Classifications

• • 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)
• Agronomy & Crop Science (AREA)
• Pest Control & Pesticides (AREA)
• Plant Pathology (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Dentistry (AREA)
• General Health & Medical Sciences (AREA)
• Wood Science & Technology (AREA)
• Zoology (AREA)
• Environmental Sciences (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2003
  • 2003-03-25 CN CN 03120882 patent/CN1201657C/zh not_active Expired - Lifetime
• 2004
  • 2004-03-19 WO PCT/CN2004/000226 patent/WO2004084632A1/zh active Application Filing
  • 2004-03-19 AU AU2004224838A patent/AU2004224838A1/en not_active Abandoned
  • 2004-03-19 TR TR2005/03847T patent/TR200503847T1/tr unknown
  • 2004-03-19 BR BRPI0409037-3A patent/BRPI0409037A/pt not_active Application Discontinuation
• 2005
  • 2005-10-04 ZA ZA200508026A patent/ZA200508026B/en unknown

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