32 mol). The toluene layer was rotary evaporated and cooled to yield a pale yellow solid. To this solid was added DMSO (650ml) and water (29ml) exactly. The mixture was heated and maintained at 155 ℃ for 3h, then the heating was stopped, the reaction solution was cooled and poured into 2.5L of cold water, a large amount of off-white solid precipitated, filtered and dried. 94g of the product 6-chloro-3-acetylpyridine is obtained, and the yield is 70.1%.
d) Synthesis of pyridine aryl ether methyl ketone (P1)
A500 ml flask was charged with 6-chloro-3-acetylpyridine (18.7g, 0.12mol), p-cresol (14.26g, 0.132mol) and cesium carbonate (39g, 0.12mol), as well as DMF (300ml) solvent. Heating and refluxing, stopping heating after 1h, and cooling. The reaction solution is poured into excessive water, stirred to separate out solid, and filtered. The crude product was recrystallized from ethyl acetate. Dry, weigh 16g, light yellow crystals, 58.7% yield.
m.p.125-127℃,1H NMR,δ：2.24(s,3H)2.57(s,3H)；7.00(q,1H,J＝0.68Hz)；7.12(m,2H,J＝3.20Hz)；7.40(m,2H,J＝3.24Hz)；8.27(dd,1H,J＝2.48Hz)；8.74(dd,1H,J＝0.67Hz).
(2) Preparation of substituted benzyloxyamines (P2)
Adding a solvent DMF100ml into a 250ml three-neck flask provided with a stirrer and a condenser, adding 16.3g (0.1mol) of N-hydroxyphthalimide, heating, completely dissolving the solid, adding corresponding halogenated alkane according to the mass ratio of 1:1, slowly heating to 60 ℃, reacting for five minutes, adding triethylamine according to the mass ratio of 1:1.1, heating to 60 ℃ under stirring for reaction, detecting that the reaction is complete by a point plate, slowly cooling to room temperature, pouring ice water, precipitating the solid, filtering and drying to obtain the product N-substituted benzyloxy-phthalimide.
A250 mL single-neck flask was charged with a stirrer, 100mL of methanol as a solvent was added, and N-substituted benzyloxyphthalimide (0.1mol) was added thereto and stirred in a mass ratio of 1:1, adding hydrazine hydrate solid dropwise, dissolving completely, generating turbidity again for a moment, detecting that the raw material reaction is finished after 2h, performing suction filtration, and directly using the methanol solution of the product P2 in the next step.
(3) Synthesis of Compound Ia
A250 mL three-necked bottle is filled with a stirrer, 100mL of a methanol solution of P2 is added, the same amount of the pyridine aryl ether methyl ketone (P1) is added, a small amount of acetic acid is added, and the mixture is stirred for 24 hours at room temperature. Detecting the reaction by a point plate until the raw materials are completely reacted, separating by a column, and performing separation by using petroleum ether: ethyl acetate 10:1 as eluent, the product was isolated. Yield 76% as a white solid.
The structure confirmation data is:1H NMR(300MHz,CDCl3)δ8.40(d,J＝1.9Hz,1H),8.02(dd,J＝8.7,2.5Hz,1H),7.58–7.50(m,1H),7.44(dtd,J＝12.7,7.3,1.7Hz,2H),7.29–7.21(m,3H),7.13–7.02(m,2H),6.90(d,J＝8.7Hz,1H),5.17(s,2H),4.08(s,3H),3.87(s,3H),2.41(s,3H),2.22(s,3H).13C NMR(75MHz,CDCl3)δ164.14,162.98,151.83,151.26,149.32,145.19,136.69,135.84,134.14,129.90,129.57,129.02,128.50,128.26,127.39,126.78,120.80,110.56,74.48,63.41,52.51,20.55,11.89.HRMS(ESI)m/z calcd for C25H26N3O5(M+H)+448.1867,found 448.1871.
example 2: synthesis of Compound Ib
(1) Preparation of pyridine aryl ether methyl ketone (P3)
a) Triethylamine (183.2g, 1.8mol) and diethyl malonate (119g, 0.9mol) were charged in a 2L three-necked flask, and dried toluene (700ml) was added thereto, followed by addition of magnesium chloride (51g, 0.53mol) with stirring. The reaction was stirred at room temperature (25 ℃ C.) for 1.5 h.
b) 2-Chloronicotinic acid (120g, 0.75mol), thionyl chloride (300ml) and dry toluene (200ml) were added to a 1L three-necked flask, and two drops of DMF were added dropwise thereto, followed by heating and refluxing for 2 hours. After cooling slightly, the reflux apparatus was changed to a distillation apparatus, and excess thionyl chloride and the solvent toluene were distilled off. Immediately after completion, heating was stopped, and after cooling, the remaining toluene was evaporated by using a rotary evaporator.
c) Adding a proper amount of dry toluene into the product obtained after distillation in the step b) for dilution, and slowly adding the diluted product into the reaction liquid stirred at room temperature in the step a). Stirring was continued for 40min and then acidified with concentrated HCl solution (261g, 2.32 mol). The toluene layer was rotary evaporated and cooled to yield a pale yellow solid. To this solid was added DMSO (650ml) and water (29ml) exactly. Heating the mixture at 155 deg.C for 3h, stopping heating, cooling the reaction solution, pouring into 2.5L cold water to precipitate off-white solid, filtering, and drying. 96g of the product 2-chloro-3-acetylpyridine is obtained, and the yield is 72 percent.
d) Synthesis of pyridine aryl ether methyl ketone (P3)
A500 ml flask was charged with 2-chloro-3-acetylpyridine (18.7g, 0.12mol), o-cresol (14.26g, 0.132mol) and cesium carbonate (39g, 0.12mol), as well as DMF (300ml) solvent. Heating and refluxing, stopping heating after 1h, and cooling. The reaction solution is poured into excessive water, stirred to separate out solid, and filtered. The crude product was recrystallized from ethyl acetate. Dry, weigh 16.8g, white crystals, 62% yield.
m.p.36-37℃,1H NMR(300MHz,CDCl3)δ8.38–8.18(m,2H),7.33(dd,J＝13.7,7.6Hz,2H),7.24(dt,J＝7.4,3.7Hz,1H),7.11(dd,J＝10.4,3.9Hz,2H),2.85(s,3H),2.25(s,3H).
(2) Preparation of substituted benzyloxyamines (P2)
Adding a solvent DMF100ml into a 250ml three-neck flask provided with a stirrer and a condenser, adding 16.3g (0.1mol) of N-hydroxyphthalimide, heating, completely dissolving the solid, adding corresponding halogenated alkane according to the mass ratio of 1:1, slowly heating to 60 ℃, reacting for five minutes, adding triethylamine according to the mass ratio of 1:1.1, heating to 60 ℃ under stirring for reaction, detecting that the reaction is complete by a point plate, slowly cooling to room temperature, pouring ice water, precipitating the solid, filtering and drying to obtain the product N-substituted benzyloxy-phthalimide.
A250 mL single-neck flask was charged with a stirrer, 100mL of methanol as a solvent was added, and N-substituted benzyloxyphthalimide (0.1mol) was added thereto and stirred in a mass ratio of 1:1, adding hydrazine hydrate solid dropwise, dissolving completely, generating turbidity again for a moment, detecting that the raw material reaction is finished after 2h, performing suction filtration, and directly using the methanol solution of the product P2 in the next step.
(3) Synthesis of Compound Ib
A250 mL three-necked bottle is filled with a stirrer, 100mL of a methanol solution of P2 is added, the same amount of the pyridine aryl ether methyl ketone (P3) is added, a small amount of acetic acid is added, and the mixture is stirred for 24 hours at room temperature. Detecting the reaction by a point plate until the raw materials are completely reacted, separating by a column, and performing separation by using petroleum ether: ethyl acetate 10:1 as eluent, the product was isolated. Yield 73%, oily liquid.
The structure confirmation data is:1H NMR(300MHz,CDCl3)δ8.41(d,J＝1.9Hz,1H),8.02(dd,J＝8.7,2.4Hz,1H),7.58–7.49(m,1H),7.49–7.35(m,2H),7.34–7.23(m,4H),7.22–7.06(m,2H),6.89(d,J＝8.7Hz,1H),5.20(s,2H),4.06(s,3H),3.84(s,3H),2.22(s,6H).13C NMR(75MHz,CDCl3)δ163.82,162.95,151.84,151.79,149.35,145.28,136.81,135.90,131.07,130.36,129.69,129.01,128.53,128.33,127.41,126.84,126.62,125.07,121.59,109.99,74.53,63.34,52.43,16.04,11.85.HRMS(ESI)m/z calcd for C25H26N3O5(M+H)+448.1867,found 448.1867.
example 3: determination of biological activity of high-activity imido phenylacetate compound
The indoor bactericidal activity test of the high-activity imido phenylacetic acid ester compounds is carried out by reference to literature methods, and the specific steps are as follows:
(1) preparation of PDA Medium
PDA culture medium (1L deionized water: potato 200 g: agar 20 g: glucose 20g) preparation: cleaning potato, peeling, cutting into small pieces, weighing 1400g, wrapping with two double-layer gauzes, boiling with deionized water, adding wrapped potato, and decocting for 30 min; taking out the potatoes after 30min, slowly adding 140g of agar strips soaked by deionized water, and stirring while boiling until the agar strips are completely dissolved; and (3) completely dissolving the agar strips within about 30min, adding 140g of glucose, uniformly stirring, and adding water to a constant volume of 7L. Subpackaging with conical flask, sealing with sterile culture container, sterilizing with autoclave, maintaining at 121 deg.C for 30min, and taking out.
(2) Liquid medicine preparation
Respectively weighing 20mg of the compound to be detected, the azoxystrobin and the trifloxystrobin by using a ten-thousandth balance, adding the compound to be detected, the azoxystrobin and the trifloxystrobin into a 1ml centrifuge tube, and dissolving the mixture with 5ml DMSO for ultrasonic treatment to prepare a mother solution of 20000 mg/L; sterilizing a super clean bench for 30min, diluting the prepared mother solution into 50mg/L of culture medium with drugs by using a PDA (PDA dextrose agar) culture medium under the aseptic condition of the super clean bench, pouring into culture dishes with 15ml of each dish to obtain a flat plate with the culture medium with drugs; the experiment was set up with a blank control without agent and a DMSO solvent control, each treatment was repeated three times.
(3) Experimental methods
Sterilizing a perforator with a diameter of 5mm by an alcohol lamp on an aseptic super clean bench by adopting a hypha growth rate method, cooling to room temperature, and perforating various activated pathogenic bacteria by the perforator; inoculating the fungus cake to the center of the cooled flat plate with the drug culture medium by using a No. 11 surgical blade, covering the plate with a dish cover, placing the plate in an incubator at 25 ℃ in the dark for culturing, wherein the three are parallel, and taking an average value when counting results.
(4) Investigation and calculation
And (4) inspecting the growth condition of the hyphae of the pathogenic bacteria according to the growth condition of the colonies in the blank control culture dish, and measuring the diameter of each treated colony by a cross method after the colonies in the blank control culture dish fully grow.
The hypha growth inhibition rate calculation formula is as follows:
the hypha growth inhibition ratio (%) × 100% (control colony growth diameter-agent-treated colony growth diameter)/(control colony growth diameter-7)).
In vitro bactericidal activity the results of the in-house bactericidal activity measurements are shown in table 2. At a concentration of 50mg/L, most compounds showed good in vitro bacteriostatic activity against the 7 tested pathogens. Part of the compounds have the highest overall activity on sclerotium napellus (SS) and have the inhibiting activity equivalent to that of the control medicaments of azoxystrobin and trifloxystrobin.
TABLE 2 in vitro fungicidal Activity of part of the target Compounds
Sclerotinia sclerotiorum (Lib.) de bark; BC (Botrytis cinerea); PI ═ Phytophthora infestans (Mont.) De Bary); pythium aphanidermatum (Pythium aphanidermatum); rhizoctonia solani (Rhizoctonia solani); PG ═ Pyricularia grisea (Pyricularia grisea); colletotrichum gloeosporioides (colletotrichum orbicular. (Berk. & ent.))
Determination of EC of target Compounds on Sclerotinia sclerotiorum50In this case, the experimental method was also the colony diameter method. Setting six concentration gradients, calculating the inhibition rate of the target compound on sclerotinia rot of rape under each concentration, and obtaining the EC of the target compound through statistical calculation of IBM SPSSStatics 20 software50The value is obtained. The measurement results are shown in Table 3. As can be seen, the compound I in the general formula is equivalent to azoxystrobin and trifloxystrobin in a biological activity test, and the EC of part of compounds on sclerotium rolfsii50Is better than the similar commercialized azoxystrobin. Due to the positive characteristics of the imido phenylacetic acid ester compound, the imido phenylacetic acid ester compound can powerfully protect crops, horticultural plants, fruits and vegetables and the like, and has very good prevention and treatment effects on diseases caused by germs.
TABLE 3 EC of part of the Compounds on sclerotium of Brassica napus50
| Numbering | EC50(μg·mL-1) | 95% confidence Limit |
| 1 | 0.474 | 0.177-0.915 |
| 4 | 0.853 | 0.398-1.510 |
| 7 | 2.278 | 1.293-3.874 |
| 29 | 3.253 | 1.235-8.896 |
| 30 | 1.441 | 0.754-2.478 |
| 31 | 1.055 | 0.560-1.750 |
| Azoxystrobin | 0.791 | 0.445-1.440 |
Example 4: preparation of Compound 3 wettable powder
The compound 3 wettable powder consists of the following substances in percentage by mass:
the compound and the components are fully mixed and crushed by an ultrafine crusher to obtain a 50 percent wettable powder product.
Example 5: preparation of Compound 33 suspending agent
The compound 33 suspending agent consists of the following substances in percentage by mass:
compound 33 and the components were mixed thoroughly to give a suspension product of 35% compound 33.
Example 6: preparation of Compound 56 aqueous Dispersion
The compound 56 water dispersant comprises the following substances in percentage by mass:
the compound 56 and the components are fully mixed and crushed, and then added with water to be kneaded, and then the mixture is added into a granulator with a 10-100 mesh screen to be granulated, and then the mixture is dried and screened.
Example 7: preparation of compound 35 and pyraclostrobin composition
The compound 35 and the pyraclostrobin composition consist of the following substances in percentage by mass:
and fully mixing the compound 35, the pyraclostrobin and the components to obtain the composition of the compound 35 and the pyraclostrobin.
Claims (8)
1. An imido phenylacetic acid ester compound is characterized in that the imido phenylacetic acid ester compound is a compound shown in a formula I,
in the formula I, R1、R2、R3、R4And R5Respectively is hydrogen, halogen, nitro, cyano, hydroxyl, amino, acetamido, methyl ketone, C1-C12Alkyl, halo C1-C12Alkyl radical, C1-C12Alkoxy radical, C1-C12Alkylthio radical, C1-C12Alkanesulfonyl group, C1-C12Alkylcarbonyl, benzyloxy, phenoxy or pyridyloxy.
2. The method for preparing imido phenylacetic acid esters according to claim 1, which comprises the steps of:
1) diethyl malonate reacts with magnesium chloride to obtain diethyl carboxylic acid methyl magnesium chloride, chloronicotinic acid reacts with thionyl chloride to obtain chloronicotinoyl chloride, the diethyl carboxylic acid methyl magnesium chloride reacts with the chloronicotinoyl chloride to obtain a compound shown in a structural formula 1, the compound shown in the structural formula 1 is decomposed by a ketone formula to obtain a compound shown in a structural formula 2, and then the compound is reacted with polysubstituted phenol to obtain a compound shown in an intermediate 1;
2) preparing a compound shown in a structural formula 4 by taking N-hydroxyphthalimide and a compound shown in a structural formula 3 as raw materials, and then reacting the compound with hydrazine hydrate to obtain a compound shown in an intermediate 2;
3) and reacting the intermediate 1 with the intermediate 2 to obtain the compound shown in the formula I.
3. The use of an iminophenylacetic acid ester compound of claim 1 in the preparation of a fungicide.
4. The use as claimed in claim 3, wherein the active ingredient of the bactericide is the iminophenylacetic acid ester compound as claimed in claim 1.
5. The wettable bactericide powder is characterized by comprising the following substances in percentage by mass: 40% of the imidophenylacetic acid ester compound of claim 1, 2% of sodium dodecyl sulfate, 3% of sodium lignosulfonate, 5% of naphthalene sulfonic acid formaldehyde condensate and 50% of light calcium carbonate.
6. The bactericide suspending agent is characterized by comprising the following substances in percentage by mass: 50% of the iminophenyl acetic acid ester compounds described in claim 1, 10% of ethylene glycol, 6% of nonylphenol polyethylene glycol ether, 10% of sodium lignosulfonate, 1% of carboxymethyl cellulose, 0.2% of 37% by mass aqueous formaldehyde solution, 0.8% of 75% by mass aqueous silicone oil emulsion and 22% of water.
7. The bactericide water dispersible granule is characterized by comprising the following substances in percentage by mass: 45% of the iminophenylacetic acid ester compounds of claim 1, 12% of naphthalenesulfonic acid-formaldehyde condensate, 8% of sodium N-methyl-N-oleoyl-taurate, 2% of polyvinylpyrrolidone and 3% of kaolin.
8. The bactericide composition is characterized by comprising the following substances in percentage by mass: 20% of the imido phenylacetic acid ester compound of claim 1, 20% of pyraclostrobin, 20% of a dispersing agent, 0-1% of organic bentonite, 1-5% of polyethylene glycol (PEG) 2000 and 34% -39% of water.
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| US5194662A (en) * | 1990-06-27 | 1993-03-16 | Basf Aktiengesellschaft | O-benzyloxime ethers and crop protection agents containing these compounds |
| WO1999011129A1 (en) * | 1997-09-04 | 1999-03-11 | E.I. Du Pont De Nemours And Company | Enantiomerically enriched compositions and their pesticidal use |
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| US5194662A (en) * | 1990-06-27 | 1993-03-16 | Basf Aktiengesellschaft | O-benzyloxime ethers and crop protection agents containing these compounds |
| WO1999011129A1 (en) * | 1997-09-04 | 1999-03-11 | E.I. Du Pont De Nemours And Company | Enantiomerically enriched compositions and their pesticidal use |
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| Title |
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| 取代苯氧基-3-乙酰吡啶类中间体的合成;万川等;《化学试剂》;20131015;第35卷(第10期);871-872页 1.2 合成部分 * |
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