WO2010043122A1 - Composé de pyréthroide, son procédé de préparation et ses utilisations - Google Patents

Composé de pyréthroide, son procédé de préparation et ses utilisations Download PDF

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Publication number
WO2010043122A1
WO2010043122A1 PCT/CN2009/070835 CN2009070835W WO2010043122A1 WO 2010043122 A1 WO2010043122 A1 WO 2010043122A1 CN 2009070835 W CN2009070835 W CN 2009070835W WO 2010043122 A1 WO2010043122 A1 WO 2010043122A1
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Prior art keywords
compound
tetrafluoro
insecticide
composition
present
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PCT/CN2009/070835
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Chinese (zh)
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WO2010043122A9 (fr
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欧志安
李国江
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贵阳柏丝特化工有限公司
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Publication of WO2010043122A1 publication Critical patent/WO2010043122A1/fr
Publication of WO2010043122A9 publication Critical patent/WO2010043122A9/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N53/00—Biocides, pest repellants or attractants, or plant growth regulators containing cyclopropane carboxylic acids or derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
    • C07C69/74—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring
    • C07C69/743—Esters of carboxylic acids having an esterified carboxyl group bound to a carbon atom of a ring other than a six-membered aromatic ring of acids with a three-membered ring and with unsaturation outside the ring
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention provides a compound and a synthetic method and application thereof, the compound being a compound of an organic insecticide, and more particularly to a novel pyrethroid compound containing heptafluorocarbon and a synthetic method thereof.
  • Insecticides are a well-established commodity, and household insecticides, such as methrin, methrin, permethrin, etc., which are mainly insecticidal active compounds, are widely used and have long been measured for these compounds.
  • the indicators are mainly focused on both knockdown and lethality.
  • the family insecticides, the methrin, the methrin, the permethrin, etc. have a high knockdown force, the toxicity is large, and the amount is not ideal, and other similar compounds such as deltamethrin. , its lethality is better, but the ability to knock down, irritability, and safety are not ideal.
  • the pyrethroid compound can be used for controlling mosquitoes and has high insecticidal activity. It is widely known.
  • U.S. Patent No. 4,370,346 discloses the compound for the first time, and its structural formula is fixed to contain four fluorine atoms; Reports on the commercialization of insect products have some public information at home and abroad.
  • Tefluthrin is also a highly effective pyrethroid. Its main function is the insecticide of soil, because the structure of tefluthrin contains chlorine.
  • the present invention is an in-depth study of pyrethroid compounds of different structures and conformations under the above technical background, and proposes a novel racemic compound with a high biological activity and a pyrethroid compound in the art, and proposes The use of the compound for controlling sanitary pests.
  • the inventors of the present invention have conducted intensive studies on the insecticidal activity of such compounds in the prior art, and found that a compound having a known core structure has a branching compound having 7 fluorine atoms and no other halogen atoms. Its insecticidal activity is about ten times that of the traditional Es-methrin, and it also exceeds the currently commercially available methrin series, tetrafluthrin, and chlorofluoroether. Pyrethroid, and very low toxicity. Accordingly, the present application is intended to protect such a novel structure of the compound and its synthetic process.
  • heptamethrin 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro -1-propenyl)-2,2-dimethylcyclopropanecarboxylate
  • the present invention provides a fluorine-containing compound which is 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1 -propenyl)-2,2-dimethylcyclopropanecarboxylate, in the present invention, the compound is an ester compound having a molecular weight of 414 and having 7 fluorine atoms, and therefore may be simply referred to as heptafluoromethyl ether.
  • Pyrethroid which has the following structure:
  • the above compounds can reduce the amount of the drug to be administered without lowering the drug effect, thereby reducing the toxicity to non-target organisms, improving safety, and reducing environmental pollution of residual drugs.
  • the above compounds of the present invention have high-efficiency, low-toxic insecticidal activity against mosquitoes, flies, cockroaches, etc., which have extremely high knockdown ability and killing ability, are suitable for use in the field of household hygiene products, and can be used as household insecticides.
  • the present invention also provides a synthesis process of the above-mentioned heptamethrin compound, which is 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3, 3,3-Trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate, the synthesis process comprises at least the following steps:
  • the trifluoromethylcyclopropanecarboxylate and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol are placed in an organic solvent, and the ester is catalyzed by titanate Ti (OR) 4
  • the synthesized product is the sevofluthrin of the present invention, that is, the compound of the present invention having the above structural formula 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3, 3,3-Trifluoropropenyl)-2,2-dimethylcyclopropanecarboxylate; wherein, the trifluoromethylcyclopropanecarboxylate and 2,3,5,6-tetra
  • the molar ratio of fluoro-4-methoxymethylbenzyl alcohol is 1.0 to 1.3: 1; trifluoromethylcyclopropanecarboxylic acid
  • the molar ratio of the ester to the titanate is 1.0: 0.01 to 0.1; the organic solvent is an anthracen
  • the method index for judging the completion of the above synthesis reaction or the completion of the synthesis reaction is a technical means commonly used in the art, for example, sampling and tracking analysis can be carried out after completion of the alcohol reaction; and then trifluoromethylcyclopropanecarboxylate can be recovered.
  • the above synthesis process is carried out by reacting in a temperature range of 80 to 150 °C.
  • the time of the above synthesis reaction is generally from 4 to 10 hours.
  • the solvent environment required for the synthesis reaction of the present invention is an organic solvent, which is an anthracene hydrocarbon, a benzene or a mercapto-substituted benzene having a total carbon number of not more than 12 in the chemical structural formula, and preferably a terpene hydrocarbon having a carbon number of 1 to 10 , benzene and/or 1-6 mercapto-substituted benzene, in a preferred embodiment of the invention, the organic solvent required for the synthesis reaction is more preferably an anthracene hydrocarbon of 5-8 carbon atoms, benzene and/or 1-3 mercapto substituted benzenes.
  • the organic solvent may be any one or a combination of two or more of cyclohexane, hydrazine, octyl, benzene, toluene, and xylene.
  • trifluoromethylcyclopropanecarboxylate is preferably racemic (racemic) of trifluoromethylcyclopropanecarboxylate, ie, the elimination of trifluoromethylcyclopropanecarboxylate
  • racemate refers to an equimolar mixture of an optically active (optical isomer) chiral molecule (ie, chiral) with its enantiomer.
  • the above-mentioned racemic trifluoromethylcyclopropanecarboxylate includes cis or trans racemic trifluoromethylcyclopropane carboxylate, or the above-mentioned cis, trans-racemic trifluoromethyl ring.
  • 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol referred to as benzyl alcohol
  • benzyl alcohol used in the above synthetic process, and its synthesis method is well known in the art, for example, 2, 3, 5, 6-tetrafluoro Para-xylene is obtained by reacting monobromide with hydrobromic acid and sodium methoxide.
  • the raw material of the above synthesis reaction is subjected to a transesterification reaction in an organic solvent under a certain temperature condition, preferably 80 to 150 ° C under the catalysis of titanate Ti (OR) 4 , which is the synthesis reaction of the present invention, which is the reverse
  • a transesterification reaction in an organic solvent under a certain temperature condition, preferably 80 to 150 ° C under the catalysis of titanate Ti (OR) 4 , which is the synthesis reaction of the present invention, which is the reverse
  • OR titanate Ti
  • the chemical name of the trifluoromethylcyclopropanecarboxylate is: 3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropene Methyl carboxylate, its structure is as follows:
  • the trifluoromethylcyclopropanecarboxylate used in the above synthetic reaction of the present invention may have a linear or branched fluorenyl group of 1 to 6 carbon atoms in the structural formula, preferably a methyl group or a Base, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, tert-butyl or neopentyl; more preferably methyl or ethyl, ie, trifluoromethylcyclopropanecarboxylate
  • the acid ester is preferably methyl 3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylic acid
  • the compound of the present invention has been subjected to three kinds of structural analysis instruments: infrared spectrometer (IR), gas chromatography/mass spectrometer (GC/MS) and nuclear magnetic resonance spectrometer (NMR) through the analysis and testing center of Fudan University.
  • IR infrared spectrometer
  • GC/MS gas chromatography/mass spectrometer
  • NMR nuclear magnetic resonance spectrometer
  • the iHNMR spectrum demonstrates the position of H in the structure in the compound as follows:
  • the two sets of peaks near ⁇ 1.2 are six H peaks of two -CH 3 on cyclopropene;
  • ⁇ 1.7 is an H peak close to -COO- on the cyclopropene
  • ⁇ 3.3 is the three H peaks of the methyl group on the -CH 2 OCH 3 on the phenyl ring;
  • ⁇ 4.5 is the two H peaks of the methylene group on the -CH 2 OCH 3 on the benzene ring;
  • ⁇ 5.2 is the two H peaks of the methylene group on -COOCH 2 -;
  • the chemical name of the compound is: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-di Methylcyclopropane carboxylate.
  • the compound of the present invention which is a synthetic compound of the above synthetic process, can be used as an active ingredient of a novel organic insecticide, and the compound has a high knockdown ability against mosquitoes, cockroaches, etc., and is also high.
  • the compound of the present invention exhibits high knockdown ability and strong lethality to insects; its insecticidal activity including knockdown ability and lethality exceeds that of permethrin and allylmethrin .
  • the compound of the present invention heptamethrin, is: 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propene) -2,2-dimethylcyclopropanecarboxylate, a highly effective insecticide that can be used as a household sancicide to kill insecticides such as mosquitoes, house flies, and cockroaches, and can also be considered for application to farmland , as a new type of high-efficiency and low-toxic pesticides to develop and use.
  • the synthesis process of the above compound provided by the present invention can also be classified into a one-step process as follows: 3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropane
  • the hydrazine carboxylate and 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl alcohol are subjected to alcohol transesterification in the presence of titanate Ti (OR) 4;
  • the purity is improved, and the target product obtained by the above one-step synthesis process is obtained by recovering the solvent, 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl 3-(3,3,3-trifluoro-1- Propenyl)-2,2-dimethylcyclopropanecarboxylate.
  • the above one-step method of the invention can meet the requirements of the invention, the process is easy to control, the process conditions are safer than other synthetic processes, and the process raw materials, process routes and wastes are simple and easy to handle, the product yield is high, and the purity can be achieved. More than 95%, therefore, the above synthetic process is a process route and a preparation method in the field with broad industrial application prospects.
  • the insecticidal activity of the heptamethrin compound of the present invention is cis or trans racemic trifluoromethylcyclopropanecarboxylic acid
  • the transesterification reaction occurs with benzyl alcohol under the catalysis of titanate.
  • the synthesized reactant is the heptamethrin compound of the present invention, and the specific chemical name is 2,3,5,6-tetrafluoro-4-methyl.
  • the above compounds of the present invention have high-efficiency, low-toxic insecticidal activity against mosquitoes, flies, cockroaches, etc., which have extremely high knockdown ability and killing ability, are suitable for use in the field of household hygiene products, and can be used as household insecticides.
  • the present invention also provides a compound containing 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro Insecticidal composition (insecticide) of -1-propenyl)-2,2-dimethylcyclopropanecarboxylate (sevoflurane), the composition of the composition comprising the composition Total weight 0.001-5 % by weight of 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-
  • the dimethylcyclopropanecarboxylate (active ingredient compound) preferably contains the active ingredient compound in an amount of 0.005 to 5% by weight, more preferably 0.01% to 3% by weight, and the composition further contains a pesticide adjuvant conventional in the art.
  • the pesticidal compositions of the present invention are preferably in the form of a liquid, solid or aerosol.
  • the compound of the present invention can be prepared as a pesticidal active ingredient in a conventional manner into a composition, i.e., an insecticide, for use in addition to mosquito, fly or cockroach pests.
  • the composition may be in various forms of insecticides, including pan-type insecticidal, electrothermal mosquito-repellent tablets, liquid mosquito coils or aerosols, and the like.
  • composition of the compound of the present invention as an active ingredient, which composition comprises various forms of insecticide, and a detailed description of the use of the compound in the insecticide, but is not an exhaustive example :
  • the discicidal insecticidal scent is prepared by adding a compound of the present invention to a liquid form and then adding it to a substrate by a conventional method in the art, wherein the compound of the present invention 2, 3, 5, 6-tetrafluoro-4
  • the content of methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate is from 0.01 to 3.0 w/w%.
  • the liquid form of the above-mentioned liquid form of the compound of the present invention generally comprises an emulsifiable concentrate or a kerosene and other solvents known in the art as active ingredient dissolving solutions for solid insecticides.
  • the solvent of the emulsifiable concentrate or the like preferably further contains a surfactant and other auxiliary agents;
  • the surfactant include mercaptosulfate, mercaptosulfonate, mercaptoarylsulfonate, polyoxyalkylenesulfonyl group One or a mixture of two or more of an ether, a polyoxyalkylene aryl aryl ether, a polyoxyalkylene styryl phenyl ether, a polyol ether or a sugar alcohol derivative;
  • examples of the other auxiliaries include a fragrance, One or a mixture of two or more of a coloring agent or a bactericide; the above are well known in the art and will not be described in detail herein.
  • the substrate of the disc insecticide generally consists of one or more combustible materials and one or more binders, wherein the weight ratio of the combustible material to the binder is 90: 10 to 99.9: 0.1 .
  • the flammable substance may include a powder selected from wood flour, pyrethrum extract powder, citrus peel powder, palm oil powder, coconut shell powder or walnut shell powder. At least one of the dry powder of the plant, or at least one selected from the group consisting of charcoal powder, activated carbon powder or pulverized coal powder, or a mixture thereof; the binder may be selected from starch (including tapioca starch, corn starch or wheat starch), Any of casein, methylcellulose, carboxymethylcellulose, polyvinyl alcohol or a mixture thereof.
  • the disc type insecticide such as mosquito coil
  • the substrate is generally prepared by mixing a combustible substance with a binder and then mixing with water, molding and drying;
  • the shape of the obtained product is not limited and may be a disk shape or a strip shape.
  • the specific embodiment may be prepared by the following process: adding the active ingredient compound and adding water to the substrate when preparing the substrate (mosquito), and mixing into the substrate to form a concentration of the compound containing the active ingredient in the product.
  • a two-wire mosquito coil is typically formed from a conventional coiled substrate having a diameter of about 10-15 cm and a thickness of 3-5 mm.
  • the disc-type insecticide obtained above can be used in a conventional manner.
  • SP igniting the disc insecticide of the present invention in or near the pest habitat (e.g., house, office, barn).
  • the compound of the present invention 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethyl ring Propionate carboxylate can be volatilized when the product is in a burning state.
  • the active ingredient in the air reaches a certain concentration, it will cause irritation, expulsion, paralysis, knockdown and lethal effect on pests such as mosquitoes, cockroaches and the like.
  • the electrothermal mosquito-repellent tablet is a product obtained by dropping and/or coating a solution containing the compound of the present invention on a carrier, and the carrier may also be a porous-based substrate; unit (sheet) mosquito-repellent tablet in the invention
  • the content of the compound is generally not more than 30 mg, and may be, for example, 1 to 20 mg per tablet depending on the nature of the active ingredient compound.
  • the solution containing the compound of the present invention may further contain, as needed, an additive selected from any one or a mixture of an antioxidant, a fumigant conditioner, a fragrance or a dye, as needed.
  • the carrier or porous material mainly comprising the above-mentioned electrothermal mosquito-repellent sheet comprises pulp, asbestos, synthetic porous resin, porous inorganic powder, glass fiber, sulfonated powder or porous ceramic material; the size of the carrier determines the electric mosquito-repellent sheet product Dimensions, for ease of application and the like, the carrier and the product are generally sheets having a length of 30-35 mm, a width of 20-22 mm, and a thickness of 1.5-2 mm. From the standpoint of absorbing and retaining the insecticidal active ingredient, the carrier is preferably in a natural fibrous material. In a preferred embodiment of the invention, the carrier is A sheet containing 50% by weight of cotton fibers and 50% by weight of pulp fibers.
  • the electrothermal mosquito-repellent sheet of the present invention When the electrothermal mosquito-repellent sheet of the present invention is used in or near the habitat of the pest, a certain temperature is controlled by the electric heating plate, so that the active ingredient compound in the electric mosquito-repellent sheet is slowly cast and volatilized. When the effective component of the space reaches a certain concentration, it can stimulate, explode, paralyze, knock down and kill the mosquitoes, cockroaches and other health pests, thereby achieving the insecticidal effect.
  • the liquid mosquito coil is prepared by dissolving a compound of the present invention in an aliphatic hydrocarbon, preferably an aliphatic hydrocarbon of a C12-15 component, and then adding 0.1-0.5% of an antioxidant, 0.1-1% of a fragrance, to prepare a compound of the invention.
  • the product accounts for about 0.1-3% by weight of the mosquito liquid, which is much less than the traditional formula.
  • Liquid mosquito coils are generally applied by electrical heating, also known as electrothermal liquid mosquito coils.
  • the principle of application of electrothermal liquid mosquito coil is: through the capillary action of the carrier mandrel, the mosquito liquid is taken from the bottom of the mandrel to the upper part of the new plate, and under the heating action of the electric heater, the active ingredient is slowly applied, when the effective active ingredient of the space reaches A certain concentration can produce insecticidal effects.
  • the insecticidal aerosol is a composition in which a compound of the present invention, kerosene, and optionally a synergist, a fragrance, and a bactericide are mixed at room temperature or under heating, and is placed in a container with a control valve. And the control valve is prepared by adding a propellant to the tank under pressure.
  • the propellant is preferably liquefied petroleum gas, propanol, dimethyl ether or compressed air, which accounts for about 10-70% of the total weight of the aerosol.
  • the content of the active ingredient compound in the aerosol is generally not more than 0.8 w/w%, and may be, for example, 0.001 to 0.5 w/w%.
  • control valve When in use, the control valve is opened, and under the pressure of the propellant, a high-speed airflow is generated in the container of the aerosol, and the compound liquid containing the active ingredient is dispersed and atomized to form tiny liquid particles suspended in the air, and the mosquito Fly, cockroaches and other pests can achieve the effect of killing pests quickly.
  • the inventors conducted a pharmacodynamic experiment using a disk type mosquito coil and a liquid mosquito coil as an example.
  • the experimental method is a drum method well known in the art, and the experimental results are shown in the following table.
  • the compounds of the present invention have a concentration of 10-30 times lower in the product than the similar pyrethroid products by batch experiments under the same KT50 and 24-hour lethality index. It has been further confirmed that when the content of the compound of the present invention is 0.01-0.6%, the insecticides applied to different dosage forms are superior to the existing varieties.
  • the active ingredient compound 2,3,5,6-tetrafluoro-4-methoxy which plays an insecticidal action in the above insecticidal composition of the present invention
  • Methylbenzyl-3-(3,3,3-trifluoro-1-propenyl)-2,2-dimethylcyclopropanecarboxylate occupies a lower proportion, therefore, the compound of the present invention and
  • the insecticide of this compound has the advantages of: reducing the amount of the insecticidal active agent while ensuring an efficient insecticidal effect.
  • the method for preparing the insecticide comprises a conventional preparation method of a coiled mosquito coil, a liquid mosquito coil, an electric heating mosquito coil and an aerosol, etc., and the insecticidal composition of the invention, that is, the insecticide of the invention, can be prepared, and the method is simple and convenient , reducing the process of industrial operation, can effectively ensure the quality of de-worming, and greatly reduce the amount of pesticide components, and improve the insecticidal effect of the unit composition.
  • the present invention also provides the use of the above composition for insecticidal and deworming.
  • the "worm” of the present invention includes mosquitoes, cockroaches and the like which are harmful to humans and animals.
  • Stability investigation Stability inspection of multiple batches of products, sampling and analysis results, no quality differences, within a reasonable range.
  • the above experiments are part of many experiments of the present invention, and more experimental data are temporarily owed due to space limitations.
  • the object of the present invention is to independently research and develop a new high-efficiency pyrethroid compound with independent intellectual property rights, and to provide a preparation method of the compound, and the requirement for the compound should be useful for household hygiene to eliminate mosquitoes and cockroaches.
  • the insecticidal active ingredient in the low-toxic insecticide, and the synthesis process and the industrial production method of the compound are required to improve the yield of the product and reduce the production cost, and are simple, safe, easy to industrialize, and reduce the dosage. Improve the quality of the product.
  • the above experiment proves that the chemical name of the present invention is 2, 3, 5, 6-tetrafluoro-4-methoxymethylbenzyl 3-(3,3,3-trifluoro-1-propenyl)
  • Example 1 The present invention will be described in detail below with reference to the examples, but without limiting the scope of the invention.
  • Example 1
  • the compound prepared by the method of Example 1 was dissolved in kerosene to a concentration of 0.3-0.5 w/v% solution. 4 ml of the above solution was uniformly added to the above-mentioned linear base material, and left at room temperature for about 2 to 5 hours.
  • the obtained product has a diameter of 12.0 cm and a thickness of 3.5-5 mm, one set of two, and one set weighing about 40 g.
  • Example 6 After comparison with the most commonly used 10mg/piece of acetylethrin electrothermal mosquito-repellent tablets according to GB13917.5-92, the experiment was carried out using a closed drum device. The results showed that the insecticidal efficacy of the compound of Example 1-4 and the product of Example 5 was 20 times higher than that of Es-methrin, which was significantly better than that of allylmethrin, tetrafluthrin, propargyl, Tefluthrin. Example 6.
  • the carrier porous mat (cotton fiber: pulp fiber approximately 1:1) was impregnated with a solution containing 2 mg of any of the compounds of Examples 1-4 and 15 mg of 2,6-di-tert-butyl-4-methylphenol), and allowed to stand at room temperature. Get electric mosquito coils.
  • Example 7 After the experiment, referring to the verification effect experiment of Example 5, the results showed that the compounds of Examples 1-4 and the product of Example 6 had an insecticidal effect of 20 times or more higher than that of Es-methrin, which was significantly better than that of allylmethrin. , tetrafluthrin, propargyl, tetrafluthrin. Example 7.
  • Example 8 0.3 part of any of the compounds of Example 1-4 (as an active ingredient) and 0.3 part of BHT, and the balance of an aliphatic hydrocarbon of C14 were mixed and heated to prepare a liquid mosquito coil.
  • the liquid mosquito coil can be filled into an electrothermal liquid mosquito coil containing 0.5w / w% of the active ingredient compound.
  • Example 9 After the experiment, referring to the verification effect experiment of Example 5, the results showed that the product of the present example had an insecticidal effect of 20 times or more higher than Es-methrin. Example 9.
  • Example 9 of the present invention was carried out in accordance with GB13917. 2-92 for the efficacy test of cockroaches, using a closed drum device. The specific process is as follows: Put the test cockroach into the tank, and after the test worm returns to normal activity, quantitatively spray from the insecticidal aerosol tank of the present invention, and after lmin, the baffle is taken out to make the test insect and the medicament contact, and the time is immediately counted. And began to record, record the number of tested down the pests at regular intervals, after 20 minutes, all the test insects were transferred to a clean insect cage, and the number of dead insects was checked after 24 hours. The results show that the aerosol of this embodiment has a good killing effect on cockroaches.

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  • Organic Chemistry (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne un composé de 2,3,5,6-tétrafluoro-4-méthoxyméthylbenzyl-3-(3,3,3-trifluoro-1- propényl)-2,2-diméthylcyclopropanecarboxylate (heptafluorométhothrine en raccourci), son procédé de préparation, ses utilisations en tant qu’insecticide, et des compositions le contenant. Le procédé de préparation réside dans la transestérification du trifluoromethylcyclopropanecarboxylate et de l’alcool 2,3,5,6-tétrafluoro-4- méthoxyméthylbenzylique dans un solvant organique en présence d’un catalyseur de titanate.
PCT/CN2009/070835 2008-10-16 2009-03-17 Composé de pyréthroide, son procédé de préparation et ses utilisations WO2010043122A1 (fr)

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CNA2008100689409A CN101367730A (zh) 2008-10-16 2008-10-16 一种拟除虫菊酯及合成
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013087709A1 (fr) 2011-12-15 2013-06-20 Bayer Intellectual Property Gmbh Associations de principes actifs ayant des propriétés insecticides et acaricides
CN113563182A (zh) * 2021-07-23 2021-10-29 内蒙古同创高科化学有限公司 三氟氯菊酸生产过程中产生的离心母液回收方法

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100584817C (zh) * 2008-10-14 2010-01-27 江苏扬农化工股份有限公司 拟除虫菊酯化合物及应用
CN101367730A (zh) * 2008-10-16 2009-02-18 贵阳柏丝特化工有限公司 一种拟除虫菊酯及合成
CN104082334A (zh) * 2009-06-05 2014-10-08 江苏扬农化工股份有限公司 飞虫驱避贴
CN104068042A (zh) * 2009-07-01 2014-10-01 江苏扬农化工股份有限公司 一种蚊虫控制剂及其制备方法和应用
CN101747199B (zh) * 2009-12-31 2011-08-31 贵阳柏丝特化工有限公司 一种含乙酰基拟除虫菊酯化合物及其合成方法和用途
CN101844985B (zh) * 2010-02-08 2011-08-31 贵阳柏丝特化工有限公司 一些含乙酰基拟除虫菊酯类化合物及其合成方法和用途
CN104430318A (zh) * 2014-11-25 2015-03-25 贵阳中精科技有限公司 一种拟除虫菊酯卫生线香
WO2018050213A1 (fr) 2016-09-14 2018-03-22 Endura S.P.A. Procédé amélioré pour la préparation de pyréthroïdes

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1648119A (zh) * 2004-01-20 2005-08-03 江苏扬农化工股份有限公司 几种新拟除虫菊酯化合物
CN101367730A (zh) * 2008-10-16 2009-02-18 贵阳柏丝特化工有限公司 一种拟除虫菊酯及合成
CN101367722A (zh) * 2008-10-16 2009-02-18 贵阳柏丝特化工有限公司 一种拟除虫菊酯中间体的制备
CN101381306A (zh) * 2008-10-14 2009-03-11 江苏扬农化工股份有限公司 拟除虫菊酯化合物及应用

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1648119A (zh) * 2004-01-20 2005-08-03 江苏扬农化工股份有限公司 几种新拟除虫菊酯化合物
CN101381306A (zh) * 2008-10-14 2009-03-11 江苏扬农化工股份有限公司 拟除虫菊酯化合物及应用
CN101367730A (zh) * 2008-10-16 2009-02-18 贵阳柏丝特化工有限公司 一种拟除虫菊酯及合成
CN101367722A (zh) * 2008-10-16 2009-02-18 贵阳柏丝特化工有限公司 一种拟除虫菊酯中间体的制备

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013087709A1 (fr) 2011-12-15 2013-06-20 Bayer Intellectual Property Gmbh Associations de principes actifs ayant des propriétés insecticides et acaricides
CN113563182A (zh) * 2021-07-23 2021-10-29 内蒙古同创高科化学有限公司 三氟氯菊酸生产过程中产生的离心母液回收方法

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