CN106946770A - High activity imido grpup phenylacetic acid ester compound and its preparation method and application - Google Patents
High activity imido grpup phenylacetic acid ester compound and its preparation method and application Download PDFInfo
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- CN106946770A CN106946770A CN201710160407.4A CN201710160407A CN106946770A CN 106946770 A CN106946770 A CN 106946770A CN 201710160407 A CN201710160407 A CN 201710160407A CN 106946770 A CN106946770 A CN 106946770A
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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
- C07D213/63—One oxygen atom
- 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
-
- 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 pesticide field, and in particular to high activity imido grpup phenylacetic acid ester compound and its preparation method and application.This invention address that the research of new methoxy acrylic ester compounds, pyridine aryl oxide structure is introduced in structure, the research of such new compound structure has been widened, it was found that high activity imido grpup phenylacetic acid ester compound.Such compound shows the bioactivity suitable with trifloxystrobin with Fluoxastrobin, has preferable effect to most pathogens, and especially Sclerotinia sclerotiorum prevention effect is protruded, still effective under low dosage.
Description
Technical field
The invention belongs to pesticide field, and in particular to high activity imido grpup phenylacetic acid ester compound and preparation method thereof and
Using.
Background technology
Methoxy acrylic bactericide is successfully developed by lead compound of natural products Strobilurin A
The important bactericide of a class out, with high-efficiency low-toxicity wide spectrum and absorbability feature, has protection, treatment and eradicant action concurrently.
Methoxy acrylic bactericide is almost to all fungal diseases, such as Basidiomycetes, Ascomycetes, deuteromycetes and oomycetes
Guiding principle etc., there is good activity, can prevent and treat the diseases such as rust, powdery mildew, downy mildew and the rice blast of various crop.Methoxy propyl
Alkene bactericide of phosphate (phosphinium) ester is mitochondrial respiratory chain inhibitor, by suppressing cytochrome b and c1Between electron transmission, prevent thin
The synthesis of born of the same parents' energy, and then suppress the effect of its mitochondrial respiratory, so as to reach bacteriostasis.Exactly its unique mechanism of action,
High-efficiency broad spectrum and it is environmentally friendly the characteristics of so that methoxy acrylic bactericide turns into the great market vitality and development is latent
The disinfectant use in agriculture kind of power, also becomes the study hotspot of pesticide field.
Current almost all of big agricultural chemicals company has been involved in the research and development of such compound.The country mainly has Shenyang chemical industry to grind
Study carefully the mechanisms such as institute, Zhejiang chemical research institute and develop such noval chemical compound with high activity, the research master of other corporate facilitys
To be compounded for the product of commercialization, the research of complex composition has tended to be ripe, but it is domestic for such change
Still deficient in the research and development of compound, the compound for developing innovative high activity is even more few.In addition, methoxy acrylic acid
Esters bactericide is long-term a large amount of irrational using easily making germ develop immunity to drugs, and germ is insensitive to bactericide and causes funeral
Lose drug effect.
The content of the invention
The purpose of the present invention is to propose to high activity imido grpup phenylacetic acid ester compound and its preparation method and application, specifically
Technical scheme is as follows：
High activity imido grpup phenylacetic acid ester compound is compound shown in Formulas I,
R in Formulas I1、R2、R3、R4And R5Respectively hydrogen, halogen, nitro, cyano group, hydroxyl, amino, substituted-amino, acetyl ammonia
Base, MIBK, substitution oxime benzyl oxide, C1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkylthio group, C1-C12Alkane
Sulfonyl, C1-C12Alkyl-carbonyl, benzyloxy or aryloxy group.
The aryloxy group is phenoxy group and pyridine epoxide.
The preparation method of described high activity imido grpup phenylacetic acid ester compound, comprises the following steps：
1) diethyl malonate obtains diethyl carboxylic acid methyl magnesium chloride, chloro-nicotinic acid and thionyl chloride with magnesium chloride
Reaction obtains chloro nicotinoyl chlorine, and diethyl carboxylic acid methyl magnesium chloride obtains compound shown in structural formula 1 with the reaction of chloro nicotinoyl chlorine,
The compound of structural formula 1 is decomposed through keto-acid and obtains compound shown in structural formula 2, then obtains intermediate 1 with polysubstituted phenol reaction
Shown compound；
2) using compound shown in HP and structural formula 3 shown in raw material preparation structure formula 4 chemical combination
Thing, then obtains compound shown in intermediate 2 with hydration hydrazine reaction；
3) intermediate 1 and intermediate 2 react, and obtain compound shown in Formulas I.
Application of the described high activity imido grpup phenylacetic acid ester compound in bactericide is prepared.
The active component of the bactericide is described high activity imido grpup phenylacetic acid ester compound.
A kind of bactericide wettable powder, by the material composition of following weight/mass percentage compositions：Described in 40% claim 1
High activity imido grpup phenylacetic acid ester compound, 2% lauryl sodium sulfate, 3% sodium lignin sulfonate, 5% naphthalene
Sulfonic formaldehyde condensation compound, 50% precipitated calcium carbonate.
A kind of bactericide suspending agent, by the material composition of following weight/mass percentage compositions：Height described in 50% claim 1
Active imido grpup phenylacetic acid ester compound, 10% ethylene glycol, 6% Nonoxynol-9,10% lignin
Sodium sulfonate, 1% carboxymethyl cellulose, the formalin of 0.2% mass fraction 37%, 0.8% mass fraction 75%
Silicone oil aqueous emulsion, 22% water.
A kind of bactericide water dispersible granule, by the material composition of following weight/mass percentage compositions：Described in 45% claim 1
High activity imido grpup phenylacetic acid ester compound, 12% naphthalene sulfonic acid-formaldehyde condensation product, 8% N- Nmethyl-N-oleoyls Ji-ox
Sodium sulfonate, 2% polyvinylpyrrolidone, 3% kaolin.
A kind of microbicide compositions, by the material composition of following weight/mass percentage compositions：Height described in 20% claim 1
Active imido grpup phenylacetic acid ester compound, 20% pyraclostrobin, 20% dispersant, 0-1% organic bentonite, 1-
5% polyethylene glycol PEG2000,34%-39% water.
Beneficial effects of the present invention are：
This invention address that the research of new methoxy acrylic ester compounds, introduces pyridine aryl oxide knot in structure
Structure, has widened the research of such new compound structure, it was found that the new methoxy acrylic ester compounds of high activity：It is sub-
Amido phenylacetic acid ester compound.Such compound shows the bioactivity suitable with trifloxystrobin with Fluoxastrobin, to most diseases
Opportunistic pathogen has preferable effect, and especially Sclerotinia sclerotiorum prevention effect is protruded, still effective under low dosage.
Embodiment
The present invention proposes high activity imido grpup phenylacetic acid ester compound and its preparation method and application, with reference to reality
Example is applied to be described further the present invention.
R in formula I1、R2、R3、R4And R5Substituent citing such as table 1, but be not limited only to this.
R in compound of formula I1、R2、R3、R4And R5Substituent
Imido grpup phenylacetic acid ester compound provided by the present invention containing fragrant oxy picolinate oxime ether structure unit, it synthesizes road
Line is as follows：
Reaction is carried out in suitable solvent, and suitable solvent is tetrahydrofuran, acetonitrile, toluene, dimethylbenzene, benzene, N, N-
Dimethylformamide, dimethyl sulfoxide, acetone, methanol etc..
Suitable acid may be selected from acetic acid, hydrochloric acid, nitric acid, sulfuric acid, methanesulfonic acid, p-methyl benzenesulfonic acid, formic acid, phosphoric acid etc..
Reaction temperature in ice bath between room temperature, usually 0-25 DEG C.
Reaction time be 0.5h to 24h, usual 20h.
The synthetic route of wherein intermediate 1 is as follows：
Reaction is carried out in suitable solvent, and suitable solvent is tetrahydrofuran, acetonitrile, toluene, dimethylbenzene, benzene, N, N-
Dimethylformamide, dimethyl sulfoxide, acetone etc..
Suitable alkali may be selected from NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, triethylamine, pyridine, first
Sodium alkoxide, caustic alcohol, potassium tert-butoxide, sodium tert-butoxide, cesium carbonate etc..
Each reaction temperature in ice bath between solvent fluidizing point temperature, usually 0-100 DEG C；Each reaction time be 0.5h extremely
20h, usual 4-8h.
The synthetic route of intermediate 2 is as follows：
Reaction is carried out in suitable solvent, and suitable solvent is tetrahydrofuran, acetonitrile, toluene, dimethylbenzene, benzene, N, N-
Dimethylformamide, dimethyl sulfoxide, acetone, methanol etc..
Suitable alkali may be selected from NaOH, potassium hydroxide, sodium carbonate, potassium carbonate, sodium acid carbonate, triethylamine, pyridine, first
Sodium alkoxide, caustic alcohol, potassium tert-butoxide, sodium tert-butoxide etc..
Each reaction temperature in ice bath between solvent fluidizing point temperature, usually 0-100 DEG C；Each reaction time be 0.5h extremely
20h, usual 4-8h.
Experimental method described in following embodiments, unless otherwise specified, is conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
Embodiment 1：Compound Ia synthesis
(1) preparation of pyridine aryl oxide MIBK (P1)
A) triethylamine (183.2g, 1.8mol) and diethyl malonate (119g, 0.9mol) are added in 2L there-necked flasks,
Dry toluene (700ml), stirring is lower to add magnesium chloride (51g, 0.53mol).This reaction solution under room temperature (25 DEG C) in stirring 1.5h.
B) 6- chlorine apellagrins (120g, 0.75mol), thionyl chloride (300ml) and dry toluene are added in 1L there-necked flasks
(200ml), instills two and drips DMF, be heated to reflux 2h.After slightly cold, reflux makes distilling apparatus into, by excessive thionyl chloride with
And solvent toluene is steamed.At the end of fast, stop heating, after cooling, steamed the toluene of remaining using rotary evaporating device.
C) added after being distilled to step b) in product after appropriate dry toluene dilution, be slowly added into step a) and stir at room temperature
In the reaction solution mixed.Continue to stir after 40min and be acidified with dense HCl solution (261g, 2.32mol).Rotary evaporation toluene layer, cooling
After produce faint yellow solid.It is accurate in this solid to add DMSO (650ml) and water (29ml).Mixture is heated and maintained at
155 DEG C, stop heating after 3h, poured into after the cooling of question response liquid in 2.5L cold water, there are a large amount of pale solids to separate out, filter, do
It is dry.Obtain the chloro- 3- acetylpyridines 94g of product 6-, yield 70.1%.
D) synthesis of pyridine aryl oxide MIBK (P1)
The addition chloro- 3- acetylpyridines (18.7g, 0.12mol) of 6- in 500ml flasks, p-cresol (14.26g,
0.132mol) with cesium carbonate (39g, 0.12mol), and DMF (300ml) solvent.It is heated to reflux, stops heating, cooling after 1h.
Reaction solution is poured into excessive water, and stirring separates out solid, filtering.Crude product re-crystallizing in ethyl acetate.Dry, weigh 16g, yellowish
Color crystal, yield 58.7%.
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 benzyloxy amine (P2)
In the 250ml there-necked flasks of stirrer and condenser pipe are loaded onto, solvent DMF 100ml is added, the adjacent benzene of N- hydroxyls is added
Dicarboximide 16.3g (0.1mol), heating, solid all dissolves, then compares 1 by the amount of material:The 1 corresponding alkyl halide of input
Hydrocarbon, is to slowly warm up to 60 DEG C, the amount 1 of material is pressed in reaction after five minutes:1.1 add triethylamine, and 60 DEG C of reactions are heated under stirring,
Point plate detection reaction is complete, is slowly cooled to room temperature, pours frozen water into, separates out solid, and suction filtration drying obtains product N- substituted benzyl oxygens
Base phthalimide.
Stirrer is loaded onto in 250mL single port bottles, solvent methanol 100ml is added, N- substituted benzyloxy O-phthalics are added
Acid imide (0.1mol), stirring, compares 1 by the amount of material：1 is added dropwise hydrazine hydrate solid, and all dissolving, reappears muddiness for a moment,
Put plate detection raw material reaction after 2h to finish, product P2 methanol solution is directly used in next step by suction filtration.
(3) compound Ia synthesis
Load onto stirrer in 250mL there-necked flasks, add P2 methanol solution 100ml, the pyridine of the amount of material such as add
Aryl oxide MIBK (P1), adds a small amount of acetic acid, 24h is stirred at room temperature.Point plate detection reaction, until raw material reaction is complete, crosses post point
From with petroleum ether：Ethyl acetate=10:1 is eluant, eluent, isolated product.Yield 76%, white solid.
Structure confirmation data is：1H NMR(300MHz,CDCl3) δ 8.40 (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.
Embodiment 2：Compound Ib synthesis
(1) preparation of pyridine aryl oxide MIBK (P3)
A) triethylamine (183.2g, 1.8mol) and diethyl malonate (119g, 0.9mol) are added in 2L there-necked flasks,
Dry toluene (700ml), stirring is lower to add magnesium chloride (51g, 0.53mol).This reaction solution under room temperature (25 DEG C) in stirring 1.5h.
B) 2- chlorine apellagrins (120g, 0.75mol), thionyl chloride (300ml) and dry toluene are added in 1L there-necked flasks
(200ml), instills two and drips DMF, be heated to reflux 2h.After slightly cold, reflux makes distilling apparatus into, by excessive thionyl chloride with
And solvent toluene is steamed.At the end of fast, stop heating, after cooling, steamed the toluene of remaining using rotary evaporating device.
C) added after being distilled to step b) in product after appropriate dry toluene dilution, be slowly added into step a) and stir at room temperature
In the reaction solution mixed.Continue to stir after 40min and be acidified with dense HCl solution (261g, 2.32mol).Rotary evaporation toluene layer, cooling
After produce faint yellow solid.It is accurate in this solid to add DMSO (650ml) and water (29ml).Mixture is heated and maintained at
155 DEG C, stop heating after 3h, the cooling of question response liquid is poured into 2.5L cold water, there are a large amount of pale solids to separate out, is filtered, dries.
Obtain the chloro- 3- acetylpyridines 96g of product 2-, yield 72%.
D) synthesis of pyridine aryl oxide MIBK (P3)
The addition chloro- 3- acetylpyridines (18.7g, 0.12mol) of 2- in 500ml flasks, o-cresol (14.26g,
0.132mol) with cesium carbonate (39g, 0.12mol), and DMF (300ml) solvent.It is heated to reflux, stops heating, cooling after 1h.
Reaction solution is poured into excessive water, and stirring separates out solid, filtering.Crude product re-crystallizing in ethyl acetate.Dry, weigh 16.8g, in vain
Crystal, yield 62%.
m.p.36-37℃,1H NMR (300MHz, CDCl3) δ 8.38-8.18 (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 benzyloxy amine (P2)
In the 250ml there-necked flasks of stirrer and condenser pipe are loaded onto, solvent DMF 100ml is added, the adjacent benzene of N- hydroxyls is added
Dicarboximide 16.3g (0.1mol), heating, solid all dissolves, then compares 1 by the amount of material:The 1 corresponding alkyl halide of input
Hydrocarbon, is to slowly warm up to 60 DEG C, the amount 1 of material is pressed in reaction after five minutes:1.1 add triethylamine, and 60 DEG C of reactions are heated under stirring,
Point plate detection reaction is complete, is slowly cooled to room temperature, pours frozen water into, separates out solid, and suction filtration drying obtains product N- substituted benzyl oxygens
Base phthalimide.
Stirrer is loaded onto in 250mL single port bottles, solvent methanol 100ml is added, N- substituted benzyloxy O-phthalics are added
Acid imide (0.1mol), stirring, compares 1 by the amount of material：1 is added dropwise hydrazine hydrate solid, and all dissolving, reappears muddiness for a moment,
Put plate detection raw material reaction after 2h to finish, product P2 methanol solution is directly used in next step by suction filtration.
(3) compound Ib synthesis
Load onto stirrer in 250mL there-necked flasks, add P2 methanol solution 100ml, the pyridine of the amount of material such as add
Aryl oxide MIBK (P3), adds a small amount of acetic acid, 24h is stirred at room temperature.Point plate detection reaction, until raw material reaction is complete, crosses post point
From with petroleum ether：Ethyl acetate=10:1 is eluant, eluent, isolated product.Yield 73%, oily liquids.
Structure confirmation data is：1H NMR (300MHz, CDCl3) δ 8.41 (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), (s, the 6H) of 6.89 (d, J=8.7Hz, 1H), 5.20 (s, 2H), 4.06 (s, 3H), 3.84 (s, 3H), 2.2213C 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.
Embodiment 3：The biological activity determination of high activity imido grpup phenylacetic acid ester compound
The indoor bactericidal activity test reference literature method of high activity imido grpup phenylacetic acid ester compound is carried out, specific step
Suddenly it is：
(1) preparation of PDA culture medium
PDA culture medium (1L deionized waters：Potato 200g：Agar 20g：Glucose 20g) configuration step：Potato is washed
Only, remove the peel, be cut into small pieces, weigh 1400g, wrapped up with two double gauzes, after deionized water is boiled, add the Ma Ling wrapped
Potato boils 30min；Potato is pulled out after 30min, is slowly added into the soaked agar strip 140g of deionized water, is stirred when boiling
Until agar strip is completely dissolved；The dissolving of about 30min or so agar strips is complete, adds glucose 140g, stirs, and it is fixed to add water
Hold to 7L.Dispensed with conical flask, seal bottle film with sterile culture container and seal, after sterilized with high-pressure sterilizing pot, keep 121 DEG C of sterilizings
Taken out after 30min standby.
(2) decoction is configured
Weigh testing compound, Fluoxastrobin and trifloxystrobin active compound 20mg respectively with a ten thousandth balance, be added to 1ml centrifugations
Guan Zhong, dissolves ultrasound with 5ml DMSO, is prepared into 20000mg/L mother liquor；First by super-clean bench sterilize 30min after, in super-clean bench
Under aseptic condition, the mother liquor configured is diluted to 50mg/L band medicine culture medium with PDA culture medium, culture dish is poured into, each
Ware 15ml or so, obtains band medicine culture medium flat plate；Blank control and DMSO solvent control of the Setup Experiments without medicament, each processing
In triplicate.
(3) experimental method
Using mycelial growth rate method, on sterile super-clean bench, by diameter 5mm card punch alcolhol burner sterilization,
Put to room temperature, the various pathogens activated are punched with card punch；Again with No. 11 knife blades by pure culture biscuits involvng inoculation in after cooling
The center with medicine culture medium flat plate, cover ware lid, upside down dark culturing in 25 DEG C of incubators, three are parallel, statistics
Averaged when as a result.
(4) investigate and calculate
Pathogen mycelial growth situation is investigated according to the growing state of bacterium colony in blank control culture dish, treated in blank control
After bacterium colony fully grows, the colony diameter of each processing is measured with crossing method.
Mycelial growth inhibition rate computing formula：
Mycelial growth inhibition rate (%)=(control bacterium colony increases diameter-chemicals treatment bacterium colony and increases diameter)/(control bacterium
Fall to increase diameter -7)) × 100%.
In vitro bactericidal activity indoor bactericidal activity measurement result is as shown in table 2.Under 50mg/L concentration, majority of compounds
Preferable Antifungal Activity in Vitro is shown to 7 kinds of pathogens of test.General activity of the part of compounds to rape sclerotium (SS)
Highest is suitable with the inhibitory activity of comparison medicament Fluoxastrobin and trifloxystrobin.
The in vitro bactericidal activity of the partial target compound of table 2
SS=sclerotinite (Sclerotinia sclerotiorum (Lib.) de Bary)；BC=Botrytis cinereas China pink becomes
Plant (Botrytis cinerea)；PI=phytophthora infestans (Phytophthora infestans (Mont.) De Bary)；PA=
Melon and fruit corruption is mould (Pythium aphanidermatum)；RS=Rhizoctonia solani Kuhns (Rhizoctonia solani)；PG=rice blasts
Germ (Pyricularia grisea)；CO=anthrax bacterias (Colletotrichum.orbiculare (Berk.＆Ment.))
Determine EC of the target compound to Sclerotinia sclerotiorum50During value, experimental method equally uses colony diameter method.Set six
Individual concentration gradient, calculates target compound under each concentration and, to the inhibiting rate of Sclerotinia sclerotiorum, passes through IBM SPSS
The software statistics of Statistics 20 are calculated, and draw the EC of target compound50Value.Measurement result is as shown in table 3.It can be seen that, it is generalized
Compound I is suitable with Fluoxastrobin and trifloxystrobin in biological activity test, EC of the part of compounds to rape sclerotium50It is better than similar business
Product chemical drug agent Fluoxastrobin.Due to its positive characteristic, the protection farming that high activity imido grpup phenylacetic acid ester compound can be strong
Thing, gardening plant, fruits and vegetables etc., have extraordinary preventive and therapeutic effect to disease caused by germ.
EC of the part of compounds of table 3 to rape sclerotium50
| 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 |
| Fluoxastrobin | 0.791 | 0.445-1.440 |
Embodiment 4：The preparation of the wettable powder of compound 3
The wettable powder of compound 3 by following weight/mass percentage compositions material composition：
Compound and each component are sufficiently mixed, after ultra-fine pulverizer disintegrating, 50% wettable powder product is obtained.
Embodiment 5：The preparation of the suspending agent of compound 33
The suspending agent of compound 33 by following weight/mass percentage compositions material composition：
Compound 33 and each component are sufficiently mixed, the suspending agent product of 35% compound 33 is obtained.
Embodiment 6：The preparation of the water dispersant of compound 56
The water dispersant of compound 56 by following weight/mass percentage compositions material composition：
Compound 56 and each component are sufficiently mixed crushing, added water after kneading, the comminutor of 10-100 eye mesh screens is added
It is middle to be granulated, then again through drying, screening.
Embodiment 7：The preparation of compound 35 and pyraclostrobin composition
Compound 35 and pyraclostrobin composition by following weight/mass percentage compositions material composition：
Compound 35, pyraclostrobin and each component are sufficiently mixed, the combination of compound 35 and pyraclostrobin is obtained
Thing.
Claims (9)
1. high activity imido grpup phenylacetic acid ester compound, it is characterised in that the high activity imido grpup phenylacetic acid ester chemical combination
Thing is compound shown in Formulas I,
R in Formulas I1、R2、R3、R4And R5Respectively hydrogen, halogen, nitro, cyano group, hydroxyl, amino, substituted-amino, acetylamino, first
Base ketone, substitution oxime benzyl oxide, C1-C12Alkyl, halo C1-C12Alkyl, C1-C12Alkoxy, C1-C12Alkylthio group, C1-C12Alkane sulphonyl
Base, C1-C12Alkyl-carbonyl, benzyloxy or aryloxy group.
2. high activity imido grpup phenylacetic acid ester compound according to claim 1, it is characterised in that the aryloxy group is
Phenoxy group and pyridine epoxide.
3. the preparation method of the high activity imido grpup phenylacetic acid ester compound described in claim 1 or 2, it is characterised in that bag
Include following steps：
1) diethyl malonate obtains diethyl carboxylic acid methyl magnesium chloride with magnesium chloride, and chloro-nicotinic acid reacts with thionyl chloride
Chloro nicotinoyl chlorine is obtained, diethyl carboxylic acid methyl magnesium chloride obtains compound shown in structural formula 1, structure with the reaction of chloro nicotinoyl chlorine
The compound of formula 1 is decomposed through keto-acid and obtains compound shown in structural formula 2, is then obtained with polysubstituted phenol reaction shown in intermediate 1
Compound；
2) using compound shown in HP and structural formula 3 shown in raw material preparation structure formula 4 compound, so
Afterwards compound shown in intermediate 2 is obtained with hydration hydrazine reaction；
3) intermediate 1 and intermediate 2 react, and obtain compound shown in Formulas I.
4. application of the high activity imido grpup phenylacetic acid ester compound in bactericide is prepared described in claim 1 or 2.
5. application according to claim 4, it is characterised in that the active component of the bactericide is described in claim 1
High activity imido grpup phenylacetic acid ester compound.
6. a kind of bactericide wettable powder, it is characterised in that by the material composition of following weight/mass percentage compositions：40% right
It is required that the high activity imido grpup phenylacetic acid ester compound described in 1,2% lauryl sodium sulfate, 3% lignin sulfonic acid
Sodium, 5% naphthalene sulfonic acid-formaldehyde condensation product, 50% precipitated calcium carbonate.
7. a kind of bactericide suspending agent, it is characterised in that by the material composition of following weight/mass percentage compositions：50% claim
High activity imido grpup phenylacetic acid ester compound described in 1,10% ethylene glycol, 6% Nonoxynol-9,10%
Sodium lignin sulfonate, 1% carboxymethyl cellulose, the formalin of 0.2% mass fraction 37%, 0.8% quality
The silicone oil aqueous emulsion of fraction 75%, 22% water.
8. a kind of bactericide water dispersible granule, it is characterised in that by the material composition of following weight/mass percentage compositions：45% right
It is required that the high activity imido grpup phenylacetic acid ester compound described in 1,12% naphthalene sulfonic acid-formaldehyde condensation product, 8% N- methyl-N-
Oleoyl-sodium taurocholate, 2% polyvinylpyrrolidone, 3% kaolin.
9. a kind of microbicide compositions, it is characterised in that by the material composition of following weight/mass percentage compositions：20% claim
High activity imido grpup phenylacetic acid ester compound described in 1,20% pyraclostrobin, 20% dispersant, 0-1%'s is organic
Bentonite, 1-5% polyethylene glycol PEG2000,34%-39% water.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892636A (en) * | 2018-06-25 | 2018-11-27 | 华中农业大学 | A kind of benzyl carboxylate ester type compound and its purposes for preventing and treating farm crop fungus disease |
| WO2022033906A1 (en) * | 2020-08-11 | 2022-02-17 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii |
| EP3970494A1 (en) * | 2020-09-21 | 2022-03-23 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii |
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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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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108892636A (en) * | 2018-06-25 | 2018-11-27 | 华中农业大学 | A kind of benzyl carboxylate ester type compound and its purposes for preventing and treating farm crop fungus disease |
| WO2022033906A1 (en) * | 2020-08-11 | 2022-02-17 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii |
| EP3970494A1 (en) * | 2020-09-21 | 2022-03-23 | Basf Se | Use of strobilurin type compounds for combating phytopathogenic fungi containing an amino acid substitution f129l in the mitochondrial cytochrome b protein conferring resistance to qo inhibitors viii |
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