WO2004084632A1 - Fungicides containing methoxy acrylic acid methyl ester compound - Google Patents

Fungicides containing methoxy acrylic acid methyl ester compound Download PDF

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Publication number
WO2004084632A1
WO2004084632A1 PCT/CN2004/000226 CN2004000226W WO2004084632A1 WO 2004084632 A1 WO2004084632 A1 WO 2004084632A1 CN 2004000226 W CN2004000226 W CN 2004000226W WO 2004084632 A1 WO2004084632 A1 WO 2004084632A1
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Prior art keywords
compound
powdery mildew
mildew
composition according
composition
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PCT/CN2004/000226
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French (fr)
Chinese (zh)
Inventor
Tianming Xu
Dinghua Chen
Xiaolin Kong
Weigang Zhu
Yunhong Zheng
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Zhejiang Chemical Industry Research Institute
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Priority to AU2004224838A priority Critical patent/AU2004224838A1/en
Priority to BRPI0409037-3A priority patent/BRPI0409037A/en
Publication of WO2004084632A1 publication Critical patent/WO2004084632A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/66—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety
    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/36—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a singly bound oxygen or sulfur atom attached to the same carbon skeleton, this oxygen or sulfur atom not being a member of a carboxylic group or of a thio analogue, or of a derivative thereof, e.g. hydroxy-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/31—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
    • C07C67/333—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton
    • C07C67/343—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

Definitions

  • the invention relates to an ethoxylated methacrylate bactericidal agricultural fungicide, and further relates to an ethoxylated methacrylate acrylate compound having a high-efficiency bactericidal effect, a preparation method thereof, a bactericide composition thereof, and uses thereof.
  • Methyloxy acrylate fungicides are highly effective agricultural fungicides derived from natural compounds through structural transformation. They are characterized by wide sterilization, low toxicity to other organisms, and good environmental compatibility. Many major pesticide companies in the world have carried out research in this area and found several methyloxyacrylate compounds with good market prospects. The market share of such fungicides is increasing, and it may replace triazole fungicides as the largest variety of agricultural fungicides.
  • the present invention provides new ethoxylated methacrylate and its preparation method, and its bactericide composition and use.
  • the chemical name of the methoxy methacrylate bactericide compound of the present invention is:
  • the compounds of the invention can be prepared by the following methods:
  • Compound I can be prepared by adding 2, 5 "difluorenylphenol of formula II and 2- ( 2 -halomethylphenyl) -3-methoxymethylacrylate in formula III in a suitable solvent. It can be prepared by adding appropriate base and reacting at appropriate temperature and time. Among them, X leaving group such as halogen, and the preferred solvent is acetone or tetrahydrofuran.
  • the bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, 4A carbonate, and the like.
  • the preferred base in the present invention is sodium carbonate or potassium carbonate.
  • the preferred temperature is 0-1 00. C.
  • the method for preparing compound I in method two is as follows: In a suitable solvent, add 2,5-difluorenylphenol of formula II and a compound of formula IV, and then add the appropriate base and react at the appropriate temperature and time for the preparation.
  • V X leaving group such as halogen, preferably chlorine, bromine or iodine.
  • V in an appropriate solvent then add an appropriate base, add an appropriate amount of methyl gallate, and react at an appropriate temperature and in an appropriate time to obtain
  • the preferred solvent is acetone or tetrahydrofuran.
  • the bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, and the like.
  • the preferred base in the present invention is sodium carbonate or potassium carbonate.
  • the preferred temperature is 0-100 ° C.
  • the preferred base is sodium alkoxide or sodium hydride; the preferred solvent is diethyl ether or methanol. Preferred temperature Degrees are minus 5-100 C.
  • the preferred solvent is acetone or tetrahydrofuran.
  • the bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, and the like.
  • the preferred base in the present invention is sodium carbonate or potassium carbonate.
  • the preferred temperature is 0-100 ° C.
  • Compound I of the present invention is an effective fungicide. Particularly suitable for controlling the following plant diseases: barley and wheat powdery mildew, vegetable powdery mildew, melons powdery mildew, fruit tree powdery mildew, grape powdery mildew, strawberry powdery mildew and flower powdery mildew; wheat and barley stripe rust, leaf rust and other rust diseases .
  • the invention also provides a bactericidal composition of a compound as defined above and a method for preparing the same.
  • composition of the present invention preferably contains the active ingredient of formula (I) from 0.1 to 99.0% by weight. If desired, suitable carriers and surfactants can be added to the composition.
  • composition of the present invention is prepared by mixing Compound I with at least one carrier. This composition may also contain other pesticide active ingredients.
  • the carrier of the present invention is a substance that satisfies the following conditions: it is formulated with an active ingredient to facilitate application to the site to be treated, such as plants, seeds, or soil; or it is convenient for storage, transportation, or handling.
  • the carrier can be a solid or a liquid, and any carrier commonly used in formulating insecticidal and bactericidal compositions can be used.
  • Suitable solid carriers include natural and synthetic silicates, such as diatomaceous earth, talc, wollastonite, aluminum silicate (kaolin), montmorillonite, and mica; calcium carbonate, calcium sulfate, ammonium sulfate; synthetic silicic acid Calcium or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl and styrene polymers and copolymers; solid polychlorophenol; bitumen; waxes such as beeswax, paraffin wax.
  • natural and synthetic silicates such as diatomaceous earth, talc, wollastonite, aluminum silicate (kaolin), montmorillonite, and mica
  • calcium carbonate, calcium sulfate, ammonium sulfate such as calcium sulfate, ammonium sulfate
  • synthetic silicic acid Calcium or aluminum silicate elements such as carbon and sulfur
  • natural and synthetic resins such as benzofuran
  • Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene And mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene, and trichloroethane, and usually mixtures of these liquids are also suitable.
  • the pesticidal and germicidal composition is usually processed into a concentrate and used for transportation, and it is diluted by the user before application.
  • a surfactant carrier facilitates the dilution process.
  • the composition according to the present invention preferably contains a surfactant.
  • the surfactant can be an emulsifier, dispersant or wetting agent: it can be an ionic surfactant or a non-ionic surfactant.
  • a surfactant can be an emulsifier, dispersant or wetting agent: it can be an ionic surfactant or a non-ionic surfactant.
  • compositions of the invention are wettable powders, powders, granules, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols.
  • Wettable powders usually contain 20-80% by weight of active ingredient, and usually contain 2-10% by weight of dispersant in addition to the solid inert carrier, and if necessary or added 0-10% by weight of stabilizers and other additives such as penetration Agent or adhesive.
  • the powder can usually be shaped into a powder concentrate having a similar composition to a wettable powder, but with a dispersant, and further diluted with a solid carrier in the ground to obtain a composition usually containing 0.5 to 10% by weight of active ingredient.
  • Granules are usually made in 10 and 100 mesh sizes and can be prepared by agglomeration or injection techniques. Generally, granules contain 0.1 to 80% by weight of active ingredients and 0 to 10% by weight of additives such as stabilizers, surfactants, sustained release agents, and the like. The so-called "flowable dry powder" consists of relatively small particles with a relatively high concentration of active ingredient. In addition to solvents, emulsifiable concentrates usually contain co-solvents when needed, 1-50% W / V active ingredient, 2-20 W / V emulsifier and 0-20 W / V other additives such as stabilizers, penetrants and corrosion Inhibitor.
  • Suspension concentrates usually contain 10-80% by weight of active ingredients, 0.5-15% by weight of dispersant, and 0.1-10% by weight of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and Adhesive.
  • Aqueous dispersants and emulsifiers such as compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention.
  • the emulsion can be of two types: water-in-oil or oil-in-water.
  • fungicides By adding one or more other fungicides to the composition, it can be made more active than the compound (I) alone.
  • other fungicides may have a synergistic effect on the fungicidal activity of the compound (I).
  • Examples of fungicide compounds that may be included in the composition of the present invention clotrimam, sterilant, azoxystrobin, tridemorpholine, chlorobenzene.
  • Insecticides that can be combined with the compounds of the present invention to form a composition include: insecticides bromomester, diclofenac, methyl 1605, 1605, fenitrothion, diamnon, bupropion, chlorpyrifos, sharp Exterminator, Exterminator, Methomyl, Insecticidal Mono, Insecticidal Double, Badan, Avermectin, Permethrin, Cypermethrin, Permethrin, Stefluthrin, Cyfluthrin, Fenvalerate, Fluoride Diflubenzuron, diflubenzuron, diflubenzuron, pyraclostrobin, imidacloprid, dioxocarb, triazophos, quinacloprid, chlorfenuron, pyridaben, tetrabenazine, etc.
  • the inventors have synthesized some of these compounds, which have broad-spectrum fungicidal activity and can be used to control crops from the class Algae and Oomycetes Diseases caused by a variety of fungi such as Zygomycetes and Deuteromycetes, and the high biological activity of this compound makes it possible to obtain good control effects at very low doses.
  • These compounds show good biological activity against powdery mildew, downy mildew, and anthracnose, as well as controlling black pox and white rust of grapes.
  • the compounds provided by the present invention not only have high biological activity, but also are very friendly to the environment and have no pollution to the environment.
  • the compound provided by the invention not only has high biological activity, but also has low production cost compared with similar products in the world, and is a very promising new agricultural fungicide.
  • the compound of the present invention is 10 kg, talc powder is 89 kg, and polyoxyethylene alkyl propyl ether is kg.
  • the above ingredients are uniformly mixed and pulverized to obtain a powder containing 10% of the active ingredient.
  • the compound of the present invention is 5 kg, clay is 73 kg, bentonite is 20 kg, sodium dioctyl thiosuccinate is 1 kg, and sodium phosphate is 1 kg. All the above ingredients are mixed and mixed thoroughly, and an appropriate amount of water is added. After further mixing, granulation and drying, granules containing 5% of the active ingredient are obtained.
  • the compound of the present invention has good biological activity compared with existing fungicides, and can effectively prevent and treat diseases caused by fungi at very low doses. 3 It is particularly good for powdery mildew, rust, downy mildew, and anthracnose. Effect. Such as wheat, barley powdery mildew, cucumber powdery mildew, pumpkin powdery mildew, strawberry powdery mildew, grape powdery mildew, wheat, barley rust, grape downy mildew, cucumber downy mildew, cucumber anthracnose. Another one has a certain inhibitory effect on grapevine black pox and white rust.
  • the test agent was Compound I of the present invention (emulsion oil with a content of 5%) and six concentrations of 10 5 2. 5 1. 25 0. 625 0. 3125 ppm were set.
  • Control ZA-1963 ie Syngenta's icoxys trobin, which is a commercial compound in a similar patent
  • 5% emulsifiable concentrate was set at six concentrations of 10 5, 2. 5 1. 25 0. 625 0. 3125 ppm.
  • Control agent 20% triazolone EC set 100 50 25ppm 0 Select two potted cucumber plants growing from two leaves and one heart stage to spray the cucumber seedlings, spray for prevention test 24 hours after spraying, 24 hours after treatment test inoculation Spray medicine. After inoculation, young cucumbers were placed in an artificial climatic chamber for moisturizing culture, and the control effect was investigated 7 days later. The results are shown in Table 1:
  • the test agent was Compound I of the present invention (emulsion oil with a content of 5%), and six concentrations of 25, 12.5.6.25, 3.125, 1.563, and 0.781 ppm were set.
  • Control ZA-1963 namely Syngenta's picoxys trobin, which is a compound commercialized in similar patents
  • 5% EC is set to 25, 12. 5, 6. 25, 3. 125, 1. 563, 0.
  • Control agent 20% triazolone EC set 100, 50, 25 ppm.
  • the potted wheat growing up to the two-leaf one-heart stage was sprayed.
  • the vaccine was inoculated 24 hours after spraying in the preventive test, and sprayed 24 hours after seeding in the treatment test. After the inoculation, the wheat was placed in an artificial climate chamber for moisturizing culture, and the control effect was investigated 7 days later. The results are shown in Table 2
  • Compound (I) concentration was 50, 25, 12. 5, 6. 25, 3. 125ppm, a process control agent ZA- 1963 the same concentration of compound I, treatment concentration triadimefon of 100, 50, 25ppm 0 to Potted wheat was cultivated to the 4-5 leaf stage, and allowed to naturally develop to the middle stage. Foliar spray treatment was performed at the concentration set above, and the control effect was investigated after 10 days. The results are shown in Table 3.
  • the treatment concentration of Compound I and the control agent ZA-1963 was 50, 25 mg / l, and the test object was wheat powdery mildew. Spray the two real leaves of potted wheat when they are flat, inoculate the powdery mildew of wheat 24 hours after spraying, move the inoculated wheat to the greenhouse for moisturizing culture, and investigate the prevention effect at 7, 10, 15, 20, 25, and 30 days after treatment .
  • Table 4 Validity period test results
  • the duration test showed that the duration of Compound I was slightly longer than that of ZA-1963 under artificial greenhouse inoculation.
  • Compound I (10% aqueous suspension) was set at four concentrations of 50, 25, 12.5, and 6.25ppm, and the control agent was 20% fentanin EC and the concentration was set at 100ppm. Another set of water control. Each treatment was repeated 4 times. Investigation was made 7 days after application. The results are shown in Table 5. Table 5 Results of Control Tests (Field) on pumpkin Powdery Mildew
  • the CK prevention effect column is the added value of sick fingers.
  • the CK prevention effect column is the added value of sick fingers.
  • the treatment concentration of compound I was 100, 50, 25, 12.5, 6.25 ppm.
  • the treatment concentration of the control agent ZA-1963 was the same as that of compound I, and the treatment concentration of metalaxyl was 500 ppm.
  • Compound I (5% emulsifiable concentrate) was set at five concentrations of 200, 100, 50, 25, 12.5 ppm, and the control agent was 72% DuPont Crewe wettable powder at a concentration of 1000 ppm. A blank control was set up, and each treatment was repeated 4 times. Investigation after spraying the next day. The results are shown in Table 8.
  • Compound I is equivalent to 200 ppm of Cremonol at a control level of 200 ppm in the control of Plasmopara viticola.
  • Compound I (5% emulsifiable concentrate) was set at five concentrations of 200, 100, 50, 25, 12. 5 ppm.
  • the 72% DuPont Crewe wettable powder is set at 1000 ppm. A blank control was set up, and each treatment was repeated 4 times. Investigation 7 days after spraying. The results are shown in Table 9
  • the treatment concentration of compound I and the control agent ZA-1963 was 500, 250, 125, 62.5, 31. 25 ppm.
  • the test object was cucumber anthracnose.
  • the potted cucumber seedlings were sprayed when they grew to a true leaf stage.
  • the anthracnose spore suspension was inoculated after spraying for 24 hours. After the inoculation, they were moved to an artificial climate chamber and the humidity was maintained at 100%. The relative humidity should be 85% after 24 hours of inoculation. Investigation was conducted after 7 days. The results are shown in Table 10.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
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  • Engineering & Computer Science (AREA)
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Abstract

The invention relates to fungicidal compositions which contain 2-(2-((2,5-dimethyl phenoxy)methyl phenyl))-3-methoxy acrylic acid methyl ester of fomula I and steroisomers thereof , their use-method, and active ingredient compound mentioned above and preparation thereof. Biological activity determination shows: compound I has high biological activity on preventing agricultural diseases caused by fungi, especially effective against powdery mildew, downy mildew and anthracnose.

Description

甲氣某丙烯酸曱酯类化合物杀菌剂 技术领域  Methyl Acrylic Acrylate Compound Bactericide Technical Field
本发明涉及一种曱氧基丙烯酸曱酯类农用杀菌剂, 进一步的是关于一种具 有高效杀菌效果的曱氧基丙烯酸曱酯化合物、其制备方法和其杀菌剂组合物及 其用途。  The invention relates to an ethoxylated methacrylate bactericidal agricultural fungicide, and further relates to an ethoxylated methacrylate acrylate compound having a high-efficiency bactericidal effect, a preparation method thereof, a bactericide composition thereof, and uses thereof.
背景技术 Background technique
在 US 4 , 914 , 128号专利申请中公开了一些曱氧基丙烯酸曱酯类化合物, 并公开了其中的化合物具有杀菌活性。  In US Pat. No. 4,914,128, a number of ethoxylated methacrylate compounds are disclosed, and the compounds therein have bactericidal activity.
本申请人意外地发现, 其通式结构中的一些未具体公开的化合物, 具有优 异的杀真菌活性， 并由此完成了本发明。  The applicant has unexpectedly discovered that some compounds not specifically disclosed in its general structure have excellent fungicidal activity, and thus completed the present invention.
曱氧基丙烯酸甲酯类杀菌剂是从天然化合物通过结构改造而来的高效农 用杀真菌剂。 它们特点是杀菌广、 对其它生物毒性低、 环境相容性好。 世界上 有许多农药大公司进行这方面研究，发现了几个有很好市场前景的曱氧基丙烯 酸甲酯类化合物。该类杀菌剂市场占有比例越来越大，将可能取代三唑类杀菌 剂成为农用杀菌剂第一大品种。  Methyloxy acrylate fungicides are highly effective agricultural fungicides derived from natural compounds through structural transformation. They are characterized by wide sterilization, low toxicity to other organisms, and good environmental compatibility. Many major pesticide companies in the world have carried out research in this area and found several methyloxyacrylate compounds with good market prospects. The market share of such fungicides is increasing, and it may replace triazole fungicides as the largest variety of agricultural fungicides.
发明内容 Summary of the Invention
本发明提供了新的曱氧基丙烯酸曱酯类化合物和其制备方法， 及其杀菌剂 组合物和用途。 本发明甲氧基丙烯酸曱酯杀菌剂化合物的化学名称为：  The present invention provides new ethoxylated methacrylate and its preparation method, and its bactericide composition and use. The chemical name of the methoxy methacrylate bactericide compound of the present invention is:
(E) -2- (2- ( (2， 5-二曱基苯氧基）曱基苯基)） -3-曱氧基丙烯酸甲酯 结构式为：
Figure imgf000003_0001
The structural formula of (E) -2- (2-((2,5-Difluorenylphenoxy) fluorenylphenyl))-3-methyloxyacrylate is:
Figure imgf000003_0001
I  I
本发明的化合物可以通过以下方法制备:  The compounds of the invention can be prepared by the following methods:
方法一 反应如下： Method 1 The response is as follows:
Figure imgf000003_0002
II III I
Figure imgf000003_0002
II III I
化合物 I可以这样来制备： 在适当的溶剂中， 加入式 II的 2 , 5」二曱基苯 酚和式 III的 2 - (2-卤代甲基苯基） - 3 -甲氧基丙烯酸曱酯， 再加入适当的碱， 在适当的温度下和适当时间内反应制得。其中 III中的 X离去基团如卤素，优选 优选溶剂为丙酮或四氢呋喃。 Compound I can be prepared by adding 2, 5 "difluorenylphenol of formula II and 2- ( 2 -halomethylphenyl) -3-methoxymethylacrylate in formula III in a suitable solvent. It can be prepared by adding appropriate base and reacting at appropriate temperature and time. Among them, X leaving group such as halogen, and the preferred solvent is acetone or tetrahydrofuran.
其中碱包括有机碱和无机碱: 有机碱包括三乙胺、 吡啶等； 无机碱包括氢 氧化钠、 氢氧化钾、 氢化钠、 碳酸钠、 碳酸 4甲等。 本发明优选碱为碳酸钠或碳 酸钾。  The bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, 4A carbonate, and the like. The preferred base in the present invention is sodium carbonate or potassium carbonate.
优选温度为 0 - 1 00。C。  The preferred temperature is 0-1 00. C.
方法二 反应如下： Method 2 The reaction is as follows:
Figure imgf000004_0001
Figure imgf000004_0001
VI I  VI I
方法二制备化合物 I过程为： 在适当的溶剂中， 加入式 II的 2 , 5 -二曱基 苯酚和式 IV化合物， 最加入适当的碱，在适当的温度下和适当时间内反应制得 The method for preparing compound I in method two is as follows: In a suitable solvent, add 2,5-difluorenylphenol of formula II and a compound of formula IV, and then add the appropriate base and react at the appropriate temperature and time for the preparation.
V。 其中 III中的 X离去基团如卤素， 优选氯、 溴或碘。 V在适当的溶剂中， 再 加入适当的碱，加入适量的曱酸甲酯，在适当的温度下和适当时间内反应制得V. Among them, X leaving group such as halogen, preferably chlorine, bromine or iodine. V in an appropriate solvent, then add an appropriate base, add an appropriate amount of methyl gallate, and react at an appropriate temperature and in an appropriate time to obtain
VI。 VI在适当的溶剂中， 加入曱基化试剂， 如硫酸二甲酯、 碘曱烷等， 再加入 适当的碱， 在适当的温度下和适当时间内反症制得化合物 I 。 VI. VI In a suitable solvent, add a fluorenating reagent, such as dimethyl sulfate, iodopane, etc., and then add a suitable base, at the appropriate temperature and in a suitable time to obtain the compound I.
其中在制备 V时： 优选溶剂为丙酮或四氢呋喃。  Among them, when preparing V: The preferred solvent is acetone or tetrahydrofuran.
其中碱包括有机碱和无机碱： 有机碱包括三乙胺、 吡口走等; 无机碱包括氢 氧化钠、 氢氧化钾、 氢化钠、 碳酸钠、 碳酸钾等。 本发明优选碱为碳酸钠或碳 酸钾。 优选温度为 0 - 1 00°C。  The bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, and the like. The preferred base in the present invention is sodium carbonate or potassium carbonate. The preferred temperature is 0-100 ° C.
在制备 VI时优选碱为曱醇钠或氢化钠等； 优选溶剂为乙醚或甲醇。 优选温 度为零下 5 - 100 C。 In preparing VI, the preferred base is sodium alkoxide or sodium hydride; the preferred solvent is diethyl ether or methanol. Preferred temperature Degrees are minus 5-100 C.
其中在制备 I时： 优选溶剂为丙酮或四氢呋喃。  Among them, when preparing I: The preferred solvent is acetone or tetrahydrofuran.
其中碱包括有机碱和无机碱: 有机碱包括三乙胺、 吡啶等； 无机碱包括氢 氧化钠、 氢氧化钾、 氢化钠、 碳酸钠、 碳酸钾等。 本发明优选碱为碳酸钠或碳 酸钾。  The bases include organic bases and inorganic bases: organic bases include triethylamine, pyridine, etc .; inorganic bases include sodium hydroxide, potassium hydroxide, sodium hydride, sodium carbonate, potassium carbonate, and the like. The preferred base in the present invention is sodium carbonate or potassium carbonate.
优选温度为 0 - 100°C。  The preferred temperature is 0-100 ° C.
本发明的化合物 I是有效的杀真菌剂。 特别适合于防治下列植物病害： 大麦和小麦白粉病、 蔬菜白粉病、 瓜类白粉病、 果树白粉病、 葡萄白粉病、 草莓白粉病及花卉白粉病; 小麦和大麦条锈病、 叶锈病和其它锈病。  Compound I of the present invention is an effective fungicide. Particularly suitable for controlling the following plant diseases: barley and wheat powdery mildew, vegetable powdery mildew, melons powdery mildew, fruit tree powdery mildew, grape powdery mildew, strawberry powdery mildew and flower powdery mildew; wheat and barley stripe rust, leaf rust and other rust diseases .
黄瓜霜霉病， 葡萄霜霉病； 瓜类上的炭疽病等病害。  Cucumber downy mildew, grape downy mildew; diseases such as anthracnose on melons.
本发明还提供了如上所定义的化合物的杀菌组合物及其制备方法。  The invention also provides a bactericidal composition of a compound as defined above and a method for preparing the same.
本发明的组合物， 优选含从 0. 1 - 99. 0%重量的式（I)的活性成份。 需要时 可在组合物中加入合适的载体和表面活性剂成分。  The composition of the present invention preferably contains the active ingredient of formula (I) from 0.1 to 99.0% by weight. If desired, suitable carriers and surfactants can be added to the composition.
本发明组合物的制备方法是将化合物 I和至少一种载体混合。 这种组合物 还可以含有其它的农药活性成分。  The composition of the present invention is prepared by mixing Compound I with at least one carrier. This composition may also contain other pesticide active ingredients.
本发明的载体系满足下述条件的物质:它与活性成分配制后便于施用于待 处理的位点， 例如可以是植物、 种子或土壤； 或者有利于贮存、 运输或操作。 载体可以是固体或液体，和可使用任何通常在配制杀虫、 杀菌组合物中所用的 载体。  The carrier of the present invention is a substance that satisfies the following conditions: it is formulated with an active ingredient to facilitate application to the site to be treated, such as plants, seeds, or soil; or it is convenient for storage, transportation, or handling. The carrier can be a solid or a liquid, and any carrier commonly used in formulating insecticidal and bactericidal compositions can be used.
合适的固体载体包括天然和合成的硅酸盐、 例如硅藻土、 滑石、 硅镁土、 硅酸铝（高岭土）、 蒙脱石和云母； 碳酸钙、 硫酸钙、 硫酸铵； 合成的氧化硅酸 钙或硅酸铝； 元素如碳和硫； 天然的和合成的树脂如苯并呋喃树脂， 聚氯乙烯 和苯乙烯聚合物和共聚物； 固体多氯苯酚； 沥青； 蜡如蜂蜡、 石腊。  Suitable solid carriers include natural and synthetic silicates, such as diatomaceous earth, talc, wollastonite, aluminum silicate (kaolin), montmorillonite, and mica; calcium carbonate, calcium sulfate, ammonium sulfate; synthetic silicic acid Calcium or aluminum silicate; elements such as carbon and sulfur; natural and synthetic resins such as benzofuran resins, polyvinyl and styrene polymers and copolymers; solid polychlorophenol; bitumen; waxes such as beeswax, paraffin wax.
合适的液体载体包括水； 醇如异丙醇和乙醇； 酮如丙酮、 曱基乙基酮、 曱 基异丁基酮和环己酮； 醚； 芳烃如苯、 甲苯和二甲苯； 石油馏分如煤油和矿物 油； 氯代烃如四氯化碳、 全氯乙烯和三氯乙烷, 通常， 这些液体的混合物也是 合适的。  Suitable liquid carriers include water; alcohols such as isopropanol and ethanol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; ethers; aromatic hydrocarbons such as benzene, toluene and xylene; petroleum fractions such as kerosene And mineral oils; chlorinated hydrocarbons such as carbon tetrachloride, perchloroethylene, and trichloroethane, and usually mixtures of these liquids are also suitable.
杀虫、 杀菌组合物通常加工成浓缩物的形式并以此用于运输， 在施用之前 由使用者将其稀释。 少量的表面活性剂载体的存在有助于稀释过程。 这样， 按 照本发明的组合物中， 优选含有表面活性剂。 表面活性剂可以是乳化剂、 分散剂或润湿剂： 它可以是离子表面活性剂或 非离子表面活性剂。 如： 聚丙烯酸和木质素磺酸的钠盐或钙盐； 分子中含至少The pesticidal and germicidal composition is usually processed into a concentrate and used for transportation, and it is diluted by the user before application. The presence of a small amount of a surfactant carrier facilitates the dilution process. Thus, the composition according to the present invention preferably contains a surfactant. The surfactant can be an emulsifier, dispersant or wetting agent: it can be an ionic surfactant or a non-ionic surfactant. Such as: sodium salt or calcium salt of polyacrylic acid and lignin sulfonic acid;
12 个碳原子的脂肪酸或脂肪胺或酰胺; 环氧乙烷和或环氧丙烷的缩合物; 甘 醇， 山梨醇、蔗糖或季戊四醇脂肪酸脂及这些酯与环氧乙烷和或环氧丙环的缩 合物；脂肪醇或烷基苯酚如对辛基苯酚或对辛基苯酚与环氧乙烷和或环氧丙烷 的缩合物； 这些缩合产物的硫酸盐或磺酸盐； 在分子中含有至少 10个碳原子 的硫酸或磺酸酯的碱金属或碱土金属盐， 优选钠盐， 例如硫酸月桂酯钠， 硫酸 仲烷基酯钠 5 磺化蓖麻油钠盐， 磺酸烷基芳基酯钠如十二烷基苯磺酸钠盐。 Fatty acids or fatty amines or amides of 12 carbon atoms; condensates of ethylene oxide and or propylene oxide; glycol, sorbitol, sucrose or pentaerythritol fatty acid esters and these esters with ethylene oxide and / or propylene oxide Condensates of fatty alcohols or alkyl phenols such as p-octylphenol or condensates of p-octylphenol with ethylene oxide and or propylene oxide; sulfate or sulfonate salts of these condensation products; Alkali or alkaline earth metal salts of sulfuric acid or sulfonate of 10 carbon atoms, preferably sodium salts, such as sodium lauryl sulfate, secondary alkyl sulfate sodium 5 sulfonated castor oil sodium salt, sodium alkylaryl sulfonate Such as dodecylbenzenesulfonic acid sodium salt.
本发明的组合物的实例是可湿性粉剂、 粉剂、 颗粒剂、 可乳化的浓缩剂、 乳剂、 悬浮浓缩剂、 气雾剂和烟雾剂。 可湿性粉剂通常含 20 - 80%重量活性成 分， 且通常除固体惰性载体之外， 还含有 2 - 10%重量分散剂， 且若需要或加 入 0 - 10%重量稳定剂和或其它添加剂如渗透剂或粘着剂。 粉剂通常可成型为 具有可湿性粉剂相似的组成但有分散剂的粉剂浓缩剂，在地里进一步用固体载 体稀释， 得到通常含 0. 5 - 10%重量活性成分的组合物。 粒剂通常制成具有 10 和 100 目大小， 且可用成团或注入技术制备。 通常， 粒剂含 0. 1 - 80%重量的 活性成分和 0 - 10%重量添加剂如稳定剂、表面活性剂、緩释剂等。 所谓的 "可 流动干粉"由具有相对高浓度活性成分的相对小的颗粒组成。可乳化浓缩剂除 溶剂外， 当需要时通常含有共溶剂， 1 - 50%W/V活性成分， 2 - 20W/V乳化剂 和 0 - 20 W/V其他添加剂如稳定剂、渗透剂和腐蚀抑制剂。 悬浮浓缩齐通常含 有 10 - 80%重量的活性成分、 0. 5 - 15%重量的分散剂、 0. 1 - 10%重量的其它添 加剂如消泡剂、 腐蚀抑制剂、 稳定剂、 渗透剂和粘着剂。  Examples of the composition of the invention are wettable powders, powders, granules, emulsifiable concentrates, emulsions, suspension concentrates, aerosols and aerosols. Wettable powders usually contain 20-80% by weight of active ingredient, and usually contain 2-10% by weight of dispersant in addition to the solid inert carrier, and if necessary or added 0-10% by weight of stabilizers and other additives such as penetration Agent or adhesive. The powder can usually be shaped into a powder concentrate having a similar composition to a wettable powder, but with a dispersant, and further diluted with a solid carrier in the ground to obtain a composition usually containing 0.5 to 10% by weight of active ingredient. Granules are usually made in 10 and 100 mesh sizes and can be prepared by agglomeration or injection techniques. Generally, granules contain 0.1 to 80% by weight of active ingredients and 0 to 10% by weight of additives such as stabilizers, surfactants, sustained release agents, and the like. The so-called "flowable dry powder" consists of relatively small particles with a relatively high concentration of active ingredient. In addition to solvents, emulsifiable concentrates usually contain co-solvents when needed, 1-50% W / V active ingredient, 2-20 W / V emulsifier and 0-20 W / V other additives such as stabilizers, penetrants and corrosion Inhibitor. Suspension concentrates usually contain 10-80% by weight of active ingredients, 0.5-15% by weight of dispersant, and 0.1-10% by weight of other additives such as defoamers, corrosion inhibitors, stabilizers, penetrants and Adhesive.
水分散剂和乳化剂， 例如通过用水稀释按照本发明的可湿性粉剂或浓缩物 得到的组合物，也列入本发明范围。所说的乳剂可具有油包水或水包油两个类 型。  Aqueous dispersants and emulsifiers, such as compositions obtained by diluting a wettable powder or concentrate according to the invention with water, are also included in the scope of the invention. The emulsion can be of two types: water-in-oil or oil-in-water.
通过在组合物中加入其他一种或多种杀真菌剂，使其能比单独的化合物（I) 具有更广的活性。 此外， 其他杀真菌剂可对化合物（I)的杀菌活性具有增效作 用。可以包含在本发明组合物中的杀真菌剂化合物的实例中：克菌丹、灭菌丹、 嘧霉胺、 十三吗啉、 氯苯。密啶醇、 咯菌腈、 氧化亚酮、 恶醚唑、 代森锌、 代森 锰锌、 福美双、敌菌丹、 异菌脲、 甲基菌核利、 曱乙菌核利、 己唑醇、 腈菌唑、 戊唑醇、 戊菌隆、 霜脲氰、 双胍辛醋酸盐、硫菌威、 环菌胺、 氟吗啉、 氟哇唑、 SSF-129 , picoxys trobin , metrafenone > pyraclos trobin、 resveratro 、 dimoxys trobin、 UBF-307 、 BASF490F, ICIA5504 、 TH- 164、 RH7592, 酯 菌脲、 烯唑醇、 氟酰脲、 多菌灵、 苯菌灵、 三唑酮、 环唑醇、 乙霉威、 甲基托 布津、 土菌消、 丁苯吗啉、 霜霉威、 甲霜灵、 呋霜灵、 苯霜灵、 恶酰胺、 磺菌 威、 啶斑肟、 苯 4秀啶、 嘧菌胺、 烯酰吗啉、 拌种咯、 拌种强、 丙环唑、 百菌清、 二嗪哝、 硫酸铜、 抑菌灵、 乙磷铝、 恶霉灵、 等。 By adding one or more other fungicides to the composition, it can be made more active than the compound (I) alone. In addition, other fungicides may have a synergistic effect on the fungicidal activity of the compound (I). Examples of fungicide compounds that may be included in the composition of the present invention: clotrimam, sterilant, azoxystrobin, tridemorpholine, chlorobenzene. Melidixol, flupronil, oxymethylene oxide, oxadiazole, zinc zem, mancozeb, formamide, dicarbendazol, isoxuron, methyl sclerotin, acetonitrile, hexazole Alcohol, Myclobutanil, Tebuconazole, Pentosalone, Cyproteril, Biguanide Acetate, Thiacarb, Cyclosporin, Flumorph, Fluoxazole, SSF-129, picoxys trobin, metrafenone> pyraclos trobin, resveratro, dimoxys trobin, UBF-307, BASF490F, ICIA5504, TH-164, RH7592, carbamuron, enazolol, fluoxuron, carbendazim, benomyl, benomyl , Triazolone, cycloconazole, ethicarb, methyltobrazine, terbendazim, butylmorpholine, metronidazole, metalaxyl, furasyl, benalaxyl, oxacarb, sulfacarb, Imidoxime, benzoxamidine, azoxystrobin, enosylmorpholine, seed dressing, dressing strength, propiconazole, chlorothalonil, diazine, copper sulfate, bacteriochlor, ethidium Mildew, etc.
可以与本发明的化合物混合形成组合物的杀虫剂有： 杀虫剂溴螨酯、 三氯 杀螨醇、 甲基 1605、 1605 , 杀螟松、 地亚农、 丁硫克百威、 毒死蝉、 锐尽特、 除尽、 灭多威、 杀虫单、 杀虫双、 巴丹、 阿维菌素、 氯菊酯、 氯氰菊酯、 胺菊 酯、 七氟菊酯、 氟氯氰菊酯、 氰戊菊酯、 氟虫脲、 杀虫脲、 定虫脲、 唑螨酯、 吡虫啉、 双氧威、 三唑磷、 喹螨酯、 杀螨隆、 哒螨灵、 四螨嗪等。  Insecticides that can be combined with the compounds of the present invention to form a composition include: insecticides bromomester, diclofenac, methyl 1605, 1605, fenitrothion, diamnon, bupropion, chlorpyrifos, sharp Exterminator, Exterminator, Methomyl, Insecticidal Mono, Insecticidal Double, Badan, Avermectin, Permethrin, Cypermethrin, Permethrin, Stefluthrin, Cyfluthrin, Fenvalerate, Fluoride Diflubenzuron, diflubenzuron, diflubenzuron, pyraclostrobin, imidacloprid, dioxocarb, triazophos, quinacloprid, chlorfenuron, pyridaben, tetrabenazine, etc.
为了获得在很小的剂量下就可以控制各种真菌病害化合物， 本发明发明者 们合成了其中的一些化合物，这些化合物具有广谱杀菌活性可用于防治作物上 的由藻菌纲、 卵菌纲、 子嚢菌纲和半知菌纲等多种真菌引起的病害， 而且由于 这一化合物具有艮高的生物活性使得在很低的剂量下就可以获得很好防治效 果。 本类化合物对白粉病、 霜霉病、 炭疽病表现出很好的生物活性外， 对葡萄 的黑痘病、 葡萄白锈病也有防治作用。  In order to obtain compounds that can control various fungal diseases at very small doses, the inventors have synthesized some of these compounds, which have broad-spectrum fungicidal activity and can be used to control crops from the class Algae and Oomycetes Diseases caused by a variety of fungi such as Zygomycetes and Deuteromycetes, and the high biological activity of this compound makes it possible to obtain good control effects at very low doses. These compounds show good biological activity against powdery mildew, downy mildew, and anthracnose, as well as controlling black pox and white rust of grapes.
本发明提供的化合物不但具有很高的生物活性， 而且对环境非常友好， 对 环境没有污染。本发明提供化合物不但具有很高的生物活性， 而且同世界类似 产品比较生产成本低， 是一个非常有前途的农用杀菌剂新品种。  The compounds provided by the present invention not only have high biological activity, but also are very friendly to the environment and have no pollution to the environment. The compound provided by the invention not only has high biological activity, but also has low production cost compared with similar products in the world, and is a very promising new agricultural fungicide.
具体实施方式 detailed description
通过以下具体的实例来对本发明进行详细的说明， 除非另外指明， 本申请 中的份数一重量计：  The present invention will be described in detail through the following specific examples. Unless otherwise specified, the parts in this application are by weight:
合成实施例：  Synthesis Example:
在室温下将 12. 2g 2, 5-二曱基苯酚加到 500ml盛有 150ml干燥丙酮的三 口瓶中， 然后加入 13. 8g 碳酸钾， 室温搅拌 20 分钟， 然后慢慢加入 28. 5g (E) -2- (2- (溴甲基)苯基) -3-曱氧基丙烯酸甲酯。然后回流反应 3小时结 束， 过滤， 浓缩， 得粗品。 用乙酸乙酯和石油醚的混合液（1: 4.)为洗脱液进行 柱层析得到化合物 I 26. 08g , 为白色固体， 收率为 80°/。。 熔点： 108 - 110°C, 1腿 MR: 2. 235 (3H, s) , 2. 279 (3Η, s) , 3. 706 (3H， s) , 3. 835 (3H, s)， 4. 944 (2H, s ) , 6. 584 (1H, s) At room temperature, 12.2g of 2,5-difluorenylphenol was added to a 500ml three-necked bottle containing 150ml of dry acetone, and then 13.8g of potassium carbonate was added, stirred at room temperature for 20 minutes, and then 28.5g (E ) Methyl-2- (2- (bromomethyl) phenyl) -3-methoxyoxyacrylate. The reaction was then refluxed for 3 hours to complete, filtered, and concentrated to obtain a crude product. Column chromatography was performed using a mixed solution of ethyl acetate and petroleum ether (1: 4) as the eluent to obtain Compound I 26. 08g as a white solid with a yield of 80 ° /. . Melting point: 108-110 ° C, 1 leg MR: 2. 235 (3H, s), 2. 279 (3Η, s), 3. 706 (3H, s), 3. 835 (3H, s), 4. 944 (2H, s ), 6. 584 (1H, s)
6. 655-6. 673 (1H, d) , 7. 013-7. 032 (1H, d)， 7. 164-7. 168 (2H, d)， 7. 300-7. 7. 382 (2H, m) , 7. 596 (1H, s) , 7. 617 (1H, s)  6. 655-6. 673 (1H, d), 7. 013-7. 032 (1H, d), 7. 164-7. 168 (2H, d), 7. 300-7. 7. 382 (2H , m), 7. 596 (1H, s), 7. 617 (1H, s)
注： 丽 R谱是用 CDC13溶剂记录。 在实验中所用的缩写如下： Note: Rei R spectra were recorded with CDC1 3 solvent. The abbreviations used in the experiments are as follows:
丽 R=核磁共振 s=单峰 d=双峰 m=多峰  Rei R = nuclear magnetic resonance s = singlet d = doublet m = multimodal
制剂实施例 1  Formulation Example 1
本发明的化合物 40公斤、 硅藻土 53公斤、 C12-20醇硫酸酯 4公斤、 十二 烷基苯磺酸钠 3公斤， 将以上成分均匀混合， 粉碎， 得含有效成分 40%的可湿 性粉剂。  40 kg of the compound of the present invention, 53 kg of diatomaceous earth, 4 kg of C12-20 alcohol sulfate, and 3 kg of sodium dodecylbenzenesulfonate. The above ingredients are uniformly mixed and pulverized to obtain a 40% wettability of the active ingredient. powder.
制剂实施例 2  Formulation Example 2
本发明的化物 30公斤、 二甲苯 33公斤、 二甲基曱酰胺 30公斤、 聚氧乙烯 烷基丙醚 7公斤， 将以上成分均匀混合、 溶解、 得含有效成分 30%的乳剂。  30 kg of the compound of the present invention, 33 kg of xylene, 30 kg of dimethylarsinamide, and 7 kg of polyoxyethylene alkylpropyl ether. The above ingredients are uniformly mixed and dissolved to obtain an emulsion containing 30% of the active ingredient.
制剂实施例 3  Formulation Example 3
本发明的化合物 10公斤、 滑石粉 89公斤、 聚氧乙烯烷基丙醚公斤， 将以 上成分均匀混合， 粉碎， 得含有效成分 10%的粉剂。  The compound of the present invention is 10 kg, talc powder is 89 kg, and polyoxyethylene alkyl propyl ether is kg. The above ingredients are uniformly mixed and pulverized to obtain a powder containing 10% of the active ingredient.
制剂实施例 4  Formulation Example 4
本发明的化合物 5公斤、 粘土 73公斤、 膨润土 20公斤、 二辛基硫代丁二 酸钠 1公斤、磷酸钠 1公斤，将以上成分均勾混合，充分粉碎后，加入适量水。 再充分混合， 造粒， 干燥后， 得含有效成分 5%的颗粒剂。  The compound of the present invention is 5 kg, clay is 73 kg, bentonite is 20 kg, sodium dioctyl thiosuccinate is 1 kg, and sodium phosphate is 1 kg. All the above ingredients are mixed and mixed thoroughly, and an appropriate amount of water is added. After further mixing, granulation and drying, granules containing 5% of the active ingredient are obtained.
制剂实施例 5  Formulation Example 5
本发明的化合物 10公斤，木质素磺酸钠 4公斤，十二烷基苯磺酸钠 1公斤， 黄原酸 1公斤， 水 84公斤， 将以上成分均匀混合， 湿式研磨到粒度为 1微米 以下， 得到含有效成分为 10%的胶悬剂。  10 kg of the compound of the present invention, 4 kg of sodium ligninsulfonate, 1 kg of sodium dodecylbenzenesulfonate, 1 kg of xanthogenic acid, and 84 kg of water. To obtain a suspension agent containing 10% of the active ingredient.
制剂实施例 6  Formulation Example 6
本发明化合物 8公斤、 代森锰锌 50公斤、 高岭土 30公斤、 十二垸基苯磺 酸钠 4公斤、 木质素磺酸钠 8公斤， 将上述成分混合， 充分粉碎后， 得混剂含 量为 58%的可湿性粉剂。  8 kg of the compound of the present invention, 50 kg of mancozeb, 30 kg of kaolin, 4 kg of sodium dodecylbenzenesulfonate, and 8 kg of sodium lignin sulfonate. After mixing the above components, the content of the mixture is obtained as follows: 58% wettable powder.
制剂实施例 7  Formulation Example 7
本发明化合物 1公斤、 三唑酮 20公斤、 高岭土 64公斤、 十二烷基苯 酸 钠 6公斤、 木质素磺酸钠 9公斤， 将以上成分均匀混合， 充分粉碎后， 得混合 含量为 21%的可湿性粉剂。 1 kg of the compound of the present invention, 20 kg of triazolone, 64 kg of kaolin, 6 kg of sodium dodecyl benzoate, and 9 kg of sodium lignin sulfonate. Wettable powder with 21% content.
药效实施例：  Examples of medicinal effects:
本发明的化合物， 同现有杀菌剂比具有很好的生物活性， 可以在很低的剂 量下很好地防治由真菌引起的病害 3 对白粉病、 锈病、 霜霉病、 炭疽病有特别 好的效果。 如小麦、 大麦的白粉病、 黄瓜白粉、 南瓜白粉、 草莓白粉病、 葡萄 白粉病， 小麦、 大麦锈病， 葡萄霜霉病、 黄瓜霜霉病， 黄瓜炭疽病。 另位对葡 萄黑痘病、 白锈病也有一定的抑制作用。 The compound of the present invention has good biological activity compared with existing fungicides, and can effectively prevent and treat diseases caused by fungi at very low doses. 3 It is particularly good for powdery mildew, rust, downy mildew, and anthracnose. Effect. Such as wheat, barley powdery mildew, cucumber powdery mildew, pumpkin powdery mildew, strawberry powdery mildew, grape powdery mildew, wheat, barley rust, grape downy mildew, cucumber downy mildew, cucumber anthracnose. Another one has a certain inhibitory effect on grapevine black pox and white rust.
药效实施例 1 : 防治黄瓜白粉病保护与治疗作用试验（室内）  Efficacy Example 1: Test of Protection and Treatment of Cucumber Powdery Mildew (Indoor)
试验药剂为本发明化合物 I (含量 5%的乳油）设 10 5 2. 5 1. 25 0. 625 0. 3125ppm六个浓度。 对照 ZA- 1963 (即先正达公司 icoxys trobin,即相似专 利中商品化的化合物）（含量 5%的乳油）设 10 5、 2. 5 1. 25 0. 625 0. 3125ppm 六个浓度。 对照药剂 20%三唑酮乳油， 设 100 50 25ppm0 选择生长至 2叶一 心期的盆栽两片真叶平展的黄瓜健苗喷药， 预防试验喷药后 24小时接种， 治 疗试验接种后 24小时喷药。 接种后黄瓜幼移置人工气候箱内保湿培养， 7天 后调查防效。 结果见表 1 : The test agent was Compound I of the present invention (emulsion oil with a content of 5%) and six concentrations of 10 5 2. 5 1. 25 0. 625 0. 3125 ppm were set. Control ZA-1963 (ie Syngenta's icoxys trobin, which is a commercial compound in a similar patent) (5% emulsifiable concentrate) was set at six concentrations of 10 5, 2. 5 1. 25 0. 625 0. 3125 ppm. Control agent 20% triazolone EC, set 100 50 25ppm 0 Select two potted cucumber plants growing from two leaves and one heart stage to spray the cucumber seedlings, spray for prevention test 24 hours after spraying, 24 hours after treatment test inoculation Spray medicine. After inoculation, young cucumbers were placed in an artificial climatic chamber for moisturizing culture, and the control effect was investigated 7 days later. The results are shown in Table 1:
表 1黄瓜白粉病保护与治疗作用试验结果：  Table 1 Test results of protection and treatment of cucumber powdery mildew:
黄瓜白粉病  Cucumber powdery mildew
药剂 浓度 (ppm)  Concentration (ppm)
预防效果（%) 治疗效果 (%)  Prevention effect (%) Treatment effect (%)
10 100 98. 89  10 100 98. 89
5 100 97. 53  5 100 97. 53
2. 5 97. 22 88. 89  2. 5 97. 22 88. 89
化合物（I)  Compound (I)
1. 25 90. 28 85. 71  1. 25 90. 28 85. 71
0. 625 85. 31 64. 81  0. 625 85. 31 64. 81
0. 315 63. 11 29. 63  0. 315 63. 11 29. 63
10 98. 15 86. 11  10 98. 15 86. 11
5 88. 89 68. 52  5 88. 89 68. 52
2. 5 81. 75 36. 11  2. 5 81. 75 36. 11
ZA-1963  ZA-1963
1. 25 75. 60  1. 25 75. 60
0. 625 47. 63 8. 33  0. 625 47. 63 8. 33
0. 315 41. 67 0. 0 „ 50 81. 25 0. 315 41. 67 0. 0 „50 81. 25
25 45. 40  25 45. 40
保护及治疗试验结果表明： 化合物 I预防略优于治疗。 0. 625ppm预防为 85. 31%, 治疗为 64. 81%。 同时发现化合物（I)的预防和治疗效果的明显活性优 于 ZA-1963 , 特别是治疗作用。 化合物 I的生物活性远远好于三唑酮。  The results of protection and treatment tests show that: Compound I prevention is slightly better than treatment. 0. 625ppm prevention was 85. 31%, and treatment was 64. 81%. At the same time, it was found that the significant activity of the preventive and therapeutic effects of compound (I) was better than ZA-1963, especially the therapeutic effect. The biological activity of compound I is much better than triazolone.
药效实施例 2 防治小麦白粉病保护与治疗作用试验（室内）  Efficacy Example 2 Test for Protection and Treatment of Wheat Powdery Mildew (Indoor)
试验药剂为本发明化合物 I (含量 5%的乳油）设 25、 12. 5 . 6. 25、 3. 125、 1. 563、 0. 781ppm六个浓度。 对照 ZA- 1963 (即先正达公司 picoxys trobin,即 相似专利中商品化的化合物) (含量 5%的乳油）设 25、 12. 5、 6. 25、 3. 125、 1. 563、 0. 781ppm六个浓度。 对照药剂 20%三唑酮乳油， 设 100、 50、 25ppm。 选择生 长至 2叶一心期的盆栽小麦喷药， 预防试验喷药后 24小时接种， 治疗试验接 种后 24小时喷药。 接种后小麦移置人工气候箱内保湿培养， 7天后调查防效。 结果见表 2  The test agent was Compound I of the present invention (emulsion oil with a content of 5%), and six concentrations of 25, 12.5.6.25, 3.125, 1.563, and 0.781 ppm were set. Control ZA-1963 (namely Syngenta's picoxys trobin, which is a compound commercialized in similar patents) (5% EC) is set to 25, 12. 5, 6. 25, 3. 125, 1. 563, 0. Six concentrations of 781ppm. Control agent 20% triazolone EC, set 100, 50, 25 ppm. The potted wheat growing up to the two-leaf one-heart stage was sprayed. The vaccine was inoculated 24 hours after spraying in the preventive test, and sprayed 24 hours after seeding in the treatment test. After the inoculation, the wheat was placed in an artificial climate chamber for moisturizing culture, and the control effect was investigated 7 days later. The results are shown in Table 2
表 2小表白粉病保护与治疗作用试验结果  Table 2 Test results of protection and treatment of powdery mildew
小麦白粉病  Wheat powdery mildew
药剂 浓度 (ppm)  Concentration (ppm)
预防效果（》/») 治疗效果（  Preventive effect (>> / ») Treatment effect (
25 100 100  25 100 100
12. 5 100 100  12. 5 100 100
6. 25 100 100  6. 25 100 100
化合物（I)  Compound (I)
3. 125 100 100  3. 125 100 100
1. 563 98. 33 97. 33  1. 563 98. 33 97. 33
0. 781 87. 43 84. 13  0. 781 87. 43 84. 13
25 100 99. 77  25 100 99. 77
12. 5 99. 60  12. 5 99. 60
6. 25 91. 30 82, 95  6. 25 91. 30 82, 95
ZA-1963  ZA-1963
3. 125 93. 61 73. 15  3. 125 93. 61 73. 15
1. 563 78. 18 71. 97  1. 563 78. 18 71. 97
0. 781 53. 05 38. 97  0. 781 53. 05 38. 97
三唑酮 100 50 Triazolone 100 50
25  25
保护及治疗试验结果表明：发现化合物 I的预防和治疗效果的明显活性优 于 ZA-1963, 治疗作用更加明显。 化合物 I的生物活性远远好于三唑酮。 药效实施例 3 对小麦白粉病模拟田间试验  The results of the protection and treatment tests showed that the obvious activity of the preventive and therapeutic effects of Compound I was found to be better than that of ZA-1963, and the therapeutic effect was more obvious. The biological activity of compound I is much better than triazolone. Efficacy Example 3 Simulated Field Test on Wheat Powdery Mildew
化合物（I)处理浓度为 50, 25 , 12. 5 , 6. 25 , 3. 125ppm,对照药剂 ZA- 1963 的处理浓度与化合物 I相同， 三唑酮的处理浓度为 100, 50, 25ppm0 将盆栽 小麦培养至 4- 5叶期，任其自然发病至中期，按上述所设浓度进行叶面喷雾处 理， 10天后调查防效。 结果见表 3 Compound (I) concentration was 50, 25, 12. 5, 6. 25, 3. 125ppm, a process control agent ZA- 1963 the same concentration of compound I, treatment concentration triadimefon of 100, 50, 25ppm 0 to Potted wheat was cultivated to the 4-5 leaf stage, and allowed to naturally develop to the middle stage. Foliar spray treatment was performed at the concentration set above, and the control effect was investigated after 10 days. The results are shown in Table 3.
表 3对小麦白粉病模拟田间试验  Table 3 Simulated field tests on powdery mildew of wheat
Figure imgf000011_0001
Figure imgf000011_0001
模拟田间试验结果表明， 化合物 I对盆栽小麦自然发病至中期时施药， 仍 表现出很高的防治作用， 并且防效优于对照药剂 ZA- 1963和三唑酮。  The results of simulated field tests showed that Compound I still showed a high control effect on pot wheat when it was spontaneous to mid-term, and its control effect was better than the control agents ZA-1963 and triazolone.
药效实施例 4 持效期试验  Example of efficacy 4 Duration test
化合物 I和对照药剂 ZA-1963的处理浓度为 50, 25mg/l , 测试对象为小麦 白粉病。 在盆栽小麦两片真叶平展时喷药， 喷药后 24小时接种小麦白粉菌， 接种后的小麦移至温室内保湿培养， 处理后 7、 10、 15、 20、 25、 30天调查防 效。 结果见表 4 表 4持效期试验结果 The treatment concentration of Compound I and the control agent ZA-1963 was 50, 25 mg / l, and the test object was wheat powdery mildew. Spray the two real leaves of potted wheat when they are flat, inoculate the powdery mildew of wheat 24 hours after spraying, move the inoculated wheat to the greenhouse for moisturizing culture, and investigate the prevention effect at 7, 10, 15, 20, 25, and 30 days after treatment . The results are shown in Table 4. Table 4 Validity period test results
Figure imgf000012_0001
Figure imgf000012_0001
持效期试验表明： 在温室人工接种的条件下， 化合物 I的持效期比 ZA - 1963略长。  The duration test showed that the duration of Compound I was slightly longer than that of ZA-1963 under artificial greenhouse inoculation.
药效实施例 5 对南瓜白粉病的防效试验（田间 )  Efficacy Example 5 Control Effect on Pumpkin Powdery Mildew (Field)
田间防效南瓜白粉病试验 2002年 6月在浙江绍兴市现代农业园区的大棚内 进行。  A field trial of pumpkin powdery mildew control in June 2002 was conducted in a greenhouse in a modern agricultural park in Shaoxing, Zhejiang.
化合物 I (10%水悬剂）设 50, 25 , 12. 5 , 6. 25ppm 四个浓度， 对照药剂为 20%粉锈宁 EC设浓度为 100ppm。 另设清水对照。 每处理 4次重复。 施药 7天 后调查。 结果见表 5 表 5对南瓜白粉病的防效试验（田间）结果  Compound I (10% aqueous suspension) was set at four concentrations of 50, 25, 12.5, and 6.25ppm, and the control agent was 20% fentanin EC and the concentration was set at 100ppm. Another set of water control. Each treatment was repeated 4 times. Investigation was made 7 days after application. The results are shown in Table 5. Table 5 Results of Control Tests (Field) on Pumpkin Powdery Mildew
Figure imgf000012_0002
Figure imgf000012_0002
注： CK防效栏为病指增加值。  Note: The CK prevention effect column is the added value of sick fingers.
从表 5中可以看出：化合物在 6. 25ppm对南瓜白粉有很高的活性，明显优于 对照药剂粉锈宁。  It can be seen from Table 5 that the compound has a high activity on pumpkin white powder at 6.25 ppm, which is significantly better than that of the control agent Fenning.
药效实施例 6 对黄瓜白粉病的防效试验（田间 )  Effectiveness example 6 Control test for cucumber powdery mildew (field)
田间防治黄瓜白粉病试验 2002年 6月在浙江绍兴市现代农业园区的大棚内进 行。 化合物 I (10%水悬剂）设 50, 25 , 12. 5 , 6. 25ppm 四个浓度， 对照药剂为 20%粉锈宁 EC设浓度为 100ppm。 另设清水对照。 每处理 4次重复。 施药 7天 后调查。 结果见表 6 A field trial of cucumber powdery mildew in June 2002 was conducted in a greenhouse in a modern agricultural park in Shaoxing, Zhejiang. Compound I (10% aqueous suspension) was set at four concentrations of 50, 25, 12. 5 and 6. 25 ppm, and the control agent was 20% fentanin EC and the concentration was set at 100 ppm. Another set of water control. Each treatment was repeated 4 times. Investigation 7 days after application. The results are shown in Table 6.
表 6对黄瓜白粉病的防效试验（田间）结果  Table 6 Results of field tests on cucumber powdery mildew
Figure imgf000013_0001
Figure imgf000013_0001
注： CK防效栏为病指增加值。  Note: The CK prevention effect column is the added value of sick fingers.
从表 6中可以看出：化合物 I在 6. 25ppm对黄瓜白粉有很高的活性， 明显 优于对照药剂粉锈宁。  It can be seen from Table 6 that Compound I has a high activity on cucumber white powder at 6.25 ppm, which is significantly better than that of the control agent Fenning.
药效实施例 7 化合物（I)对黄瓜霜霉病防效试验（室内）  Efficacy Example 7 Compound (I) Test for Cucumber Downy Mildew (Indoor)
化合物 I处理浓度为 100 , 50， 25 , 12. 5 , 6. 25ppm, 对照药剂 ZA-1963 的处理浓度与化合物 I相同， 甲霜灵处理浓度为 500ppm。 选择生长至 1叶一 心期的盆栽两片真叶平展的黄瓜健苗喷药， 预防试验喷药后 24小时接种， 治 疗试验接种后 24 小时喷药。 接种后黄瓜幼移置人工气候箱内保湿培养， 7天 后调查防效， 结果见表 7  The treatment concentration of compound I was 100, 50, 25, 12.5, 6.25 ppm. The treatment concentration of the control agent ZA-1963 was the same as that of compound I, and the treatment concentration of metalaxyl was 500 ppm. Select two potted cucumber plants that grow to one leaf and one heart period to spray the cucumber seedlings. Spray for 24 hours after spraying for prevention test and spray for 24 hours after treatment test. After inoculation, young cucumbers were placed in an artificial climate chamber for moisturizing culture, and the control effect was investigated after 7 days. The results are shown in Table 7
表 7对黄瓜霜霉病的防效试验（室内）结果 药剂 浓度 (ppm) 防效（%)  Table 7 Results of laboratory test on indoor downy mildew (indoor) Concentration (ppm) Control effectiveness (%)
化合物（I) 100 100  Compound (I) 100 100
50 100  50 100
25 100  25 100
12. 5 97. 18  12. 5 97. 18
6. 25 91. 55  6. 25 91. 55
3. 125 77. 46  3. 125 77. 46
100 91. 55 50 60. 56 100 91. 55 50 60. 56
25 46. 48  25 46. 48
12. 5 40. 84  12. 5 40. 84
6. 25 26. 76  6. 25 26. 76
3. 125 9. 86  3. 125 9. 86
T相 500 70. 11 在温室条件下化合物 I对黄瓜霜霉病的防效在相同浓度下明显优于对照 药剂 ZA-1963 , 明显优于甲霜灵。 药效实施例 8 对葡萄霜霉病的防效试验（田间）  Phase T 500 70. 11 Under greenhouse conditions, the control effect of compound I on cucumber downy mildew was significantly better than the control agent ZA-1963 at the same concentration, and it was significantly better than metalaxyl. Efficacy Example 8 Control effect on grape downy mildew (field)
田间防治葡萄霜霉病试验 2002年 7月在安微省马鞍山市当涂县石桥乡农 业科技示范场进行。  A field trial to control grape downy mildew was conducted in July 2002 at the Agricultural Science and Technology Demonstration Farm in Shiqiao Township, Dangtu County, Ma'anshan City, Anwei Province.
化合物 I (5%乳油）设 200, 100, 50 , 25 , 12. 5ppm五个浓度， 对照药剂 72%杜邦克露可湿性粉剂设 l OOOppm浓度。 另设空白对照， 每处理重复 4次。 喷药 Ί天后调查。 结果如表 8  Compound I (5% emulsifiable concentrate) was set at five concentrations of 200, 100, 50, 25, 12.5 ppm, and the control agent was 72% DuPont Crewe wettable powder at a concentration of 1000 ppm. A blank control was set up, and each treatment was repeated 4 times. Investigation after spraying the next day. The results are shown in Table 8.
表 8对葡萄霜霉病的防效试验（田间）结果  Table 8 Results of control experiments (field) on grape downy mildew
Figure imgf000014_0001
Figure imgf000014_0001
从结果可以看出， 化合物 I在防治葡萄霜霉在 200ppm 与对照药克露 l OOOppm相当。  From the results, it can be seen that Compound I is equivalent to 200 ppm of Cremonol at a control level of 200 ppm in the control of Plasmopara viticola.
药效实施例 9 对黄瓜霜霉病的防效试验（田间）  Effectiveness Example 9 Control effect on cucumber downy mildew (field)
田间防治黄瓜霜霉病试验 2002年 7月在安微省马鞍山市当涂县石桥乡农 业科技示范场进行。 Field trial of cucumber downy mildew control in July 2002 in Shiqiao Township, Dangtu County, Maanshan City, Anwei Province Industry technology demonstration site.
化合物 I (5%乳油）设 200, 100, 50 , 25， 12. 5ppm五个浓度， 对照药剂 Compound I (5% emulsifiable concentrate) was set at five concentrations of 200, 100, 50, 25, 12. 5 ppm.
72%杜邦克露可湿性粉剂设 1000ppm。 另设空白对照， 每处理重复 4次。 喷药 7 天后调查。 结果如表 9 The 72% DuPont Crewe wettable powder is set at 1000 ppm. A blank control was set up, and each treatment was repeated 4 times. Investigation 7 days after spraying. The results are shown in Table 9
表 9对黄瓜霜霉病的防效试验 (田间）结果  Table 9 Results of field trials of cucumber downy mildew
Figure imgf000015_0001
从结果可以看出， 化合物 I在防治黄瓜霜霉在 200ppm 与对照药克露 l OOOppm相当。 药效实施例 10 对黄瓜炭疽病防效果试验（室内）
Figure imgf000015_0001
It can be seen from the results that the compound I in controlling cucumber downy mildew at 200 ppm is equivalent to the control drug Kelu lOOppm. Effectiveness Example 10 Test on Cucumber Anthrax (Indoor)
化合物 I和对照药剂 ZA- 1963 的处理浓度为 500 , 250, 125, 62. 5 , 31. 25ppm。 测试对象为黄瓜炭疽病， 盆栽黄瓜苗生长至一张真叶期时喷药， 喷 药 24 小时后接种炭疽病孢子悬浮液， 接种后移入人工气候箱内， 保持湿度 100%, 温度为 20度， 接种 24小时后保持相对湿度为 85%。 7天后进行调查。 结果见表 10  The treatment concentration of compound I and the control agent ZA-1963 was 500, 250, 125, 62.5, 31. 25 ppm. The test object was cucumber anthracnose. The potted cucumber seedlings were sprayed when they grew to a true leaf stage. The anthracnose spore suspension was inoculated after spraying for 24 hours. After the inoculation, they were moved to an artificial climate chamber and the humidity was maintained at 100%. The relative humidity should be 85% after 24 hours of inoculation. Investigation was conducted after 7 days. The results are shown in Table 10.
表 10对黄瓜炭疽病试验结果（室内） 药剂 浓度（ppm) 防效 (%)  Table 10 Test results of cucumber anthracnose (indoor) Concentration (ppm) Control effect (%)
化合物（I) 500 98. 51  Compound (I) 500 98. 51
250 89. 94  250 89. 94
125 88. 02 125 88. 02
Figure imgf000016_0001
Figure imgf000016_0001
在温室条件下化合物 I对黄瓜炭疽病的防效在相同浓度下略优于对照药 -1963  Under greenhouse conditions, the control effect of compound I on cucumber anthracnose is slightly better than the control drug at the same concentration -1963

Claims

权利要求书 Claim
1. 一种甲氧基丙烯酸甲酯类化合物杀菌剂组合物， 其特征在于组合物中 包含具有化学结构式 (I)的化合物及其异构体：
Figure imgf000017_0001
1. A fungicide composition of methyl methacrylate compound, characterized in that the composition contains a compound having chemical structural formula (I) and isomers thereof:
Figure imgf000017_0001
2. 根据权利要求 1所述的杀菌剂组合物， 其特征在于有效成分（I)在制剂 中所占有的比例为 0. 1 - 99. 0%重量。 2. The fungicide composition according to claim 1, characterized in that the proportion of the active ingredient (I) in the preparation is from 0.1 to 99.0% by weight.
3.根据权利要求 1 , 2所述的杀菌剂组合物，其特征在于可将有效成分（I) 配制成乳剂、 粉剂、 可湿性粉剂、 胶悬剂、 颗粒剂。  3. The fungicide composition according to claim 1, wherein the active ingredient (I) can be formulated into an emulsion, a powder, a wettable powder, a suspension, and a granule.
4. 根据上述任一权利要求的组合物的使用方法， 其特征在于可单独使用 上述组合物也可和 1种或 2种以上的杀菌剂、杀虫剂、除草剂或植物生长调节 剂复配成二元或三元混合制剂应用。  4. A method for using a composition according to any one of the preceding claims, characterized in that the above composition can be used alone or in combination with one or two or more fungicides, insecticides, herbicides or plant growth regulators Application as a binary or ternary mixed preparation.
5. 根据权利要求 4的组合物的使用方法， 其特征在于使用到作物上防治 在各种作物上由藻菌纲、卵菌纲、子嚢菌纲和半知菌纲等多种真菌引起的病害。  5. The method of using the composition according to claim 4, characterized in that it is applied to crops to prevent and treat diseases caused by various fungi such as Algae, Oomycetes, Zygomycetes, and Deuteromycetes on various crops .
6. 根据权利要求 4的组合物的使用方法， 其特征在于使用到作物上防治 麦类白粉病、瓜类白粉病、 麦类锈病、蔬菜白粉病、 水果白粉病、花类白粉病； 黄瓜霜霉病、 葡萄霜霉病； 黄瓜炭疽病。  6. The method of using the composition according to claim 4, characterized in that it is used to control wheat powdery mildew, melons powdery mildew, wheat powdery mildew, vegetable powdery mildew, fruit powdery mildew, and powdery mildew on crops; Mildew, grape downy mildew; cucumber anthracnose.
7. 一种杀菌剂化合物， 其特征在于化合物为权利要求 1的式（I)的化合物 及其异构体
Figure imgf000017_0002
7. A fungicide compound, characterized in that the compound is a compound of the formula (I) and its isomers according to claim 1.
Figure imgf000017_0002
8.根据权利要求 7的化合物的制备方法,其特征在于在碱性条件下使（I I) 化合物与（I I I)化合物反应得到化合物（I)
Figure imgf000018_0001
The method for preparing a compound according to claim 7, characterized in that the compound (I) is reacted with the compound (III) under basic conditions to obtain the compound (I)
Figure imgf000018_0001
II III I  II III I
其中 in中 X为离去基团， 必要时反应可在溶剂存在下进行。 Wherein X is a leaving group, and the reaction may be performed in the presence of a solvent if necessary.
9. 根据权利要求 7的化合物的制备方法， 其特征在于反应的过程如下:  9. A method for preparing a compound according to claim 7, characterized in that the reaction process is as follows:
Figure imgf000018_0002
Figure imgf000018_0002
Figure imgf000018_0003
Figure imgf000018_0003
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2565180A4 (en) * 2010-04-21 2014-02-05 Oscotec Inc Alpha-arylmethoxyacrylate derivative, preparation method thereof, and pharmaceutical composition containing same

Families Citing this family (173)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100401889C (en) * 2005-08-17 2008-07-16 浙江化工科技集团有限公司 Fungicide composition
CN101524076B (en) * 2005-08-17 2012-11-07 浙江省化工研究院有限公司 Fungicide composition
CN101642119B (en) * 2009-08-24 2013-06-05 陕西上格之路生物科学有限公司 Agricultural sterilizing composition containing kresoxim-methyl benzene
CN102115458B (en) * 2010-11-25 2019-12-13 大连九信精细化工有限公司 Synthetic method of 3-methoxy-2-aryl methyl acrylate compound
CN102919240B (en) * 2010-12-08 2014-08-13 陕西美邦农药有限公司 Tridemorph-containing sterilizing composition
CN102835399B (en) * 2012-09-27 2014-04-30 陕西上格之路生物科学有限公司 Metrafenone-containing bactericidal composition
CN103975927B (en) * 2013-04-07 2016-06-08 海南正业中农高科股份有限公司 A kind of bactericidal composition containing cyflufenamid and pyraoxystrobin or ZJ0712 and application
CN103598193B (en) * 2013-10-23 2015-04-01 江苏丰登作物保护股份有限公司 Picoxystrobin and thiram containing sterilization composition and application thereof
PL3214937T3 (en) 2014-11-07 2024-10-14 Basf Se Pesticidal mixtures
WO2016174042A1 (en) 2015-04-27 2016-11-03 BASF Agro B.V. Pesticidal compositions
EP3371177A1 (en) 2015-11-02 2018-09-12 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
BR112018008288A2 (en) 2015-11-04 2018-10-30 Basf Se use of formula compounds, formula compounds, mixture, agrochemical composition and method for combating fungi
BR112018009579A2 (en) 2015-11-13 2018-11-06 Basf Se compound of formula i, mixture, agrochemical composition, compound use and fungal control method
BR112018009566A2 (en) 2015-11-13 2018-11-06 Basf Se compounds, mixture, agrochemical composition, use of compounds and method to combat phytopathogenic harmful fungi
JP2019502661A (en) 2015-11-19 2019-01-31 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ Substituted oxadiazoles for controlling plant pathogens
WO2017085100A1 (en) 2015-11-19 2017-05-26 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3202267A1 (en) 2016-02-05 2017-08-09 Basf Se Pesticidal mixtures
EP3205208A1 (en) 2016-02-09 2017-08-16 Basf Se Mixtures and compositions comprising paenibacillus strains or fusaricidins and chemical pesticides
US20190098899A1 (en) 2016-03-10 2019-04-04 Basf Se Fungicidal mixtures iii comprising strobilurin-type fungicides
BR112018068695B1 (en) 2016-03-16 2022-12-27 Basf Se USE OF A COMPOUND AND METHOD TO CONTROL PHYTOPATHOGENIC FUNGI
WO2017157910A1 (en) 2016-03-16 2017-09-21 Basf Se Use of tetrazolinones for combating resistant phytopathogenic fungi on cereals
BR112018068705B1 (en) 2016-03-16 2022-09-06 Basf Se METHOD TO CONTROL PHYTOPATOGENIC FUNGI
CA3020532A1 (en) 2016-04-11 2017-10-19 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CN105766919A (en) * 2016-04-22 2016-07-20 广东中迅农科股份有限公司 Bactericidal composition containing triflumizole and (E)2-[2-(2, 5-dimethylphenoxytoluene)-phenyl]-3-methoxyacrylate
US20190200612A1 (en) 2016-09-13 2019-07-04 Basf Se Fungicidal mixtures i comprising quinoline fungicides
WO2018054723A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054721A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018054711A1 (en) 2016-09-26 2018-03-29 Basf Se Pyridine compounds for controlling phytopathogenic harmful fungi
WO2018065182A1 (en) 2016-10-04 2018-04-12 Basf Se Reduced quinoline compounds as antifuni agents
WO2018073110A1 (en) 2016-10-20 2018-04-26 Basf Se Quinoline compounds as fungicides
EP3555056A1 (en) 2016-12-19 2019-10-23 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3339297A1 (en) 2016-12-20 2018-06-27 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
EP3338552A1 (en) 2016-12-21 2018-06-27 Basf Se Use of a tetrazolinone fungicide on transgenic plants
US20190359589A1 (en) 2017-01-23 2019-11-28 Basf Se Fungicidal pyridine compounds
WO2018149754A1 (en) 2017-02-16 2018-08-23 Basf Se Pyridine compounds
EP3585773B1 (en) 2017-02-21 2021-04-07 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
AU2018241628B2 (en) 2017-03-31 2022-03-17 Basf Se Pyrimidinium compounds and their mixtures for combating animal pests
US20200187500A1 (en) 2017-04-06 2020-06-18 Basf Se Pyridine compounds
CA3056347A1 (en) 2017-04-07 2018-10-11 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
WO2018188962A1 (en) 2017-04-11 2018-10-18 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
CN110678442A (en) 2017-04-20 2020-01-10 Pi工业有限公司 New aniline compounds
WO2018202428A1 (en) 2017-05-02 2018-11-08 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
WO2018202487A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted 5-(haloalkyl)-5-hydroxy-isoxazoles for combating phytopathogenic fungi
WO2018202491A1 (en) 2017-05-04 2018-11-08 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2018202737A1 (en) 2017-05-05 2018-11-08 Basf Se Fungicidal mixtures comprising triazole compounds
WO2018210658A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210660A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210659A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
WO2018210661A1 (en) 2017-05-15 2018-11-22 Basf Se Heteroaryl compounds as agrochemical fungicides
UA126679C2 (en) 2017-05-30 2023-01-11 Басф Се Pyridine and pyrazine compounds
WO2018219797A1 (en) 2017-06-02 2018-12-06 Basf Se Substituted oxadiazoles for combating phytopathogenic fungi
US20200190043A1 (en) 2017-06-19 2020-06-18 Basf Se 2-[[5-(trifluoromethyl)-1,2,4-oxadiazol-3-yl]aryloxy](thio)acetamides for combating phytopathogenic fungi
WO2019002158A1 (en) 2017-06-30 2019-01-03 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019025250A1 (en) 2017-08-04 2019-02-07 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019038042A1 (en) 2017-08-21 2019-02-28 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
EP3915379A1 (en) 2017-08-29 2021-12-01 Basf Se Pesticidal mixtures
WO2019042932A1 (en) 2017-08-31 2019-03-07 Basf Se Method of controlling rice pests in rice
EP3453706A1 (en) 2017-09-08 2019-03-13 Basf Se Pesticidal imidazole compounds
EP3684761A1 (en) 2017-09-18 2020-07-29 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019057660A1 (en) 2017-09-25 2019-03-28 Basf Se Indole and azaindole compounds with substituted 6-membered aryl and heteroaryl rings as agrochemical fungicides
US11399543B2 (en) 2017-10-13 2022-08-02 Basf Se Substituted 1,2,3,5-tetrahydroimidazo[1,2-a]pyrimidiniumolates for combating animal pests
US11147275B2 (en) 2017-11-23 2021-10-19 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
WO2019115511A1 (en) 2017-12-14 2019-06-20 Basf Se Fungicidal mixture comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
US11839214B2 (en) 2017-12-15 2023-12-12 Basf Se Fungicidal mixture comprising substituted pyridines
US20200337311A1 (en) 2017-12-20 2020-10-29 Pi Industries Ltd. Fluoralkenyl compounds, process for preparation and use thereof
WO2019121143A1 (en) 2017-12-20 2019-06-27 Basf Se Substituted cyclopropyl derivatives
IL275726B2 (en) 2018-01-09 2024-06-01 Basf Se Hetaryl silylethynyl compounds as nitrification inhibitors
WO2019137995A1 (en) 2018-01-11 2019-07-18 Basf Se Novel pyridazine compounds for controlling invertebrate pests
WO2019150311A1 (en) 2018-02-02 2019-08-08 Pi Industries Ltd. 1-3 dithiol compounds and their use for the protection of crops from phytopathogenic microorganisms
CA3088722A1 (en) 2018-02-07 2019-08-15 Basf Se New pyridine carboxamides
WO2019154665A1 (en) 2018-02-07 2019-08-15 Basf Se New pyridine carboxamides
EP3530118A1 (en) 2018-02-26 2019-08-28 Basf Se Fungicidal mixtures
EP3530116A1 (en) 2018-02-27 2019-08-28 Basf Se Fungicidal mixtures comprising xemium
WO2019166252A1 (en) 2018-02-28 2019-09-06 Basf Se Fungicidal mixtures comprising fenpropidin
IL297413B2 (en) 2018-02-28 2024-07-01 Basf Se Use of alkoxypyrazoles as nitrification inhibitors
CA3089381A1 (en) 2018-02-28 2019-09-06 Basf Se Use of pyrazole propargyl ethers as nitrification inhibitors
WO2019166560A1 (en) 2018-02-28 2019-09-06 Basf Se Use of n-functionalized alkoxy pyrazole compounds as nitrification inhibitors
WO2019166257A1 (en) 2018-03-01 2019-09-06 BASF Agro B.V. Fungicidal compositions of mefentrifluconazole
EP3533333A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3533331A1 (en) 2018-03-02 2019-09-04 Basf Se Fungicidal mixtures comprising pydiflumetofen
EP3536150A1 (en) 2018-03-06 2019-09-11 Basf Se Fungicidal mixtures comprising fluxapyroxad
WO2019175713A1 (en) 2018-03-14 2019-09-19 Basf Corporation New catechol molecules and their use as inhibitors to p450 related metabolic pathways
WO2019175712A1 (en) 2018-03-14 2019-09-19 Basf Corporation New uses for catechol molecules as inhibitors to glutathione s-transferase metabolic pathways
WO2019219464A1 (en) 2018-05-15 2019-11-21 Basf Se Substituted trifluoromethyloxadiazoles for combating phytopathogenic fungi
JP7433244B2 (en) * 2018-05-15 2024-02-19 ビーエーエスエフ ソシエタス・ヨーロピア Mixtures containing benzpyrimoxane and oxazosulfil and methods of use and application thereof
WO2019224092A1 (en) 2018-05-22 2019-11-28 Basf Se Pesticidally active c15-derivatives of ginkgolides
WO2020002472A1 (en) 2018-06-28 2020-01-02 Basf Se Use of alkynylthiophenes as nitrification inhibitors
US12151991B2 (en) 2018-07-23 2024-11-26 Basf Se Use of a substituted thiazolidine compound as nitrification inhibitor
ES2983787T3 (en) 2018-07-23 2024-10-24 Basf Se Use of substituted 2-thiazolines as nitrification inhibitors
TW202009235A (en) 2018-08-17 2020-03-01 印度商皮埃企業有限公司 1,2-dithiolone compounds and use thereof
EP3613736A1 (en) 2018-08-22 2020-02-26 Basf Se Substituted glutarimide derivatives
EP3628156A1 (en) 2018-09-28 2020-04-01 Basf Se Method for controlling pests of sugarcane, citrus, rapeseed, and potato plants
EP3628158A1 (en) 2018-09-28 2020-04-01 Basf Se Pesticidal mixture comprising a mesoionic compound and a biopesticide
WO2020064492A1 (en) 2018-09-28 2020-04-02 Basf Se Method of controlling pests by seed treatment application of a mesoionic compound or mixture thereof
EP3628157A1 (en) 2018-09-28 2020-04-01 Basf Se Method of controlling insecticide resistant insects and virus transmission to plants
EP3643705A1 (en) 2018-10-24 2020-04-29 Basf Se Pesticidal compounds
WO2020095161A1 (en) 2018-11-05 2020-05-14 Pi Industries Ltd. Nitrone compounds and use thereof
EP3670501A1 (en) 2018-12-17 2020-06-24 Basf Se Substituted [1,2,4]triazole compounds as fungicides
EP3696177A1 (en) 2019-02-12 2020-08-19 Basf Se Heterocyclic compounds for the control of invertebrate pests
BR112021015521A2 (en) 2019-02-20 2021-10-05 Basf Se PESTICIDE MIXTURES, METHOD TO CONTROL HARMFUL PHYTOPATOGENIC FUNGI AND METHOD TO PROTECT GROWING PLANTS OR PLANT PROPAGATION MATERIALS FROM ATTACK OR INFESTATION BY INVERTEBRATE PESTS
EP3730489A1 (en) 2019-04-25 2020-10-28 Basf Se Heteroaryl compounds as agrochemical fungicides
EP3975718A1 (en) 2019-05-29 2022-04-06 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
EP3769623A1 (en) 2019-07-22 2021-01-27 Basf Se Mesoionic imidazolium compounds and derivatives for combating animal pests
KR20220017940A (en) 2019-06-06 2022-02-14 바스프 에스이 fungicidal N-(pyrid-3-yl)carboxamide
WO2020244969A1 (en) 2019-06-06 2020-12-10 Basf Se Pyridine derivatives and their use as fungicides
WO2020244970A1 (en) 2019-06-06 2020-12-10 Basf Se New carbocyclic pyridine carboxamides
EP3766879A1 (en) 2019-07-19 2021-01-20 Basf Se Pesticidal pyrazole derivatives
WO2021063735A1 (en) 2019-10-02 2021-04-08 Basf Se New bicyclic pyridine derivatives
WO2021063736A1 (en) 2019-10-02 2021-04-08 Basf Se Bicyclic pyridine derivatives
WO2021130143A1 (en) 2019-12-23 2021-07-01 Basf Se Enzyme enhanced root uptake of agrochemical active compound
WO2021170463A1 (en) 2020-02-28 2021-09-02 BASF Agro B.V. Methods and uses of a mixture comprising alpha-cypermethrin and dinotefuran for controlling invertebrate pests in turf
WO2021175669A1 (en) 2020-03-04 2021-09-10 Basf Se Use of substituted 1,2,4-oxadiazoles for combating phytopathogenic fungi
WO2021209360A1 (en) 2020-04-14 2021-10-21 Basf Se Fungicidal mixtures comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
WO2021219513A1 (en) 2020-04-28 2021-11-04 Basf Se Pesticidal compounds
EP3903583A1 (en) 2020-04-28 2021-11-03 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 iii
EP3903584A1 (en) 2020-04-28 2021-11-03 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 iv
EP3903581A1 (en) 2020-04-28 2021-11-03 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 i
EP3903582A1 (en) 2020-04-28 2021-11-03 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 ii
EP3909950A1 (en) 2020-05-13 2021-11-17 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP3945089A1 (en) 2020-07-31 2022-02-02 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 v
WO2021249800A1 (en) 2020-06-10 2021-12-16 Basf Se Substituted [1,2,4]triazole compounds as fungicides
EP3960727A1 (en) 2020-08-28 2022-03-02 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 vi
EP3939961A1 (en) 2020-07-16 2022-01-19 Basf Se Strobilurin type compounds and their use for combating phytopathogenic fungi
WO2022017836A1 (en) 2020-07-20 2022-01-27 BASF Agro B.V. Fungicidal compositions comprising (r)-2-[4-(4-chlorophenoxy)-2-(trifluoromethyl)phenyl]-1- (1,2,4-triazol-1-yl)propan-2-ol
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
AR123594A1 (en) 2020-09-26 2022-12-21 Pi Industries Ltd NEMATICIDAL COMPOUNDS AND THEIR USE
EP4236691A1 (en) 2020-10-27 2023-09-06 BASF Agro B.V. Compositions comprising mefentrifluconazole
WO2022090069A1 (en) 2020-11-02 2022-05-05 Basf Se Compositions comprising mefenpyr-diethyl
WO2022090071A1 (en) 2020-11-02 2022-05-05 Basf Se Use of mefenpyr-diethyl for controlling phytopathogenic fungi
WO2022106304A1 (en) 2020-11-23 2022-05-27 BASF Agro B.V. Compositions comprising mefentrifluconazole
EP4018830A1 (en) 2020-12-23 2022-06-29 Basf Se Pesticidal mixtures
WO2022167488A1 (en) 2021-02-02 2022-08-11 Basf Se Synergistic action of dcd and alkoxypyrazoles as nitrification inhibitors
EP4043444A1 (en) 2021-02-11 2022-08-17 Basf Se Substituted isoxazoline derivatives
WO2022238157A1 (en) 2021-05-11 2022-11-17 Basf Se Fungicidal mixtures comprising substituted 3-phenyl-5-(trifluoromethyl)-1,2,4-oxadiazoles
US20240294544A1 (en) 2021-05-18 2024-09-05 Basf Se New substituted pyridines as fungicides
CN117355520A (en) 2021-05-18 2024-01-05 巴斯夫欧洲公司 Novel substituted quinolines as fungicides
WO2022243111A1 (en) 2021-05-18 2022-11-24 Basf Se New substituted pyridines as fungicides
CA3219128A1 (en) 2021-05-21 2022-11-24 Barbara Nave Use of an n-functionalized alkoxy pyrazole compound as nitrification inhibitor
EP4341245A1 (en) 2021-05-21 2024-03-27 Basf Se Use of ethynylpyridine compounds as nitrification inhibitors
EP4094579A1 (en) 2021-05-28 2022-11-30 Basf Se Pesticidal mixtures comprising metyltetraprole
US20240309022A1 (en) 2021-06-21 2024-09-19 Basf Se Metal-Organic Frameworks with Pyrazole-Based Building Blocks
EP4119547A1 (en) 2021-07-12 2023-01-18 Basf Se Triazole compounds for the control of invertebrate pests
AU2022323668A1 (en) 2021-08-02 2024-02-15 Basf Se (3-quinolyl)-quinazoline
AU2022321882A1 (en) 2021-08-02 2024-02-15 Basf Se (3-pirydyl)-quinazoline
EP4140986A1 (en) 2021-08-23 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4140995A1 (en) 2021-08-27 2023-03-01 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4151631A1 (en) 2021-09-20 2023-03-22 Basf Se Heterocyclic compounds for the control of invertebrate pests
WO2023072671A1 (en) 2021-10-28 2023-05-04 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 ix
WO2023072670A1 (en) 2021-10-28 2023-05-04 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 x
EP4194453A1 (en) 2021-12-08 2023-06-14 Basf Se Pyrazine compounds for the control of invertebrate pests
EP4198033A1 (en) 2021-12-14 2023-06-21 Basf Se Heterocyclic compounds for the control of invertebrate pests
EP4198023A1 (en) 2021-12-16 2023-06-21 Basf Se Pesticidally active thiosemicarbazone compounds
EP4238971A1 (en) 2022-03-02 2023-09-06 Basf Se Substituted isoxazoline derivatives
WO2023203066A1 (en) 2022-04-21 2023-10-26 Basf Se Synergistic action as nitrification inhibitors of dcd oligomers with alkoxypyrazole and its oligomers
CN119894889A (en) 2022-08-02 2025-04-25 巴斯夫欧洲公司 Pyrazolo pesticidal compounds
EP4342885A1 (en) 2022-09-20 2024-03-27 Basf Se N-(3-(aminomethyl)-phenyl)-5-(4-phenyl)-5-(trifluoromethyl)-4,5-dihydroisoxazol-3-amine derivatives and similar compounds as pesticides
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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914128A (en) * 1985-12-20 1990-04-03 Basf Aktiengesellschaft Acrylates and fungicides which contain these compounds

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4914128A (en) * 1985-12-20 1990-04-03 Basf Aktiengesellschaft Acrylates and fungicides which contain these compounds

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2565180A4 (en) * 2010-04-21 2014-02-05 Oscotec Inc Alpha-arylmethoxyacrylate derivative, preparation method thereof, and pharmaceutical composition containing same
US8772290B2 (en) 2010-04-21 2014-07-08 Oscotech Inc. Alpha-arylmethoxyacrylate derivative, preparation method thereof, and pharmaceutical composition containing same

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TR200503847T1 (en) 2006-04-21
CN1201657C (en) 2005-05-18
ZA200508026B (en) 2006-10-25

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