WO2005068434A1 - Composes 2-pyrimidinoxy-n-carbamidophenylbenzylamine et procede de preparation et d'utilisation de ces derniers - Google Patents

Composes 2-pyrimidinoxy-n-carbamidophenylbenzylamine et procede de preparation et d'utilisation de ces derniers Download PDF

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WO2005068434A1
WO2005068434A1 PCT/CN2004/000720 CN2004000720W WO2005068434A1 WO 2005068434 A1 WO2005068434 A1 WO 2005068434A1 CN 2004000720 W CN2004000720 W CN 2004000720W WO 2005068434 A1 WO2005068434 A1 WO 2005068434A1
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substituted
compound
mmol
catalyst
hydrogen
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PCT/CN2004/000720
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English (en)
Chinese (zh)
Inventor
Long Lu
Jie Chen
Yong Wu
Zhiping Jin
Xiaoyan Xu
Jun Yuan
Yan Zhang
Yonghua Wang
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Shanghai Institute Of Organic Chemistry, Chinese Academy Of Sciences
Zhejiang Chem-Tech Group Co., Ltd
Bayer Cropscience
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Publication of WO2005068434A1 publication Critical patent/WO2005068434A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/24—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members
    • C07D239/28—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having three or more double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, directly attached to ring carbon atoms
    • C07D239/46—Two or more oxygen, sulphur or nitrogen atoms
    • C07D239/60—Three or more oxygen or sulfur atoms
    • C07D239/62—Barbituric acids
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/30—Derivatives containing the group >N—CO—N aryl or >N—CS—N—aryl

Definitions

  • the present invention relates to a new class of 2-pyrimidinyloxy-N-ureidophenylbenzylamine compounds, a preparation method and uses thereof as agricultural chemical herbicides. Background technique
  • Pesticides are an indispensable means of production for humans to obtain food and ensure stable and high yields in agriculture.
  • pesticides such as pesticides, fungicides, and herbicides have made great contributions to civilization.
  • humans ’demand for food is also increasing, but the rate of cultivated land growth is far behind the rate of population growth.
  • Yield and improvement of crop quality require various means, such as breeding, cultivation, fertilization, and the application of pesticides is also one of the essential means.
  • Pyrimidinyloxybenzene derivatives can be used as chemical herbicides, such as Agr. Biol. Chem., Vol. 30, P896 (1966); Japanese patent 79-55729; US patents 4,248,619 and 4,427,437.
  • Representative examples include: Pyrithiobac-sodium (KIH-2031, European Patent 315889), Bispyribac-sodium (KIH-2023, European Patent 321846), Pyriminobac-methyl , KIH-6127, Japanese Patent 04368361), Pyribenzoxim (European Patent 658549), and Cyclopsalid (Pyriftalid, European Patent 768034), their mechanism of action is the same as that of sulfonylurea herbicides, all of which are acetyl Inhibitors of lactic acid synthase (ALS) disrupt the synthesis of amino acids such as valine, leucine and isoleucine in plants.
  • ALS acetyl Inhibitors of lactic acid synthase
  • pyrimidinesalicylic acid compounds have high herbicidal activity, they are currently only applicable to weeding in cotton and rice fields.
  • the present invention provides a new compound, that is, 2-pyrimidinyloxy-N-ureidophenylamine compounds, and also provides a method for preparing the above compounds and uses as an agricultural chemical herbicide.
  • the compound has the structural formula such as
  • the problem to be solved by the present invention is to provide a new compound, that is, a 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound.
  • the problem to be solved by the present invention is to provide a method for preparing the aforementioned compound.
  • Another problem to be solved by the present invention is to provide a use of the above compound.
  • the invention provides a 2-pyrimidinyloxy-N-ureidophenylbenzylamine compound having the structural formula shown in (I):
  • D and E may be the same or different groups, which are hydrogen, halogen, Q—C 4 fluorenyl, —C 4 alkoxy, Q—C 4 haloalkyl, or Q—C 4 halofluorenyl, It is particularly preferred that both D and E are methoxy.
  • X is hydrogen, halogen, nitro, cyano, carboxyl, ester, sulfonyl, Q-C 8 fluorenyl, d-C 8 halofluorenyl, d-C 8 alkoxy, C plant C 8 acyl , D—C 8 amidamido, Q—C 8 haloalkanoyl, phenyl, benzoyl, substituted phenyl, heterocyclyl or substituted heterocyclyl, etc., it is recommended that X be H or methoxy, X be in benzene
  • the ring can be in any one, two, or more of the 3, 4, 5, and 6 positions.
  • X ' is H, ureido (H 2 Nl' N , R1 , the substituents on the ureido are and), halogen atom, carboxyl
  • X is mono-, di- or poly-substituted on the benzene ring.
  • R is H, n-butyl or n-butyl, n-butyl, or, connected to-(C3 ⁇ 4) 5-.
  • RR 2 is the same or different group.
  • the ureido group (() N. ⁇ —) can be in the ortho, meta or para position of the benzene ring, or it can contain ureido group and other substituents, such as halogen, carboxyl, ester group, —C 8 ⁇ group, — C halogenated alkyl with 8, a 3 ⁇ 4-alkoxy, d-C s alkyl group, a phenyl group, a substituted phenyl group, a heterocyclic group or substituted heterocyclic group.
  • R 3 hydrogen, d-C 8 amidino, d-C 8 haloalkanoyl, benzoyl, substituted benzoyl, d-C 8 amidino.
  • the substituted phenyl, substituted heterocyclic group or substituted benzoyl group is preferably halogen, nitro, cyano , a carboxyl group, an ester group, a sulfonyl group, d -C 8 alkyl, d- C mechanized. 8 haloalkyl group, d- embankment group, C factory wide. 8 C C C alkanoyl or alkanoylamino group and the like. 8; the Substituted phenyl, substituted heterocyclyl or substituted benzoyl are recommended as mono-, di- or poly-substituted.
  • the recommended compounds of the present invention have the following structural formula:
  • the starting material (II) in the reaction can be prepared by the following reaction:
  • R is halogen, nitro, cyano, carboxyl, ester, sulfonyl, —C 8 alkyl, —C 8 haloalkyl,. Broad alkoxy, Q_C 8 alkanoyl, or -C 8 amidamido and the like.
  • Intermediate ( ⁇ -1) synthesis can be prepared by reducing nitrophenyl urea. It can be prepared by reducing nitrophenyl urea with hydrogen under the action of a catalyst.
  • the catalyst can be Raney Ni, palladium carbon or For platinum black, etc., the molar ratio of substituted nitroaniline, hydrogen and catalyst is recommended to be 1: (1—1000): (0.01 -0.5).
  • the reaction temperature is recommended from room temperature to 40 ° C.
  • the reaction time is recommended from 0.5 to 10 hours.
  • the recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol Or an alcohol solvent such as isopropyl alcohol; dimethylformamide, dimethylsulfoxide, acetonitrile, and a mixture of the above solvents can also be used, and the solvent of the reaction is more preferably an alcohol.
  • the intermediate (II-1) can also be prepared by reducing and replacing nitrophenylurea with hydrazine hydrate under the action of a catalyst.
  • the catalyst may be Raney Ni, etc., which replaces nitroaniline, hydrazine hydrate and the catalyst.
  • the molar ratio is recommended to be 1: (1 -1.5): (0.01-0.5), using more hydrazine hydrate has no effect on the reaction.
  • the reaction temperature is recommended to be room temperature to 40 ° C, and the reaction time is recommended to be 0.5 to 10 hours.
  • the recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropyl alcohol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and a mixture of the above solvents can also be used.
  • the solvent for this reaction is further recommended as an alcohol.
  • Nitrophenyl urea synthesis can be prepared by reacting nitrophenyl isocyanate with a substituted fatty amine, and the molar ratio is recommended to be 1: 1 to 1: 2.
  • the recommended solvent may be a hydrocarbon solvent such as benzene, toluene or xylene; an ether solvent such as tetrahydrofuran or dioxane; and the solvent for the reaction is further recommended as benzene.
  • the reaction temperature is preferably 5 ° C to room temperature, and the reaction time is preferably 0.5 to 12 hours.
  • Intermediate ( ⁇ -2) synthesis can be prepared by reducing nitrophenyl to replace aryl urea. Reduction conditions can be the same as those of intermediate ( ⁇ -1) synthesis.
  • Nitrophenyl substituted aryl synthesis can be performed by nitroaniline and substitution.
  • Aromatic isocyanate is prepared by reaction, and the molar ratio is recommended to be 1: 1 to 1: 1.5.
  • the recommended solvent may be a hydrocarbon solvent such as benzene, toluene, or xylene; an ether solvent such as tetrahydrofuran or dioxane; and the solvent for this reaction is further recommended as tetrahydrofuran.
  • the reaction temperature is preferably from room temperature to reflux, and the reaction time is preferably from 8 to 48 hours.
  • Intermediate ( ⁇ -3) synthesis can be prepared by reducing p-nitrophenyl fatty urea, and the reduction conditions can be the same as those of intermediate ( ⁇ -1).
  • the synthesis of p-nitrophenyl fatty urea can be performed by the following method Synthesis: Dissolve p-nitroaniline in hot glacial acetic acid, add sodium cyanate, the recommended molar ratio is 1: 1 to 1: 5, and filter to obtain p-nitrophenylurea.
  • the p-nitrophenyl urea is refluxed in dibutylamine or hexahydropyridine to obtain p-nitrophenyl fatty urea.
  • the method for synthesizing the starting material (II) containing a (X ′) n substituent on the benzene ring is the same as the above-mentioned reaction method.
  • the intermediate (III) can be synthesized by reacting ureido-substituted aniline ( ⁇ ) with salicylaldehyde or substituted salicylaldehyde.
  • the molar ratio is recommended to be 1: 0.8 ⁇ 2, and further recommended to be 1: 1 to 1: 2.
  • solvents can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroacetamidine, or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl Ketone solvents such as ketones; alcohol solvents such as methanol, ethanol, or isopropanol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and mixtures of the above solvents can also be used, and the solvents for this reaction are further recommended as alcohols.
  • hydrocarbon solvents such as benzene, toluene or xylene
  • halogenated hydrocarbon solvents such as dichloromethane, dichloroacetamidine, or chloroform
  • ether solvents such as tetrahydrofuran or dioxane
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent, and the reaction time is preferably from 0.5 to 12 hours.
  • the reaction can be performed without a catalyst.
  • the addition of a catalyst can sometimes speed up the reaction speed and increase the reaction yield.
  • the catalyst used in the reaction can be p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid or acetic acid, etc. ( ⁇ The molar ratio of) to catalyst is recommended to be 1: 0.01-1.
  • the intermediate (IV) can be synthesized by reducing compound (III).
  • the reducing agent is recommended to be sodium borohydride or potassium borohydride.
  • the molar ratio of reactant (III) to reducing agent is recommended to be 1: 0.5-2.
  • the reaction temperature Recommended room temperature to 40 degrees Celsius, reaction time recommended 0.5 to 10 hours, recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrachlorofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropanol; dimethylformyl- A mixture of amine, dimethyl sulfoxide, acetonitrile, and the above-mentioned solvents, and the solvent of the reaction is more preferably an alcohol.
  • the intermediate (IV) can also be prepared by reducing the compound (III) with hydrogen under the action of a catalyst.
  • the catalyst is recommended to be Raney Ni, palladium carbon, platinum black, etc., the reactant (II), hydrogen
  • the molar ratio to the catalyst is recommended to be 1: 1 to 1000: 0.01 -0.5. Using more hydrogen has no effect on the reaction.
  • the reaction temperature is recommended to be room temperature to 40 ° C, and the reaction time is recommended to be 0.5 to 10 hours.
  • the recommended solvents can be hydrocarbon solvents such as benzene, toluene or xylene; ether solvents such as tetrahydrofuran or dioxane; methanol, ethanol or Alcohol solvents such as isopropyl alcohol; dimethylformamide, dimethyl sulfoxide, acetonitrile, and a mixture of the above solvents can also be used.
  • the solvent for this reaction is more preferably an alcohol.
  • the base used is a hydride of a monovalent or divalent metal, an alkoxy metal compound or a carbonate thereof, such as sodium hydride, potassium hydride, calcium hydride ; Sodium methoxide or sodium ethoxide, potassium methoxide or potassium ethoxide; sodium carbonate, potassium carbonate, or calcium carbonate, etc .; or an organic base such as triethylamine, pyridine, or the like.
  • reaction solvents can be hydrocarbon solvents such as benzene, toluene or xylene; halogenated hydrocarbon solvents such as dichloromethane, dichloroacetamidine or chloroform; ether solvents such as tetrahydrofuran or dioxane; acetone or methyl isobutyl Ketone solvents such as methyl ketone; alcohol solvents such as methanol, ethanol, or isopropanol; dimethylformamide, dimethylsulfoxide, acetonitrile, and mixtures of the above solvents can also be used.
  • the best solvent for this reaction is ethers.
  • the reaction temperature is preferably from room temperature to the boiling point of the solvent, and the reaction time is preferably from 0.5 to 20 hours.
  • the molar ratio of intermediate (IV), 2-halo-4-D, 6-E-substituted pyrimidine or 2-methylsulfonyl-4-D, 6-E-substituted pyrimidine to base is recommended to be 1.0: 1.2 : 1-5.
  • the final product can be further purified by silica gel column chromatography or recrystallization.
  • alkyl, substituted fluorenyl, alkoxy, halofluorenyl, halofluorenyl, ester, alkanoyl, alkylamide, and haloalkylamide groups in the present invention refer to straight or branched chain.
  • the chain group is preferably 1 to 8 carbons, and further preferably 1 to 4 carbons.
  • the ester group mentioned in the present invention is preferably an alkoxycarbonyl group, a phenoxycarbonyl group or a substituted phenoxycarbonyl group with a carbon number of 1 to 8, and further an alkoxycarbonyl group, a phenoxycarbonyl group with a carbon number of 1 to 4 Or substituted phenoxycarbonyl group;
  • the sulfonyl group mentioned in the present invention is recommended to be an alkylsulfonyl group, a phenylsulfonyl group or a substituted phenylsulfonyl group, and further recommended to be a carbon number of 1 to 4 Alkylsulfonyl, phenylsulfonyl or substituted phenylsulfonyl;
  • the substituted phenoxycarbonyl or substituted phenylsulfonyl is recommended to be mono-, di- or poly-substituted, and the substituents are preferably halogen,
  • the compound of the present invention is used as an active ingredient of a pesticide chemical herbicide, and is formulated into various liquids, emulsifiable concentrates, suspensions, suspensions, microemulsions, (water) emulsions, powders, wettable powders, soluble powders, (water Dispersible) granules or capsules can be used for weed control in crops such as rice, soybean, wheat, cotton, corn and rape.
  • the weight percentage of the active ingredient in the preparation is recommended to be 5 to 90%, and the rest are carriers.
  • the carrier includes at least two kinds, at least one of which is a surfactant.
  • the carrier can be a solid or a liquid. Suitable solid carriers include natural or synthetic clays and silicates such as natural silica and diatomaceous earth; magnesium silicates such as talc; magnesium aluminum silicates such as kaolinite, kaolin, montmorillonite, and mica; white carbon black , Calcium carbonate, light calcium carbonate; calcium sulfate; limestone; sodium sulfate; amine salts such as ammonium sulfate, hexamethylene diamine.
  • Liquid carriers include water and organic solvents.
  • organic solvents can also be used as adjuvants or antifreeze additives.
  • Suitable organic solvents include aromatic hydrocarbons such as benzene, xylene, toluene, etc .; chlorinated compounds such as chlorobenzene, vinyl chloride, chloroform, dichloromethane, etc .; aliphatic hydrocarbons such as petroleum fractions, cyclohexane, light weight Mineral oils; alcohols such as isopropanol, butanol, ethylene glycol, glycerol and cyclohexanol; and their ethers and esters; and ketones such as acetone, cyclohexanone, and dimethylformamide And N-methyl-pyrrolidone.
  • Surfactants can be emulsifiers, dispersants or wetting agents; they can be ionic or non-ionic.
  • Non-ionic emulsifiers such as polyoxyethylene fatty acid esters, polyoxyethylene fatty alcohol ethers, polyoxyethylene fatty ammonia, and commercially available emulsifiers: agricultural milk 2201B, agricultural milk 0203B, agricultural milk 100 # , agricultural milk 500 # , Agricultural milk 600 # , Agricultural milk 600-2 # , Agricultural milk 1601, Agricultural milk 2201, Agricultural milk NP-10, Agricultural milk NP-15, Agricultural milk 507 # , Agricultural milk OX-635, Agricultural milk OX-622, Agricultural Milk OX-653, agricultural milk OX-667, Ning Ru 36 # .
  • Dispersants include sodium ligninsulfonate, pulverized powder, calcium ligninsulfonate, methylnaphthalenesulfonic acid methyl ester condensate, and the like.
  • Wetting agents are: sodium lauryl sulfate, sodium dodecylbenzenesulfonate, sodium alkylnaphthalenesulfonate, and the like.
  • preparations can be prepared by a general method.
  • the active substance is mixed with a liquid solvent and / or a solid carrier, and a surfactant such as an emulsifier, a dispersant, a stabilizer, a wetting agent is also added, and other auxiliary agents such as a binder, an antifoaming agent, and an oxidizing agent may be added.
  • a surfactant such as an emulsifier, a dispersant, a stabilizer, a wetting agent
  • other auxiliary agents such as a binder, an antifoaming agent, and an oxidizing agent may be added. Wait.
  • the herbicidally active compound of the present invention can be mixed with pesticides, fungicides, nematicides, plant growth regulators, fertilizers, and other herbicides or other agricultural chemicals.
  • the compound of the present invention and its preparation have the following characteristics and advantages:
  • a broad spectrum of weed control which can not only effectively control grass weeds in farmland, but also broad-leaved weeds and sedges. 3. It has good selectivity and is safe for certain crops, such as: wheat, soybean, cotton, rice, etc.
  • the residual period in the soil is short, and it has no adverse effect on the growth of subsequent crops.
  • the compound of formula (I) provided by the present invention has not only a simple synthetic method, but also herbicidal activity and crop selectivity, and can be used as a herbicide. Its preparation can effectively control most farmland weeds, and it can effectively control sensitive grasses, broad-leaved weeds, and sedges at lower doses.
  • Step 1 Take the synthesis of 1-p-nitrophenyl-3-diethylurea as an example: Under the protection of argon, add a 0.8 mL (5 mmol) to a 100 mL three-necked flask with a thermometer and a dropping funnel. ) P-nitrophenyl isocyanate and 5 mL of anhydrous benzene, 0.57 mL (5.5 mmol) of diethylamine dissolved in 5 mL of anhydrous benzene, cooled to 0-10 ° C, added dropwise to the reaction solution, and stirred after the addition About 30min, spin-dried and purified by column chromatography with a yield of 98%.
  • Second step Nitro reduction: 5 mmoll-p-nitrophenyl-3-diethylurea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 mmol) of 80% hydrated Add hydrazine dropwise to the reaction solution at room temperature Stir until the reaction is complete, TLC controls the end of the reaction. After filtration, the filtrate was spin-dried to obtain 1.035 g of 1-p-aminophenyl-3-diethylurea in a yield of 99%.
  • Step 1 Take the synthesis of 1-p-nitrophenyl-3- (2,4-difluorophenyl) urea as an example: Under the protection of argon, add 20 mL of anhydrous THF, 3 drops to a 50 mL Schlenck tube. Triethylamine and 1.38 g (10 mmol) of p-nitroaniline were dissolved in 1.20 mL (10 mmol) of 2,4-difluorophenyl isocyanate in 10 mL of anhydrous THF, and slowly added dropwise to the reaction solution at room temperature. Reflux until the reaction is complete, TLC controls the end of the reaction. Spin-dried and recrystallized from ethyl acetate in 52% yield.
  • Second step Nitro reduction: 5 mmoll-p-nitrophenyl-3- (2,4-difluorophenyl) urea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 80% of hydrazine hydrate was added dropwise to the reaction solution, and stirred at room temperature until the reaction was completed. TLC controlled the end of the reaction. After filtration, the filtrate was spin-dried to obtain 3.1 mmol of 1-p-aminophenyl-3- (2,4-difluorophenyl) urea in a yield of 62%.
  • Second step Nitro reduction: 5 mmoll-p-nitrophenyl-3-piperidinyl urea was dissolved in 20 mL of anhydrous methanol, 90 mg of Raney Ni was added, and 0.469 g (7.5 mmol) of 80% hydrated Hydrazine was added dropwise to the reaction solution and stirred at room temperature until the reaction was complete. TLC controlled the end of the reaction. After filtration, the filtrate was spin-dried to obtain 5 mmol of 1-p-aminophenyl-3-piperidinylurea in a yield of 99%.
  • Step 1 Condensation with salicylaldehyde: 4: 9 mmol of l-p-aminophenyl-3-diethylurea and 0.717 g (5.88 mmol) of salicylaldehyde are dissolved in 15 mL of methanol, and stirred at room temperature until the reaction Completely, TLC controls the endpoint of the reaction. Filtration gave 1.31 g of a yellow solid (III) in a yield of 86%.
  • Step 2 Schiff base reduction: Add 1.31 g of yellow solid (II) to 20 mL of absolute ethanol, add 0.242 g (6.18 mmol) of 97% sodium borohydride in portions, stir at room temperature for 30 min, and pour into ice Water, acetic acid The ethyl acetate was extracted three times, and the organic phases were combined, and the saturated brine and water were washed once, dried over anhydrous sodium sulfate, filtered and spin-dried to obtain the product (IV), with a yield of 99%.
  • Step 3 Condensation with pyrimidine sulfone:
  • Method b 1.310 g (4.2 mmol) of imine-reduced product (IV), 0.916 g (4.2 mmol) of pyrimidine sulfone and 1.159 g (8.4 mmol) of anhydrous potassium carbonate in 20 mL of DMF at room temperature for 8-9 h, TLC Control the endpoint of the reaction.
  • WP Wettable powder
  • Mq compound (I-1) (Table 1)
  • JFC lauryl alcohol polyoxyethylene ether
  • Diatomaceous earth 40 % Diatomaceous earth and 44% light calcium carbonate are evenly mixed and crushed to obtain a wettable powder.
  • Example 22 Wettable powder (WP) formula: 15% compound (I-1) (Table 1), 5% lignin sulfonate ( Mq ), 1% lauryl alcohol polyoxyethylene ether (JFC), 40 % Diatomaceous earth and 44% light calcium carbonate are evenly mixed and crushed to obtain a wettable powder.
  • Granule (GR) formulation 5% compound (I-1) (Table 1), 1% polyvinyl alcohol (PVA), 4% sodium naphthalenesulfonate formaldehyde condensate (NMO) and 90% clay are uniform It was mixed and pulverized, and then 20 parts of water was added to the 100 parts of the mixture, kneaded, and granulated by an extruder to obtain 14-32 mesh granules, and dried to obtain 5% granules.
  • Example 24 5% compound (I-1) (Table 1), 1% polyvinyl alcohol (PVA), 4% sodium naphthalenesulfonate formaldehyde condensate (NMO) and 90% clay are uniform It was mixed and pulverized, and then 20 parts of water was added to the 100 parts of the mixture, kneaded, and granulated by an extruder to obtain 14-32 mesh granules, and dried to obtain 5% granules.
  • Example 24
  • EW Water emulsion
  • an oil phase and an aqueous phase are respectively prepared, and then the two are mixed under high speed stirring to form 15% water emulsion with good dispersibility.
  • the herbicidal activity evaluation test was performed according to the following methods:
  • the test soil was a prepared sandy loam soil.
  • the diameter of the pot bowl for the herbicidal activity test was 9.5 cm, and the diameter of the pot bowl for the safety test was 12.0 cm.
  • the pre-emergence test pot was sprayed with soil surface one day after sowing.
  • the treated liquid was the compound dissolved with organic solvents such as acetone and DMF, and 0.5% Tween-80 laboratory preparation was added, and then diluted with water as needed. dose.
  • the post-emergence test pot was placed in the greenhouse for 7-9 days after sowing, and then foliar sprayed.
  • the treated liquid was a compound dissolved with organic solvents such as acetone and DMF, and 0.5% Tween-80 was added. Chamber preparation, and diluted with water to the required dose.
  • the compound treatment concentration in the first activity determination test was 300 gai / ha or 150 gai / ha
  • the compound treatment concentration in the second activity determination test was 75, 150, and 300 gai / ha or 37.5, 75, 150 gai / ha.
  • the treated pots were allowed to stand for 1 day, then placed in a greenhouse, and watered regularly. After 14 to 21 days, the herbicidal activity of the recorded compounds was observed visually.
  • the herbicidal activity of the compound was visually measured by the degree of plant damage symptoms (inhibition, malformation, yellowing, albinism). 0 means no herbicidal effect or safety to the crop, and 100% means complete weed or crop killing.
  • 70-80 is more sensitive, it can be considered extremely sensitive, serious drug damage, eliminated
  • the types of weeds and crops selected for the biological activity test are as follows:
  • Echinochloa crusgalli Tendon serrata, rice branch width, purslane number g ai / ha

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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)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention concerne une série de composés 2-pyrimidinoxy-N-carbamidophénylbenzylamine, et des procédés de préparation de ces derniers et leur utilisation comme herbicides. Les composés de l'invention sont représentés par la formule (1) suivante : dans laquelle D ou E est un hydrogène, halogène, alkyle C1-C4, alcoxy C1-C4, alkylogène C1-C4 ou alkyloxyogène C1-C4, X est un hydrogène, halogène, nitro-, cyano-, carboxyle, ester, sulfonyle, alkylamido C1-C8, halogénure d'alkylamido C1-C8, alkylacyle C1-C8, alkyle C1-C8, alkylogène C1-C8, alcoxy C1-C8, phényle, phényle benzosubstitué ou hétérocycle ; R1, R2 est un hydrogène, ester, sulfonyle, alkyle C1-C8, alkyle substitué C1-C8, alkylacyle C1-C8, phényle ou hétérocycle ; X' est H, carbamido, halogène, carboxyle, ester, alkylacyle C1-C8, alkyle C1-C8, halogénure d'alkyle C1-C8, alcoxy C1-C8, phényle, phényle substitué ou hétérocycle et al. ; R3 est un hydrogène, alkylacyle C1-C8, halogénure d'alkylacyle C1-C8, benzoyle, benzoyle substitué, alkyle C1-C8.
PCT/CN2004/000720 2003-07-04 2004-07-02 Composes 2-pyrimidinoxy-n-carbamidophenylbenzylamine et procede de preparation et d'utilisation de ces derniers WO2005068434A1 (fr)

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