WO2012003748A1 - Composés amides d'acides n-oxo-aryloxyphénoxycarboxyliques présentant des activités biologiques, leur procédé de préparation et leur application - Google Patents

Composés amides d'acides n-oxo-aryloxyphénoxycarboxyliques présentant des activités biologiques, leur procédé de préparation et leur application Download PDF

Info

Publication number
WO2012003748A1
WO2012003748A1 PCT/CN2011/074984 CN2011074984W WO2012003748A1 WO 2012003748 A1 WO2012003748 A1 WO 2012003748A1 CN 2011074984 W CN2011074984 W CN 2011074984W WO 2012003748 A1 WO2012003748 A1 WO 2012003748A1
Authority
WO
WIPO (PCT)
Prior art keywords
compound
formula
acid amide
iii
mol
Prior art date
Application number
PCT/CN2011/074984
Other languages
English (en)
Chinese (zh)
Inventor
柳爱平
成四喜
雷满香
姚远
胡志彬
何海军
伍音茵
项军
刘民华
Original Assignee
湖南化工研究院
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 湖南化工研究院 filed Critical 湖南化工研究院
Publication of WO2012003748A1 publication Critical patent/WO2012003748A1/fr

Links

Classifications

    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
    • C07D213/64—One oxygen atom attached in position 2 or 6
    • C07D213/643—2-Phenoxypyridines; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D237/00—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings
    • C07D237/02—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings
    • C07D237/06—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three double bonds between ring members or between ring members and non-ring members
    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having three 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, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D237/14—Oxygen atoms

Definitions

  • the present invention relates to an N-oxyaryloxyphenoxycarboxylic acid amide compound having herbicidal and insecticidal biological activity and a preparation thereof
  • aryloxyphenoxycarboxylic acid compounds have significant monocotylation herbicidal activity, and a plurality of such active compounds have been successfully developed into herbicides, such as clodinafop-propargyl represented by the formula ( ⁇ - ⁇ ).
  • CN 86104887 is an aryloxyphenoxypropionate herbicide developed by Syngenta Crop Protection Co., Ltd. using a dose of 40 to 60 grams of active ingredient per hectare for the control of malignant grass weeds.
  • - ⁇ The cyhalofop-butyl (EP 0302203) is developed by the Dow Agrotech in 1987 and is used in rice fields with a dose of 50 to 100 grams of active ingredient per hectare.
  • Some of the compounds show a broader spectrum of activity and better activity than the acetylene ester shown by ( ⁇ - ⁇ ): such as 07, the insecticidal activity is significantly higher than that of clodinafop, The herbicidal activity is at the same level of activity as clodinafop, and the herbicidal activity of 13, 15 is slightly higher than that of clodinafop or at the same level of activity.
  • the present invention provides a herbicidal and insecticidal biologically active oxime-oxyaryloxyphenoxycarboxylic acid amide compound represented by the formula (I) and an isomer thereof: among them:
  • R 1 is H or ⁇ C 3 fluorenyl
  • R 2 and R 3 are the same or different and represent H, halogen, fluorenyl, fluorenyl fluorenyl;
  • X is CH or N
  • R is C 3 -C 6 alkenyl, C 3 -C 6 alkynyl, C 3 -C 6 haloalkenyl, C 3 -C 6 haloalkynyl, C 3 -C 6 cyclodecyl Methyl, C 3 -C 6 halocyclodecylmethyl;
  • Halogen means fluorine, chlorine, bromine, iodine
  • ⁇ base refers to a straight or branched chain thiol
  • Halogenated fluorenyl means a straight or branched fluorenyl group in which a hydrogen atom is partially or completely substituted by a halogen atom, "haloalkenyl”, “haloalkynyl” and “halo”
  • base is the same as the term “halogenated fluorenyl”;
  • Alkenyl means a straight or branched chain having 3 to 6 carbon atoms and having a double bond at any position;
  • Alkynyl means a straight or branched chain having 3 to 6 carbon atoms and having a triple bond at any position.
  • the compounds of the invention may exist in one or more stereoisomers.
  • the various isomers include enantiomers, diastereomers, and geometric isomers.
  • geometric isomers can be formed (different configurations are represented by Z and E, respectively), and the present invention includes Z-isomers and E-isomers and mixtures thereof in any ratio.
  • the compound of the formula (I) of the present invention forms a stereoisomer by connecting four different substituents on one carbon atom (representing different configurations by R and S, respectively), and the present invention includes R type A mixture of the conformation and the S-isomer and any ratio thereof.
  • the compounds of the invention may exist in one or more stereoisomers.
  • the various isomers include enantiomers, diastereomers, and geometric isomers.
  • the invention further relates to a biologically effective amount of a compound of formula (I) for controlling weeds, pests and at least one additional composition selected from the group consisting of surfactants, solid diluents and liquid diluents.
  • the invention further relates to a composition for controlling weeds, pests comprising a biologically effective amount of a compound of formula (I) and an effective amount of at least one additional biologically active compound or formulation.
  • the invention also relates to a method of controlling weeds, pests, comprising contacting a biologically effective amount of a compound of formula (I) with weeds, pests or their environment. Also relates to such a weed, pest control method, weed, pest or environmentally effective amount of a compound of formula (I) or a compound of formula (I) and a biologically effective amount of at least one additional compound or formulation The mixture is contacted to control weeds and pests.
  • the compound of the formula (I) of the present invention has a broad spectrum of activity: some compounds can be used for controlling various grass weeds and partial broad Leaf weeds; some compounds can be used to control various harmful insects on various crops such as armyworm, diamondback moth, Spodoptera litura, beet armyworm, spider mites, aphids, and some compounds for certain target weeds, The pests have a high biological activity so that good results can be obtained at very low doses.
  • compositions of the invention are compositions containing the preferred compounds described above.
  • a preferred method is the method using the above preferred compounds.
  • the present invention will be further illustrated by the above preferred compounds of the formula (I) 01 to 18 listed in Table 1, but is not intended to limit the invention.
  • the melting points given in the present invention were uncorrected. All the compounds in Table 1 were observed in LC-MS (APCI, Pos) (Agilent 1100 Series LC/MSD) and GC-Mass (EI, 70 eV, m/z). To its molecular ion peak.
  • the 1H NMR (Varian INOVA-300 spectrometer) of the compound in Table 1 was tetramethylsilane (TMS) as an internal standard.
  • the compound of the formula (I) of the present invention can be obtained by the following Reaction Scheme 1, (II) in the reaction formula 1. It can be obtained by the following Reaction Scheme 2, and (III) in the reaction formula 1 can be obtained by the reaction formula 3, and Z in the reaction formula 2 and the reaction formula 3 is a leaving group such as chlorine, bromine, etc., other substitutions Unless otherwise specified, the basis is as defined above.
  • the compound of the formula (I) can be produced in this manner (Reaction formula 1): in a suitable solvent such as dichloromethane or toluene, at -10 ⁇
  • the compound of the formula (II) and the corresponding compound of the formula (III) are reacted at 55 ° C in the presence of a suitable base such as triethylamine or pyridine to give a compound of the formula (I).
  • a suitable base such as triethylamine or pyridine
  • DMAP 4-dimethylaminopyridine
  • the compound of formula (II) can be prepared by the following reaction (reaction formula 2): in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF) in the presence of a suitable base such as potassium carbonate at 25 to 100 ° Under the condition of C, a compound represented by the formula (II-A) and a corresponding compound represented by the formula (II-B) are reacted to obtain a compound represented by the formula (II-C), which is represented by the formula (II-C). The compound is reacted with thionyl chloride to give a compound of the formula (II).
  • reaction formula 2 reaction formula 2: in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF) in the presence of a suitable base such as potassium carbonate at 25 to 100 °
  • a compound represented by the formula (II-A) and a corresponding compound represented by the formula (II-B) are reacted to obtain
  • the compound of the formula (III) can be produced by the following reaction (reaction formula 3): in a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF) in the presence of a suitable base such as triethylamine at 25 to 100
  • a suitable solvent such as hydrazine, hydrazine-dimethylformamide (DMF)
  • a suitable base such as triethylamine at 25 to 100
  • the compound represented by the formula (III-A) and the corresponding compound represented by the formula (III-B) are reacted at ° C to obtain a compound of the formula (III-C), as shown by the formula (III-C).
  • the compound is acidified under acidic conditions (e.g., hydrochloric acid) to give a compound of the formula (III).
  • the compound of the formula (I) provided by the invention has broad-spectrum biological activity at an amount of 15 to 375 g of active ingredient per hectare, and can be used for controlling various grass weeds and some broad-leaved weeds, and can also be used for controlling various crops.
  • Various harmful insects such as armyworm, diamondback moth, Spodoptera litura, beet armyworm, spider mites, and aphids, some compounds have high weed and pest control effects, and can be obtained at very low doses. effective.
  • the compound of formula (I) provided by the invention has biological activity and some compounds have good biological activity. Especially High activity in the control of agricultural, horticultural, flower and sanitary pests and weeds.
  • the pests described here include, but are not limited to:
  • Orthoptera such as striata, pteridoptera such as cotton scorpion horse, rice scorpion horse, melon scorpion horse, Homoptera such as spider mites, locusts, locusts, lepidoptera such as oriental armyworm, Spodoptera litura, side dish Moth, beet armyworm, Spodoptera litura, Pieris rapae, Hymenoptera such as leaf bee larvae, Diptera such as Aedes, Culex, fly.
  • Homoptera such as spider mites, locusts, locusts, lepidoptera such as oriental armyworm, Spodoptera litura, side dish Moth, beet armyworm, Spodoptera litura, Pieris rapae, Hymenoptera such as leaf bee larvae
  • Diptera such as Aedes, Culex, fly.
  • Monocotyledon weeds crabgrass, valerian, foxtail, hard grass, grass, brome, amethyst, stalked wheat, alkali grass, star grass, wild oats, ryegrass;
  • Dicotyledon weeds ramie, sorghum, sylvestris, scorpion, scorpion scorpion, scorpion scorpion, etc.
  • the compound of the formula (I) of the present invention When used alone, it is effective for controlling insects and/or weeds, and they can also be used together with other biochemical substances including other insecticides, nematicides and weeding. Agent.
  • the agricultural preparation of the compound (I) provided by the present invention as an active ingredient can be prepared into any desired dosage form such as dry compressed granules, a flowable mixture, granules, wettable powders, water-dispersible granules, Emulsifying concentrates, powders, powder concentrates, microemulsions, suspending agents, emulsifiable concentrates, aqueous emulsions, soluble liquids, aqueous agents, dispersible agents, suitable adjuvants including carriers (diluents) and other adjuvants Such as spreading agents, emulsifiers, wetting agents, dispersants, adhesives and decomposers.
  • These formulations contain a compound of the invention in admixture with an inert, pharmacologically acceptable solid or liquid diluent.
  • the wettable powders, powders and powder concentrates of the present invention can be prepared by milling about 5-30% by weight of a compound of formula (I) with about 5-30% by weight of a solid anionic surfactant.
  • a suitable anionic surfactant is the dioctyl ester of sodium sulfosuccinate.
  • Inert solid diluents such as talc, kaolin, diatomaceous earth, limestone, silicates and the like are also used in these formulations in an amount of from 40% to 90% by weight.
  • the compressed granules are prepared by milling approximately equal amounts of, for example, 5 to 30 parts of the compound of formula (I) together with the solid surfactant and about 40-90 parts of gypsum, and the mixture is then compressed to about 10-100 mesh (1.676- 0.152mm) Particles of larger size or larger.
  • the solid surfactants used in the formulations of the present invention are not only anionic sodium dioctyl phenyl succinate, but also block polymers of nonionic oxirane and propylene oxide.
  • the flowable agent can be applied in situ with the aqueous solution.
  • the solid preparation of the formula (I) can be used in combination with other insecticides or herbicides, can be used as a multi-component mixture, or can be used sequentially.
  • liquid preparation of the formula (I) can also be used in combination with other insecticides, and can be mixed in a container or sequentially in the form of a liquid spray.
  • the liquid spray formulation of the present invention should contain from about 25 to about 5000 ppm of the effective compound of formula (I).
  • composition of the present invention may also be wettable powders, powders, granules and liquids, emulsifiable concentrates, Emulsions, suspension concentrates, aerosols and aerosols.
  • the wettable powder usually contains 15, 25, 50 parts by weight of the active ingredient, and usually contains 3-10% by weight of a dispersing agent in addition to the solid inert carrier, and if necessary, 0-10% by weight of a stabilizer and/or other additives such as permeation may be added.
  • Powders can generally be formed into powder concentrates having a composition similar to that of a wettable powder but without a dispersing agent.
  • Granules are typically made to have a size of 10-100 mesh (1.676-0.152 mm) and can be prepared by agglomeration or infusion techniques.
  • the granules contain 0.5-50% by weight of active ingredient and 0-10% by weight of additives such as stabilizers, surfactants, sustained release modifiers.
  • the emulsifiable concentrate may contain a cosolvent, 1-50% W/V active ingredient, 2-20% W/V emulsifier and 0-20% W/V other additives such as stabilizers, penetrants, in addition to the solvent.
  • suspension concentrates usually contain 10-75% by weight of active ingredient, 0.5-15% by weight of dispersant, 0.1-10% by weight of other additives such as antifoaming agent, corrosion inhibitor, stabilizer, penetrant And adhesives.
  • Aqueous dispersions and emulsions for example 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 emulsions referred to include both water-in-oil and oil-in-water.
  • 0-propargyl hydroxylammonium hydrochloride (111-01) In a 100 mL three-necked flask equipped with a magnetic stirrer, thermometer and condenser, hydrazine, dimethyl-dimethylformamide (DMF) (40 mL) , 3-bromo-1-propyne (7.08 g 0.06 mol) and N-hydroxyphthalic acid Methylimide (9.78 g 0.06 mol), triethylamine (7.07 g) was added dropwise. The reaction was stirred at 30 to 50 °C for 6 to 8 hours. The reaction was cooled to room temperature, poured into ice water (500 mL) and filtered and filtered.
  • DMF dimethyl-dimethylformamide
  • 0-2-methyl-2-allylhydroxylamine hydrochloride (III-C 2 ) Refer to the synthesis method of 0-propargylhydroxyammonium hydrochloride (111-01) in Example 1, using 2-A Synthesis of 0-2-methyl-2-allyl hydroxylamine hydrochloride by replacing 2-propargyl bromide with 2-ylpropenyl chloride
  • 0-2-Chloro-2-allylhydroxylamine hydrochloride (111-03) Referring to the synthesis method of 0-propargylhydroxyammonium hydrochloride (111-01) in Example 1, using 2,3-di Instead of 2-propargyl bromide, chloropropene was used to synthesize 0-2-chloro-2-allylhydroxylamine hydrochloride (111-03).
  • dichloromethane 40 mL
  • 0-2-chloro-2-allylhydroxylamine hydrochloride ⁇ -03
  • DMAP 4-dimethylamino Pyridine
  • 0-3,3-dichloro-2-allylhydroxylamine hydrochloride Referring to the synthesis method of 0-propargylhydroxyammonium hydrochloride (111-01) in Example 1, using 1, Instead of 2-propargyl bromide, 1,3-trichloropropene was synthesized to synthesize 0-3,3-dichloro-2-allylhydroxylamine hydrochloride (111-04).
  • the organic phase was washed with water (50 mL * 2), dried over anhydrous sodium sulfate and evaporated.
  • the obtained product was purified by column chromatography [jjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • the organic phase was washed with water (50 mL * 2), dried over anhydrous sodium sulfate and evaporated.
  • the obtained product was purified by column chromatography [jjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjjj
  • the organic phase was washed with water (50 mL * 2), dried over anhydrous sodium sulfate and evaporated.
  • N-(2-propargyloxy)-2-(4-(5-trifluoromethylpyridin-2-yloxy)phenoxy)propanoic acid amide (compound 18 in Table 1) with a magnetic stirrer, Toluene (40 mL), 2-(4-(5-trifluoromethylpyridin-2-yloxy)phenoxy)propionic acid ( ⁇ -d) (3.27 g) was placed in a 100 mL three-necked flask of thermometer and condenser. 0.01 mol) and thionyl chloride (3.54 g 0.03 mol). After the reaction was refluxed for 3 to 5 hours, the solvent toluene was removed.
  • Preparation of suspending agent First dilute 2-6% of the wetting and dispersing agent into 4-10% antifreeze, and slowly add a certain amount of water to the solution, then add it under the high speed shearing knife 5-80% of the active compound of the formula (I) provided by the present invention, 0.01-0.05% antiseptic, 0.01-0.05% antifoaming agent and thickener, and the like. Finally, it is poured into a sand mill for milling, and then the solvent is added to the volume. Dilute with water to any concentration required.
  • Preparation of concentrated emulsion First, a certain proportion of water, surfactant, antifreeze, antifoaming agent, thickener and preservative are mixed together to form a uniform aqueous phase, and then the compound of formula (I) provided by the present invention, Suitable solvent and emulsifier, co-emulsified The agent is mixed to make it a homogeneous oil phase. Finally, the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to any concentration required.
  • Preparation of wettable powder First, a certain proportion of water, surfactant, antifreeze, antifoaming agent, thickener and preservative are mixed together to form a homogeneous aqueous phase, and then the compound of formula (I) provided by the invention is provided. A suitable solvent, an emulsifier, and a co-emulsifier are mixed to form a homogeneous oil phase. Finally, the homogeneous oil phase is mixed with the water phase under high-speed stirring to prepare a concentrated emulsion. Dilute with water to any concentration required.
  • the compounds synthesized were tested for insecticidal, acaricidal, bactericidal and herbicidal activity, and some experimental results are now listed.
  • Potter spray method Weigh an appropriate amount of the herbicidal and insecticidal bioactive N-oxyaryloxyphenoxycarboxylic acid amide compound provided by the present invention, dissolved in N-dimethylformamide, and then emulsified by adding a small amount of Tween 80 Stir well, add a certain amount of water, prepare the required concentration, set the water as a control.
  • Fresh corn leaves are cut into pieces of substantially the same size and placed in a petri dish ( ⁇ D90mm) with filter paper in advance. Then, 10 of the 3rd instar larvae of the armyworm were placed in the dish, and placed under the Potter spray tower for quantitative spraying. The amount of the spray liquid was 1 ml, and the concentration was repeated 3 times.
  • the lid was placed, placed in a recovery chamber, and observed regularly. After 72 hours, the death of the test insects was recorded, and the mortality (%) was calculated. The results were averaged. The activity is divided into A, B, C, and D levels in terms of percentages relative to the blank control. The mortality rate is 100%-90% for grade A, the mortality rate is 90%-70% for grade B, and the mortality rate is 70%-50%. For grade C, the mortality rate is 0%-50% for grade D.
  • the acetylene ester shown by the formula ( ⁇ - ⁇ ) was used as the standard control. The results showed that some of the compounds showed obvious fungicidal activity. For example, compound 07 had 95% killing of armyworm at 1000 mg/L test concentration.
  • the preparation of the medicament is the same as in the embodiment 10.
  • the soybean meal is attached to the newly-extracted bean seedlings, and each plant is connected with more than 20 heads, and then the soybean seedlings are immersed together with the test insects in the N-oxyaryloxybenzene provided by the invention.
  • the oxycarboxylic acid amide compound solution take it out after 10 seconds, remove the excess liquid, insert it into the absorbent sponge, cover it with a glass tube, and check the number of surviving and dead insects after 24 hours. Repeat 3 times and the results are averaged.
  • the activity was compared to the blank control as a percentage, divided into four grades A, B, C, and D.
  • the classification standard was the same as that of the example io, and the acetylene ester shown by the formula (p-0) was used as a standard control, and the results showed that some of the compounds showed Significant acaricidal activity, such as Compound 13 has a 72% kill rate of Grade A activity against aphids at a test concentration of 500 mg/L, and Compound 4 and Compound 15 have a 60% of aphids at a test concentration of 500 mg/L.
  • the C-level activity was left and right, and the clodinafop-like ester of the formula ( ⁇ - ⁇ ) showed a killing rate of 20% against aphids at a test concentration of 500 mg/L, and showed no significant activity.
  • the method is as follows: (1) Quantitatively compacting the soil in a plastic pot with a cross-sectional area of 64 cm 2 and placing it in a stainless steel pot. Select seeds with full grain and uniform size, and divide the monocotyledon weeds (Dalmataria sanguinalis, Valerian) Echinochloa cms- galli, Setaria viridis, and dicotyledon weeds ( ⁇ - Abutilon theophrasti (or Stellaria media or Solanum nigrum) ⁇ Chenopodium album, Amaranthus ascedense or Amaranthus retroflexus tiller, Each 1/3 of the area of the sputum, covered with lcm thick fine soil, from the bottom of the plastic pot sputum to the upper layer of soil infiltration, placed in the greenhouse culture, the test material grows to the required leaf age for testing; (2) weigh the right amount The herbicidal and insecticidal biological activity N-oxyaryloxyphenoxycarboxylic acid amide compound provided by the invention is dissolved in
  • Treatment method The soil material before the seedling is planted the next day, the list The leaf test material grows to 1 leaf 1 heart stage, and the dicotyledon test material grows to 2 true leaf stage for post-emergence stem and leaf treatment; (4) quantitatively remove the liquid medicine according to the set dose for stem and leaf spray and soil spray treatment, respectively The spray solvent and water were used as the control, and the acetylene ester represented by formula (P-0) was used as the standard control; (5) the test material was placed in the greenhouse; (6) the ground growth was visually observed after 15-25 days of treatment.
  • Control effect (%) 100 (control plant height - treated plant height) / control plant height (7)
  • the results show that the compound of the invention is at the dose of 75 ga ⁇ / ha For monocotyledonous weeds, there is A-level herbicidal activity.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Agronomy & Crop Science (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

L'invention porte sur un type de composés amides d'acides N-oxo-aryloxyphénoxycarboxyliques, sur leur procédé de préparation et sur leur application. Lesdits composés amides d'acides N-oxo-aryloxyphénoxycarboxyliques sont représentés par la formule (I), dans laquelle R1 représente H ou un alkyle en C1-C3 ; R2 et R3 sont identiques ou différents et représentent chacun H, un halogène, un alkyle en C1-C3 ou un alkyle en C1-C3 halogéné ; X représente CH ou N ; R représente un alcényle en C3-C6, un alcynyle en C3-C6, un alcényle en C3-C6 halogéné, un alcynyle en C3-C6 halogéné, un cycloalkylméthyle en C3-C6 ou un cycloalkylméthyle en C3-C6 halogéné. Lesdits composés présentent des activités biologiques sur un large spectre et peuvent être utilisés pour la prévention et la lutte contre diverse mauvaises herbes graminées, une partie des mauvaises herbes à feuilles larges et les animaux nuisibles aux cultures tels que la noctuelle ponctuée, la fausse-teigne des crucifères, etc.
PCT/CN2011/074984 2010-07-08 2011-05-31 Composés amides d'acides n-oxo-aryloxyphénoxycarboxyliques présentant des activités biologiques, leur procédé de préparation et leur application WO2012003748A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN 201010221128 CN101885703B (zh) 2010-07-08 2010-07-08 具有生物活性的n-氧基芳氧苯氧羧酸酰胺类化合物及其制备方法
CN201010221128.2 2010-07-08

Publications (1)

Publication Number Publication Date
WO2012003748A1 true WO2012003748A1 (fr) 2012-01-12

Family

ID=43071818

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2011/074984 WO2012003748A1 (fr) 2010-07-08 2011-05-31 Composés amides d'acides n-oxo-aryloxyphénoxycarboxyliques présentant des activités biologiques, leur procédé de préparation et leur application

Country Status (2)

Country Link
CN (1) CN101885703B (fr)
WO (1) WO2012003748A1 (fr)

Families Citing this family (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101885703B (zh) * 2010-07-08 2012-06-20 湖南化工研究院 具有生物活性的n-氧基芳氧苯氧羧酸酰胺类化合物及其制备方法
CN102550597B (zh) * 2012-01-04 2014-06-18 常州科威天使环保科技有限公司 有机溴杀生剂的制备方法
CN104277033B (zh) * 2013-07-02 2017-03-08 湖南化工研究院 N‑(芳基烷基)芳氧苯氧羧酸酰胺类化合物及其制备方法与应用
CN104277034B (zh) * 2013-07-02 2017-07-04 湖南化工研究院 N‑（芳基烷氧基）芳氧苯氧羧酸酰胺类化合物及其制备方法与应用
CN104876922A (zh) * 2014-02-27 2015-09-02 南京工业大学 一类芳氧苯氧丙酸酰胺类除草剂
CN105315199B (zh) * 2014-07-14 2020-11-20 湖南化工研究院有限公司 N-吡啶芳氧苯氧羧酸衍生物及其制备方法与应用
CN104719295B (zh) * 2014-12-19 2017-01-25 湖南化工研究院有限公司 一种除草组合物
CN106632005B (zh) * 2016-11-29 2019-08-20 江苏富鼎化学有限公司 吡啶氧基苯氧基丙酸乙酯化合物及其制备方法和用途
CN106632045B (zh) * 2016-11-29 2019-08-13 江苏富鼎化学有限公司 吡唑磺酰胺类化合物及其合成方法和用途
CN107628967A (zh) * 2017-08-23 2018-01-26 连云港世杰农化有限公司 一种合成氰氟草酯的方法
CN107686454A (zh) * 2017-08-23 2018-02-13 连云港世杰农化有限公司 一种合成氰氟草酯的方法
CN107673995A (zh) * 2017-08-23 2018-02-09 连云港世杰农化有限公司 一种合成氰氟草酯的方法
CN109867624B (zh) * 2017-12-02 2021-09-10 沈阳中化农药化工研发有限公司 一种3-氟-5-氯吡啶氧基苯氧丙酰胺类化合物及其应用
CN108440516A (zh) * 2018-04-16 2018-08-24 湖南七纬科技有限公司 一种除草剂噁草醚原药及其制备方法
CN108752269A (zh) * 2018-07-06 2018-11-06 浙江工业大学 一种含手性碳的芳氧苯氧丙酰胺类化合物及其制备方法和应用

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52125626A (en) * 1976-04-14 1977-10-21 Ishihara Sangyo Kaisha Ltd Herbicides
US4740235A (en) * 1985-04-01 1988-04-26 Ciba-Geigy Corporation 3-fluoropyridyl-2-oxy-phenoxy derivatives having herbicidal activity
CN101337959A (zh) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 具有杀虫活性的邻氨基n-氧基苯甲酰胺类化合物
CN101747263A (zh) * 2008-11-28 2010-06-23 中国中化集团公司 吡啶氧基苯氧羧酸类化合物与应用
CN101885703A (zh) * 2010-07-08 2010-11-17 湖南化工研究院 具有生物活性的n-氧基芳氧苯氧羧酸酰胺类化合物及其制备方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2927532B2 (ja) * 1989-11-09 1999-07-28 塩野義製薬株式会社 含窒素異項環オキシーフェノキシ酢酸誘導体およびその除草剤としての用途

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS52125626A (en) * 1976-04-14 1977-10-21 Ishihara Sangyo Kaisha Ltd Herbicides
US4740235A (en) * 1985-04-01 1988-04-26 Ciba-Geigy Corporation 3-fluoropyridyl-2-oxy-phenoxy derivatives having herbicidal activity
CN101337959A (zh) * 2008-08-12 2009-01-07 国家农药创制工程技术研究中心 具有杀虫活性的邻氨基n-氧基苯甲酰胺类化合物
CN101747263A (zh) * 2008-11-28 2010-06-23 中国中化集团公司 吡啶氧基苯氧羧酸类化合物与应用
CN101885703A (zh) * 2010-07-08 2010-11-17 湖南化工研究院 具有生物活性的n-氧基芳氧苯氧羧酸酰胺类化合物及其制备方法

Also Published As

Publication number Publication date
CN101885703A (zh) 2010-11-17
CN101885703B (zh) 2012-06-20

Similar Documents

Publication Publication Date Title
WO2012003748A1 (fr) Composés amides d'acides n-oxo-aryloxyphénoxycarboxyliques présentant des activités biologiques, leur procédé de préparation et leur application
KR102445236B1 (ko) m-디아미드계 화합물 및 이의 제조방법과 응용
KR100718862B1 (ko) 살진균제
WO2014187297A1 (fr) Composé de n-pyridine-amide (hétéro)aromatique et procédé pour le préparer et l'utiliser
JP2006290883A (ja) 置換ヘテロ環カルボン酸アニリド誘導体、その中間体及び農園芸用薬剤並びにその使用方法
HUE026428T2 (en) Anti-malignant agent
JP3621122B2 (ja) 置換されたトリアゾリノン類
US9386769B2 (en) Thiazole methylamino pyridine compounds and preparation method therefor
CN111662269B (zh) 1-吡啶基吡唑酰胺类化合物及其制备方法与应用
CN105315199B (zh) N-吡啶芳氧苯氧羧酸衍生物及其制备方法与应用
WO2014187298A1 (fr) Composé n-pyridine-amide et procédé de préparation et utilisation de ce composé
KR20160009657A (ko) 살진균성 피라졸의 고체 형태
CN103965123A (zh) 具有生物活性的n-氧基稠杂氧苯氧羧酸酰胺类化合物及其制备方法
WO2011153866A1 (fr) Dérivés de 3-(o-méthylphényl)-2-oxo-l-oxaspiro[4,5]-déc-3-én-4-ol possédant des activités insecticides, acaricides et fongicides et leurs procédés de préparation
JP2006527172A (ja) イソインドリノン誘導体の殺虫剤としての使用
EA024175B1 (ru) Соединения, регулирующие рост растений
CN110066286B (zh) 具生物活性苯基吡唑啉类化合物及其制备方法与应用
CN115701430A (zh) 一种含异恶唑啉的苯基吡啶类化合物及其用途
JP2001302594A (ja) 除草性ベンゾイルオキシカルボキシレートおよびカルボキサミド
CN113480541B (zh) 咪唑并吡啶化合物及其中间体的制备方法
JP3048370B2 (ja) ハロゲン化ニトロエタンの製造方法およびこれを用いる殺虫性α―不飽和アミン類の製造方法
CN111662282B (zh) 氮杂环并吡啶类化合物及其中间体
WO2021053136A1 (fr) Procédé de lutte contre les champignons
CN109553615B (zh) 一种嘧啶盐类化合物及其用途
CN109574956B (zh) 一种噻二唑酰胺类化合物及其应用

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 11803102

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 11803102

Country of ref document: EP

Kind code of ref document: A1