WO2023040686A1 - Composé de pyridazinone, procédé de préparation, composition herbicide et utilisation associée - Google Patents

Composé de pyridazinone, procédé de préparation, composition herbicide et utilisation associée Download PDF

Info

Publication number
WO2023040686A1
WO2023040686A1 PCT/CN2022/116949 CN2022116949W WO2023040686A1 WO 2023040686 A1 WO2023040686 A1 WO 2023040686A1 CN 2022116949 W CN2022116949 W CN 2022116949W WO 2023040686 A1 WO2023040686 A1 WO 2023040686A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
compound
formula
agriculturally acceptable
alkoxy
Prior art date
Application number
PCT/CN2022/116949
Other languages
English (en)
Chinese (zh)
Inventor
王凤云
赵文
徐丹
白从强
张璞
吴耀军
封莹莹
Original Assignee
江苏中旗科技股份有限公司
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 江苏中旗科技股份有限公司 filed Critical 江苏中旗科技股份有限公司
Publication of WO2023040686A1 publication Critical patent/WO2023040686A1/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
    • 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 invention belongs to the technical field of pesticides, and specifically relates to a pyridazinone compound, a preparation method, a herbicide composition and use.
  • Patents WO2012/136703A1 and WO2017/178582A1 disclose that pyridazinone compounds can effectively control various problematic weeds.
  • the pyridazinone compounds disclosed in the above-mentioned patents are not good enough in selectivity to crops, and have certain toxic effects on crops in conventional dosages.
  • the novel pyridazinone compound herbicides according to the present invention not only exhibit favorable herbicidal performance and improved characteristics, but also have improved selectivity to crops. Most importantly, this new class of pyridazinone compounds can effectively control weeds while reducing the toxicity to normal crops.
  • the technical problem to be solved by the present invention is to provide a pyridazinone compound, a preparation method, a herbicide composition and its use, which can improve the selectivity and safety of normal crops while effectively eliminating weeds.
  • the present invention provides a pyridazinone compound represented by formula I or an agriculturally acceptable salt thereof,
  • R 1 represents hydrogen, halogen, C 1 ⁇ C 6 alkyl, C 3 ⁇ C 6 cycloalkyl, C 2 ⁇ C 6 alkenyl, C 2 ⁇ C 6 alkynyl, C 1 ⁇ C 6 haloalkyl, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 3 haloalkoxy, C 1 ⁇ C 6 alkoxy-C 1 ⁇ C 3 alkyl, C 1 ⁇ C 6 alkyl-S(O) p -or C 1 ⁇ C 6 haloalkyl-S(O) p -;
  • p 0, 1 or 2;
  • Ar represents one of the following groups:
  • R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, cyano, C 1 ⁇ C 6 alkyl, C 3 ⁇ C 6 cycloalkyl, C 2 ⁇ C 6 alkenyl, C 2 ⁇ C 6 alkynyl, C 1 ⁇ C 6 haloalkyl, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 3 haloalkoxy, C 1 ⁇ C 6 alkoxy-C 1 ⁇ C 3 alkyl, C 1 ⁇ C 6 alkyl-S(O) p -, C 1 ⁇ C 6 haloalkyl-S(O) p -, or one of the following groups:
  • p 0, 1 or 2;
  • R a , R b , R c , R d , R e , and R f independently represent hydrogen, halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 1 -C 6 alkoxy Or C 1 ⁇ C 6 alkoxy-C 1 ⁇ C 3 alkyl;
  • R h and R g independently represent hydrogen, halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or aryl;
  • the aryl is optionally substituted by one or more of the following groups: halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl;
  • R i and R j independently represent hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, benzyl or aryl;
  • the benzyl or aryl is optionally substituted by one or more of the following groups: halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl.
  • R 1 represents C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl; specifically, C 3 -C 6 cycloalkyl is selected from cyclopropyl, cyclobutyl, cyclo Pentyl or cyclohexyl;
  • Ar represents one of the following groups:
  • R 2 , R 3 , and R 4 independently represent hydrogen, halogen, nitro, cyano, C 1 ⁇ C 6 alkyl, C 3 ⁇ C 6 cycloalkyl, C 2 ⁇ C 6 alkenyl, C 2 ⁇ C 6 alkynyl, C 1 ⁇ C 6 haloalkyl, C 1 ⁇ C 6 alkoxy, C 1 ⁇ C 3 haloalkoxy, C 1 ⁇ C 6 alkoxy-C 1 ⁇ C 3 alkyl or the following groups
  • R a , R b , R c , R d , R e , and R f independently represent hydrogen, halogen, C 1 -C 6 alkyl or C 3 -C 6 cycloalkyl;
  • R h and R g independently represent hydrogen, halogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl or aryl;
  • the aryl is optionally substituted by one or more of the following groups: halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl;
  • R i and R j independently represent hydrogen, C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, benzyl or aryl;
  • the benzyl or aryl is optionally substituted by one or more of the following groups: halogen, C 1 -C 3 alkoxy, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl.
  • R 1 represents C 1 -C 4 alkyl or cyclopropyl; specifically, C 1 -C 4 alkyl is selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl or tert-butyl;
  • Ar represents one of the following groups:
  • R 2 , R 3 , and R 4 independently represent hydrogen, fluorine, chlorine, cyano, nitro, C 1 ⁇ C 3 alkyl, C 3 ⁇ C 6 cycloalkyl, C 1 ⁇ C 6 haloalkyl, C 1 ⁇ C 6 alkoxy group or one of the following groups:
  • R a , R b , R c , R d , R e , and R f independently represent hydrogen, fluorine, and C 1 -C 6 alkyl;
  • R h and R g independently represent hydrogen and C 1 -C 6 alkyl
  • R i and R j independently represent hydrogen, methyl, ethyl, benzyl
  • the benzyl group is optionally substituted with one or more of the following groups: chloro, fluoro, methyl, ethyl, trifluoromethyl or methoxy.
  • R a , R b , R c , R d , R e , and R f independently represent hydrogen, fluorine, and C 1 -C 4 alkyl;
  • R h and R g each independently represent hydrogen and a C 1 -C 4 alkyl group.
  • compounds of formula I may contain an asymmetric center and may exist as single enantiomers, enantiomeric pairs in any ratio; or more than one asymmetric center, including all possible ratios of asymmetric Enantiomers. Usually one of these enantiomers has enhanced biological activity;
  • the alkenes can exist in the form of E or Z or a mixture of the two in any ratio;
  • compounds of formula I may be in equilibrium with alternative tautomers.
  • compounds of formula I are described in the ketone form, alternative enol forms are also possible, as shown in formula I' below;
  • the agriculturally acceptable salts may be salts in the following forms: amines (including primary, secondary and tertiary amines, preferably ammonia, dimethylamine and triethylamine), alkali metal and alkaline earth metal bases, transition Metal or quaternary ammonium bases; preferred aluminum salts, calcium salts, cobalt salts, copper salts, iron salts, magnesium salts, potassium salts, sodium salts or zinc salts of compounds of formula I; more preferably copper salts of compounds of formula I, potassium salts or sodium salt.
  • amines including primary, secondary and tertiary amines, preferably ammonia, dimethylamine and triethylamine
  • alkali metal and alkaline earth metal bases transition Metal or quaternary ammonium bases
  • preferred aluminum salts calcium salts, cobalt salts, copper salts, iron salts, magnesium salts, potassium salts, sodium salts or zinc salts of compounds of formula I
  • copper salts of compounds of formula I potassium salts or
  • the present invention also provides a herbicide composition, which is characterized in that it includes the above-mentioned pyridazinone compound or its agriculturally acceptable salt; preferably, it also includes an agriculturally acceptable co-preparation product; more preferably, Also comprising one or more other pesticides, preferably herbicides and/or safeners;
  • the herbicide composition can be in the form of a concentrate, and these concentrates can be diluted before use, and can also be made into a ready-to-use composition; usually final dilution is performed with water, and liquid fertilizers, micronutrients, biological organisms can also be used , oil or solvent dilution;
  • the herbicidal composition comprises 0.1% to 99% by weight of the compound of formula I, preferably 0.1% to 95% of the compound of formula I; and 1% to 99.9% by weight of the co-formulation, the
  • the co-preparation product is carrier, solvent, surfactant (SAA) or adjuvant, preferably 0-25% surfactant;
  • the herbicide composition can be formulated into various dosage forms, including emulsion concentrate (EC), suspension concentrate (SC), suspoemulsion (SE), capsule suspension (CS), water-dispersible granules (WG), emulsifiable granules (EG), water-in-oil emulsion (EO), oil-in-water emulsion (EW), microemulsion (ME), oil dispersion (OD), oil suspension (OF ), oil-soluble liquid (OL), soluble concentrate (SL), ultra-low volume suspension (SU), ultra-low volume liquid (UL), parent drug (TK), dispersible concentrate (DC), Soluble powder (SP), wettable powder (WP), ZC (combination of SC and CS) or soluble granule (SG).
  • the dosage form will depend on the intended use and the physical, chemical and biological properties of the compound of formula I and all other ingredients.
  • Soluble powder can be prepared by mixing the compound of formula I with one or more water-soluble inorganic salts (such as sodium bicarbonate, sodium carbonate or magnesium sulfate) or one or more water-soluble organic solids (such as polysaccharides) and optionally One or more wetting agents, one or more dispersing agents, or mixtures of such agents are mixed to improve water dispersibility/water solubility. This mixture is then ground to a fine powder, similar compositions may also be granulated to form water soluble granules (SG).
  • water-soluble inorganic salts such as sodium bicarbonate, sodium carbonate or magnesium sulfate
  • water-soluble organic solids such as polysaccharides
  • WP Wettable powder
  • WG Water dispersible granules
  • Granules can be prepared by granulating a compound of formula I in admixture with one or more pulverulent solid diluents or carriers, or by absorbing a compound of formula I (or a solution thereof in a suitable agent) into a porous particulate material (such as pumice, attapulgite clay, fuller's earth, diatomaceous earth (kieselguhr), diatomaceous earth (diatomaceous earths) or corncob meal) or by absorbing the compound of formula I (or its solution in a suitable reagent) into hard
  • the core material such as sand, silicates, inorganic carbonates, sulfates or phosphates
  • Agents that commonly aid absorption or adsorption include solvents (such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters) and sticking agents (such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars, and vegetable oils).
  • solvents such as aliphatic and aromatic petroleum solvents, alcohols, ethers, ketones, and esters
  • sticking agents such as polyvinyl acetates, polyvinyl alcohols, dextrins, sugars, and vegetable oils.
  • One or more other additives such as emulsifying, wetting or dispersing agents may also be included in these granules.
  • DC Dispersible concentrates
  • a compound of formula I can be prepared by dissolving a compound of formula I in water or an organic solvent such as a ketone, alcohol or glycol ether.
  • organic solvent such as a ketone, alcohol or glycol ether.
  • surfactants eg to improve water dilution or to prevent crystallization in spray cans.
  • Emulsion concentrates (EC) or oil-in-water emulsions (EW) can be obtained by dissolving the compound of formula I in an organic solvent (optionally containing one or more wetting agents, one or more emulsifying agents or mixture).
  • Organic solvents suitable for EC include aromatic hydrocarbons (such as alkylbenzenes or alkylnaphthalenes, such as SOLVESSO100, SOLVESSO150 or SOLVESSO200; SOLVESSO is a registered trademark), ketones (such as cyclohexanone or methylcyclohexanone) and alcohols (such as benzyl alcohol, furfuryl alcohol or butanol) or fatty acid dimethylamide (such as C 8 ⁇ C 10 fatty acid dimethylamide).
  • EC products can spontaneously emulsify when added to water, producing an emulsion with sufficient stability to allow spray application with appropriate equipment.
  • EW oil-in-water emulsion
  • a compound of formula I in liquid state (if it is not liquid at room temperature, it can be melted at a reasonable temperature below 70 °C) or in solution (dissolving it in a suitable solvent in), the resulting liquid or solution is then emulsified under high shear into water containing one or more SAAs to produce an emulsion.
  • Solvents suitable for EW include vegetable oils, aromatic solvents such as alkylbenzenes or alkylnaphthalenes, and other available organic solvents with low solubility in water.
  • Microemulsions can be prepared by mixing water with a blend of one or more solvents and one or more SAAs, spontaneously resulting in a thermodynamically stable isotropic liquid formulation.
  • the compound of formula I is initially present in the water or solvent/SAA blend.
  • Suitable solvents for ME include those previously described for EC or EW.
  • ME can be an oil-in-water system or a water-in-oil system (which can be determined by conductivity) and is suitable for mixing water-soluble and oil-soluble pesticides in the same formulation.
  • ME is suitable for dilution into water and remains as a microemulsion or forms a conventional oil-in-water emulsion.
  • SC Suspension concentrates
  • SCs may be aqueous or non-aqueous suspensions of finely divided insoluble solid particles of a compound of formula I.
  • SCs are prepared by ball or bead milling a solid compound of formula I in a suitable medium to yield a fine particle suspension of the compound, optionally with the addition of one or more dispersing agents.
  • One or more wetting agents can be included in the composition, and suspending agents can also be included to reduce the rate of settling of the particles.
  • the compound of formula I can be dry ground and added to water containing the above reagents to obtain the desired final product.
  • Aerosol formulations comprise a compound of formula I and a suitable propellant (such as n-butane), and also include dissolving or dispersing the compound of formula I in a suitable medium (such as water or a water-miscible liquid, such as n-butane). Propanol) to obtain compositions that can be used in unpressurized hand spray pumps.
  • a suitable propellant such as n-butane
  • a suitable medium such as water or a water-miscible liquid, such as n-butane.
  • Propanol Propanol
  • Capsule suspension is similar to the method for preparing EW formulations, but includes a polymerization stage to obtain an aqueous dispersion of oil droplets, wherein each oil droplet is surrounded by a polymer shell and contains a compound of formula I and optionally a carrier or thinner.
  • the polymer shell can be prepared by interfacial polycondensation or by coacervation procedures. These compositions allow for controlled release of the compound of formula I.
  • the compound of formula I can also be dispensed in a biodegradable polymer matrix to achieve slow and controlled release of the compound.
  • Soluble concentrates can be prepared by dissolving the active ingredient in an aqueous liquid optionally with one or more wetting agents and/or one or more buffering agents.
  • the herbicidal composition may also include one or more additives to improve the biological properties of the composition
  • the additives include surfactants (SAA) or oil-based spray additives, preferably certain mineral oils or natural
  • SAA surfactants
  • oil-based spray additives preferably certain mineral oils or natural
  • MRSO methylated rapeseed oil
  • the co-formulations include: wetting agents, dispersants or emulsifiers, preferably cationic, anionic, amphoteric or nonionic SAA;
  • the cationic type of SAA includes quaternary ammonium compounds (such as cetyltrimethylammonium bromide), imidazoline or amine salts;
  • the anionic types of SAA include alkali metal salts of fatty acids, salts of aliphatic monoesters of sulfuric acid (such as sodium lauryl sulfate), salts of sulfonated aromatic compounds (such as sodium dodecylbenzenesulfonate, dodecyl Calcium phenylbenzenesulfonate, butylnaphthalenesulfonate and mixtures of sodium di-isopropyl-naphthalenesulfonate and sodium tri-isopropyl-naphthalenesulfonate), ether sulfates, alcohol ether sulfates (such as lauryl alcohol sodium polyether-3-sulfate), ether carboxylates (e.g.
  • sodium laureth-3-carboxylate phosphate esters (from one or more fatty alcohols) with phosphoric acid (mainly monoesters) or with penta Products of reactions between phosphorus oxides (mainly diesters), for example between lauryl alcohol and tetraphosphoric acid and which may be ethoxylated, also sulfosuccinamates, paraffins or olefin sulfonic acids Salt, taurate, lignosulfonate, and phosphate/sulfate esters of tristyrylphenol;
  • amphoteric type of SAA comprises betaine, propionate or glycinate
  • the non-ionic type of SAA includes condensation products of alkylene oxides (such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof) and fatty alcohols (such as oleyl alcohol or cetyl alcohol), derived from long-chain fatty acids or hexitol anhydride partial esters, condensation products of said partial esters with ethylene oxide, block polymers (containing ethylene oxide and propylene oxide), alkanolamides, monoesters (such as fatty acid polyethylene glycol glycol esters), amine oxides (such as lauryl dimethylamine oxide), lecithin, sorbitan and its esters, alkyl polyglycosides or tristyrylphenols;
  • alkylene oxides such as ethylene oxide, propylene oxide, butylene oxide or mixtures thereof
  • fatty alcohols such as oleyl alcohol or cetyl alcohol
  • alkanolamides such as fatty acid polyethylene glycol glycol esters
  • amine oxides such as lau
  • the suspending agent includes hydrophilic colloids (such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose) and swelling clays (such as bentonite or attapulgite).
  • hydrophilic colloids such as polysaccharides, polyvinylpyrrolidone or sodium carboxymethylcellulose
  • swelling clays such as bentonite or attapulgite
  • the harmful biological agent can be other herbicides or plant growth regulators
  • the herbicide composition comprises (A) a compound of formula I and (B) one or more herbicides selected from the group consisting of acetochlor, acifluorfen (trifluorocarboxy Sodium chlorpyrifos), aclofen, alachlor, dichlorpyr, ametrazine, amenzazone, sulfuron-methyl, cypropyrimidic acid, aminopyralidic acid, acetam, saponin, sulphur Grass spirit, atrazine, flubutyramid, fluoxam, fluramid, bensulfuron-methyl (including bensulfuron-methyl), thiazopine, bicyclopyrone, azafen, bismuth Sodium fenpyramid, bromoxynil, butachlor, butafluzone, fluprofen, mefentrazone, mefentrazone-ethyl (including mefentrazone-ethyl), sulfentrachlor acid
  • the compounds of formula I can also be used in mixtures with other agrochemicals (such as fungicides, nematicides or insecticides), examples of which are given in "The Pesticide Manual [ Pesticides Handbook], Sixteenth Edition, UK Crop Protection Council, 2012".
  • agrochemicals such as fungicides, nematicides or insecticides
  • the present invention also provides a method for controlling weeds, which is characterized in that it comprises applying the above-mentioned pyridazinone compound or its agriculturally acceptable salt or the above-mentioned herbicide composition to the weeds on or in its area;
  • the present invention also provides a method for selectively controlling weeds in a place including crop plants and weeds, wherein the method comprises applying a weed control amount of the above-mentioned pyridazinone compound or its agricultural method to the place. acceptable salts or the above herbicidal compositions.
  • Control means killing, reducing or retarding growth or preventing or reducing germination. Plants to be controlled are generally unwanted plants (weeds).
  • “Locus” means an area where a plant is growing or will grow. Application to the locus may be pre- and/or post-emergence of the crop plants. Some crop plants are inherently resistant to the herbicidal effect of the compounds of the formula I.
  • Preferred crop plants include corn, wheat, barley and rice.
  • Tolerance can be engineered into crop plants as desired, for example by genetic engineering.
  • the crop plants can be genetically engineered to be tolerant to 4-hydroxyphenylpyruvate dioxygenase (HPPD) inhibitors.
  • HPPD 4-hydroxyphenylpyruvate dioxygenase
  • Methods for making crop plants tolerant to HPPD inhibitors can be referred to WO0246387.
  • the crop plant contains a transgenic polynucleotide comprising a DNA sequence encoding an HPPD inhibitor-resistant HPPD enzyme, the HPPD inhibitor-resistant HPPD enzyme From a bacterium (more specifically, from Pseudomonas fluorescens or Shewanella colwelliana), or from a plant (more specifically, from a monocot or still more specifically For example, from barley, corn, wheat, rice, Brachiaria, Cenchrus, Lolium, Fescue, Setaria, Grychograss, Sorghum, or Avena species).
  • bacterium more specifically, from Pseudomonas fluorescens or Shewanella colwelliana
  • a plant more specifically, from a monocot or still more specifically For example, from barley, corn, wheat, rice, Brachiaria, Cenchrus, Lolium, Fescue, Setaria, Grychograss, Sorghum, or Avena species.
  • the application rates of the compounds of the formula I can be varied within a relatively wide range and depend on the nature of the soil, the method of application (pre- or post-emergence; seed dressing; application to seed furrows; no-till application, etc.), the crop plant, the weeds, prevailing climatic conditions, other factors governed by the method of application, timing of application, and target crop.
  • the application rate of the compound of formula I in the present invention can be 10-2000g/ha, preferably 25-1000g/ha, more preferably 25-250g/ha;
  • the herbicidal composition is applied by spraying, preferably by a sprayer mounted on a tractor over a large area, or other methods such as dusting (for powder), dripping or soaking;
  • Crop plants also include those that have been made tolerant to other herbicides or classes of herbicides (such as ALS inhibitors, GS inhibitors, EPSPS inhibitors, PPO inhibitors, and ACC enzyme inhibitors) by conventional breeding methods or genetic engineering crop plants.
  • herbicides or classes of herbicides such as ALS inhibitors, GS inhibitors, EPSPS inhibitors, PPO inhibitors, and ACC enzyme inhibitors
  • An example of a crop that has been made tolerant to imidazolinones (eg imazamox) by conventional breeding methods is summer rape (canola).
  • crops that have been genetically engineered to be tolerant to herbicides include glyphosate- or glufosinate-resistant maize varieties, which are commercially available under the trade name;
  • Crop plants also include crops that have been genetically engineered to be resistant to harmful insects, such as Bt corn (resistant to the European corn borer), Bt cotton (resistant to the boll weevil), and Bt potatoes (resistant to the Colorado beetle). sex).
  • Bt corn is the Bt 176 corn hybrid (Syngenta Seeds).
  • Bt toxins are proteins naturally formed by the soil bacterium Bacillus thuringiensis.
  • toxins or transgenic plants capable of synthesizing such toxins see EP-A-451878, EP-A-374753, WO93/07278, WO95/34656, WO03/052073 and EP-A-427529.
  • transgenic plants comprising one or more genes encoding insecticide resistance and expressing one or more toxins are corn, cotton, potato, and plant crops or seed material thereof, all resistant to both herbicides and insect ingestion ( "stacking" transgenic events).
  • seed can be resistant to glyphosate while possessing the ability to express the insecticidal Cry3 protein.
  • Crop plants also include those obtained by conventional breeding or genetic engineering and containing export traits (eg improved storage stability, higher nutritional value and improved aroma).
  • Herbicidal compositions can be used to control unwanted vegetation (collectively "weeds").
  • the weeds to be controlled can be either monocotyledonous species such as Bentgrass, Aurantium, Avena, Brachiaria, Brome, Tribulus, Cyperus, Crabgrass, Barnyardgrass , Lolium , Lolium , Yujiuhua , Cystonia , Sagittarius , Sorghum , Setaria , and Sorghum , and also dicotyledonous species such as Abutilon , Amaranthus , Ragweed , Chenopodium genus, Chrysanthemum genus, Liquorgrass genus, Lara genus, Ipomoea genus, Nasturtium genus, Chrysanthemum genus, Sinusia genus, Solanum genus, Chickweed genus, Popona genus, Viola genus and Xanthium genus.
  • monocotyledonous species such as Bentgrass, Aurantium, Avena, Bra
  • the present invention also provides the use of the above-mentioned pyridazinone compound or its agriculturally acceptable salt or the above-mentioned herbicide composition in controlling weeds.
  • the present invention also provides a method for preparing the above-mentioned pyridazinone compound or an agriculturally acceptable salt thereof, which is characterized in that it comprises the following steps:
  • R 1 and Ar are as defined in any one of claims 1 to 6;
  • R 5 represents halogen, -OH, C 1 to C 6 alkoxy, aryloxy or N-linked imidazole;
  • the compound of formula IIc is added to react with the compound of formula III to generate the compound of formula IV;
  • R and Ar are as defined in any one of claims 1 to 6;
  • LG is a suitable leaving group;
  • the present invention also provides the second preparation method of the above-mentioned pyridazinone compounds or their agriculturally acceptable salts, which is characterized in that it comprises the following steps: reacting the compound of formula V and formula III in a reaction medium to generate the compound of formula I;
  • the definitions of R1 and Ar are as described in any one of claims 1-6;
  • the reaction medium includes a palladium catalyst, a suitable phosphine ligand or a phosphine ligand salt, a suitable base and/or carbon monoxide.
  • the pyridazinone compounds described in the present invention are selected from the following Table 1 or Table 2:
  • Table 1 is selected from the compound of formula I-1
  • Table 2 is selected from the compound of formula I-2
  • the beneficial effect of the present invention is that it provides a pyridazinone compound, a preparation method, a herbicide composition and its use.
  • the herbicide has a wide application range, good safety and high selectivity, and can effectively suppress weeds.
  • the preparation method of the herbicide of the present invention is simple in operation and low in cost, and is suitable for large-scale industrial production.
  • Step 1 Preparation of ethyl 2-(benzo[d][1,3]dioxolan-5-yl)-6-methyl-3-oxo-2,3-dihydropyridazine-4-carboxylate preparation.
  • Ethyl-3-methyl-6-oxo-1H-pyridazine-5-carboxylate (5.0g, 27.4mmol) (available from the preparation method of reference CN108884074A) in dichloromethane (200mL)
  • 3,4-(methylenedioxy)phenylboronic acid (6.37 g, 38.4 mmol) (commercially available) portionwise over 5 minutes and the reaction mixture was stirred at room temperature for 16 hours.
  • Catechol (11.00g, 0.1mol) was added to a 250mL four-necked flask, then toluene (100mL) and p-toluenesulfonic acid (0.19g, 1mmol) were added, and a water trap was put on. Reflux and stir in an oil bath at 110°C for 2 hours. Then, 2,2-dimethoxypropane (45.0 g, 0.432 mol) was added dropwise to the reaction liquid, and the reflux stirring was continued until the reaction was completed. GC-MS monitored the reaction end point. After the reaction was completed, the solvent was removed, and the residue was purified by column chromatography (100% petroleum ether) to obtain 2,2-dimethylbenzo[d][1,3]bisoxazole (11.46g, 76.31% yield) .
  • reaction solution was quenched with saturated aqueous ammonium chloride solution, and the pH was adjusted to 1 with hydrochloric acid.
  • the organic phase was separated, and the aqueous phase was extracted with ethyl acetate (20mL*2). The organic phases were combined and washed with anhydrous After drying over sodium sulfate and precipitation, (2,2-dimethylbenzo[d][1,3]dioxolan-5-yl)boronic acid (3.14 g, 80% yield) was obtained.
  • 6-Methylpyridazinone (5.00g, 45mmol) was dissolved in acetic acid (100mL), then potassium acetate (13.24g, 135mmol) was added in batches, and then liquid bromine (14.38g, 90mmol) was slowly added dropwise to it And the reaction solution was stirred in an oil bath at 90°C. After the reaction was completed, the reaction solution was quenched with aqueous sodium thiosulfate solution, then extracted with ethyl acetate (20 mL*2), and the organic phase was washed with saturated sodium bicarbonate, dried over anhydrous sodium sulfate, filtered and concentrated in vacuo.
  • Step 5 Preparation of 4-bromo-2-(2,2-dimethylbenzo[d][1,3]dioxolan-5-yl)-6-methylpyridazin-3(2H)-one .
  • the reaction was stirred at 60°C for 4 hours under 10 bar pressure. After completion of the reaction, cool to room temperature, wash the reaction solution with 1M hydrochloric acid, then dry the organic phase with anhydrous sodium sulfate, and purify with column chromatography (0% ⁇ 5% methanol) after precipitation to obtain 2-(2-(2- (2,2-Dimethylbenzo[d][1,3]dioxolan-5-yl)-6-methyl-3-oxo-2,3-dihydropyridazine-4-carbonyl ) cyclohexane-1,3-dione (196 mg, 82%).
  • Embodiment 6 is a diagrammatic representation of Embodiment 6
  • reaction solution was cooled to room temperature, then poured into ice water, extracted with ethyl acetate (50mL*2), combined the organic phases and dried with anhydrous sodium sulfate, purified by column chromatography (100% petroleum ether ) to give 7-bromo-5-chloro-2,3-dihydrobenzo[b][1,4]dioxane (4.42 g, 70%) as a white solid.
  • Step 5 4-Bromo-2-(8-chloro-2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-6-methylpyridazin-3(2H)-one preparation.
  • Embodiment 7 is a diagrammatic representation of Embodiment 7:
  • Step 1 Ethyl-6-cyclopropyl-2-(2,3-dihydrobenzo[b][1,4]dioxin-6-yl)-3-oxo-2,3-di Preparation of hydropyridazine-4-carboxylate.
  • Embodiment 8 is a diagrammatic representation of Embodiment 8
  • reaction solution was cooled to room temperature, then poured into ice water, extracted with ethyl acetate (50mL*2), combined the organic phases and dried with anhydrous sodium sulfate, purified by column chromatography (100% petroleum ether ) to give 7-bromo-2,3-dihydrobenzo[b][1,4]dioxin-5-carbaldehyde (4.25 g, 70%) as a white solid.
  • Step 6 4-Bromo-2-(8-(4,5-dihydroisoxazol-3-yl)-2,3-dihydrobenzo[b][1,4]dioxin-6-yl) - Preparation of 6-methylpyridazin-3(2H)-one.
  • Step 7 2-(2-(8-(4,5-Dihydroisoxazol-3-yl)-2,3-dihydrobenzo[b][1,4]dioxin-6-yl)- Preparation of 6-methyl-3-oxo-2,3-dihydropyridazine-4-carbonyl)cyclohexane-1,3-dione (compound 1-2.216).
  • Pre-emergence test test put 8cm deep field standard soil (loam, pH value 6.7, organic matter content is 1.59%) in the plastic basin pot with diameter 7cm deep 10cm, add water to soak the soil to saturation, and each pot sows a certain amount of Evenly cover one deck soil after seed (for testing monocotyledon, dicotyledon weed seed and main crop seed); Dilute it with 1% Tween-80 static tap water to the required concentration for later use, and carry out soil spray treatment 24 hours after sowing.
  • the spray adopts the 3WP-2000 biometric spray tower produced by the Nanjing Agricultural Mechanization Research Institute of the Ministry of Agriculture. The speed is 210mm/s, the walking distance is 1340mm, and the liquid volume is 42mL.
  • Post-emergence test test put 8cm deep field standard soil (loam, pH value 6.7, organic matter content is 1.59%) in the plastic basin pot with diameter 7cm deep 10cm, add water to soak the soil to saturation, and every pot sows a certain amount of Seeds (for the monocotyledonous, dicotyledonous weed seeds and main crop seeds) are evenly covered with a layer of soil; put into a constant temperature light cultivation room to cultivate until the weeds 2-4 leaf stage.
  • the temperature in the cultivation room was set at 22°C during the day and 15°C at night or 28°C during the day and 22°C at night; the light cycle was 12:12 (D:L).
  • the activity level criteria for plant damage are as follows:
  • Level 5 The inhibition rate of fresh weight is 85% and above;
  • Fresh weight inhibition rate is greater than or equal to 60% and less than 85%;
  • Level 3 The fresh weight inhibition rate is greater than or equal to 40% and less than 60%;
  • Fresh weight inhibition rate is greater than or equal to 20% and less than 40%
  • Fresh weight inhibition rate is greater than or equal to 5% and less than 20%;
  • the compound application dose is 500g/ha.

Landscapes

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

Abstract

L'invention concerne un composé de pyridazinone, un procédé de préparation, une composition herbicide et une utilisation associée. La présente invention concerne en particulier un composé de pyridazinone représenté par la formule générale I ou un sel acceptable en agriculture de celui-ci, un procédé de préparation du composé de formule I à partir d'un composé de formule II, un composé de formule III ou un composé de formule IV, et un composé de formule III en tant que matières premières, et l'utilisation de la composition herbicide contenant le composé de formule I ou son sel acceptable en agriculture dans la lutte contre les mauvaises herbes. L'herbicide a une large gamme d'applications, une bonne innocuité et une sélectivité élevée, et n'endommage pratiquement jamais les cultures normales tout en inhibant de manière efficace les mauvaises herbes ; et le procédé de préparation de l'herbicide est facile à utiliser, à faible coût et est approprié pour une production industrielle à grande échelle.
PCT/CN2022/116949 2021-09-16 2022-09-05 Composé de pyridazinone, procédé de préparation, composition herbicide et utilisation associée WO2023040686A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN202111086969 2021-09-16
CN202111086969.1 2021-09-16

Publications (1)

Publication Number Publication Date
WO2023040686A1 true WO2023040686A1 (fr) 2023-03-23

Family

ID=85602416

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/CN2022/116949 WO2023040686A1 (fr) 2021-09-16 2022-09-05 Composé de pyridazinone, procédé de préparation, composition herbicide et utilisation associée

Country Status (1)

Country Link
WO (1) WO2023040686A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136703A1 (fr) * 2011-04-08 2012-10-11 Syngenta Limited Composés herbicides
CN108884074A (zh) * 2016-04-15 2018-11-23 先正达参股股份有限公司 除草哒嗪酮化合物
CN111406045A (zh) * 2017-10-18 2020-07-10 先正达参股股份有限公司 用于生产除草哒嗪酮化合物的方法
CN111527072A (zh) * 2017-10-18 2020-08-11 先正达参股股份有限公司 用于生产除草哒嗪酮化合物的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2012136703A1 (fr) * 2011-04-08 2012-10-11 Syngenta Limited Composés herbicides
CN108884074A (zh) * 2016-04-15 2018-11-23 先正达参股股份有限公司 除草哒嗪酮化合物
CN111406045A (zh) * 2017-10-18 2020-07-10 先正达参股股份有限公司 用于生产除草哒嗪酮化合物的方法
CN111527072A (zh) * 2017-10-18 2020-08-11 先正达参股股份有限公司 用于生产除草哒嗪酮化合物的方法

Similar Documents

Publication Publication Date Title
RU2566760C2 (ru) Сложные арилалкиловые эфиры 4-амино-6-(замещенный фенил)пиколинатов и 6-амино-2-(замещенный фенил)-4-пиримидинкарбоксилатов и их применение в качестве гербицидов
TWI253445B (en) Benzoylcyclohexanediones, process for their preparation and their use as herbicides and plant growth regulators
JP4938954B2 (ja) ベンゾイルピラゾールおよび除草剤としてのその使用
KR102445810B1 (ko) 제초제 피리다지논 화합물
EA027488B1 (ru) Производные 6-ацил-1,2,4-триазин-3,5-диона и гербициды
JP6063923B2 (ja) 除草性化合物
EA031259B1 (ru) Гербицидная комбинация, содержащая азины
KR20180011129A (ko) 제초제로서의 2-(페닐옥시 또는 페닐티오)피리미딘 유도체
CN113412256B (zh) 除草化合物
CN113423693B (zh) 除草化合物
UA124556C2 (uk) Піридазинонові гербіциди
WO2021143677A1 (fr) Composé aromatique substitué à cycle condensé, son procédé de préparation, composition herbicide et utilisation associée
WO2021088856A1 (fr) Composé aromatique contenant de l'isoxazoline substitué, procédé de préparation correspondant, composition herbicide et utilisation associée
UA117876C2 (uk) Гербіцидно активні аміди арилкарбонових кислот
CN113423692B (zh) 取代的氮杂螺环作为除草剂
EP4058438B1 (fr) Composés herbicides
CN114667063B (zh) 杂草控制方法中的氟化苯乙酸衍生物
CN111615508A (zh) 可用作除草剂的脒取代的苯甲酰基衍生物
WO2023040686A1 (fr) Composé de pyridazinone, procédé de préparation, composition herbicide et utilisation associée
CN107531648B (zh) 除草化合物
JP2023521170A (ja) 除草性化合物
EA031606B1 (ru) Гербицидные соединения
RU2822391C2 (ru) Циклические дионы в качестве гербицидных соединений
CN111867378A (zh) 植物生长调节化合物
CN109890796B (zh) 除草哒嗪酮化合物

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: 22869057

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE