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
  • A01N43/64—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with three nitrogen atoms as the only ring hetero atoms
  • A01N43/647—Triazoles; Hydrogenated triazoles
  • A01N43/653—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
  • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
  • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
  • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
  • C07D249/12—Oxygen or sulfur atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
  • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
  • C07D405/12—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

• the present invention provides a novel triazole compound and a preparation method thereof; a composition containing the compound and uses thereof in agriculture.
• the present invention provides a novel triazole compound with fungicidal activity.
• One purpose of the present invention is to provide a novel fungicide compound with a remarkable effect on the control of plant diseases, a fungicide composition and a formulation containing the fungicide compound, and uses thereof.
• the present invention provides a compound having Formula (IV) or a stereoisomer, an N-oxide, a salt thereof:
• y is 0 or 1
• q is 0 or 1
• each R 2 is independently hydrogen, CH 3 -or CH 3 CH 2 CH 2 -;
• R 3 and R 4 , R 4 and R 5 , R 5 and R 6 , or R 6 and R 7 form -O-CH 2 -O-;
• n is independently 1, 2, 3, 4 or 5;
• R 3 , R 4 , R 5 , R 6 and R 7 are chlorine, at least one of the rest is not hydrogen, and R 3 and R 7 are not chlorine at the same time;
• R 5 when R 5 is -OCH 3 , at least one of R 3 , R 4 , R 6 and R 7 is not hydrogen, and R 4 or R 6 is not fluorine;
• the present invention provides a compound having one of the following structures or a stereoisomer, an N-oxide, or a salt thereof:
• composition comprising the compound disclosed herein. Unless otherwise indicated, all tautomers, racemates, hydrates, solvates, metabolites, metabolic precursors and prodrugs of the compound of the invention are within the scope of the present invention.
• composition disclosed herein further comprises a pesticidally acceptable surfactant and/or carrier.
• the compound or the composition disclosed herein in the control of plant diseases, in particular as a fungicide.
• the plant disease is caused by a phytopathogenic fungus.
• the plant disease is caused by a pseudoperonospora cubensis.
• fungicide in a further aspect, is use of the compound or a composition disclosed herein as a fungicide.
• the compound or the composition disclosed herein for use in the control of plant diseases, in particular as a fungicide.
• the plant disease is caused by a phytopathogenic fungus.
• the plant disease is caused by a pseudoperonospora cubensis.
• provided herein is the compound or a composition disclosed herein for use as a fungicide.
• a method for controlling the plant diseases comprising administering an effective amount of the compound or the composition disclosed herein to the plant or the growth environment thereof.
• the plant disease is caused by a phytopathogenic fungus.
• the plant disease is caused by a pseudoperonospora cubensis.
• a method for sterilizing comprising administering an effective amount of the compound or the composition disclosed herein to the plant or the growth environment thereof.
• Isotopically enriched compounds have the structure of the compound of formula (IV) or the compound disclosed herein, except that one or more atoms are replaced by an atom having a selected atomic mass or mass number.
• Exemplary isotopes that may be incorporated into the compounds of the invention include isotopes of hydrogen, carbon, nitrogen, oxygen, phosphorus, sulfur, fluorine, and chlorine, such as 2 H, 3 H, 11 C, 13 C, 14 C, 15 N, 17 O, 18 O, 18 F, 31 P, 32 P, 35 S, 36 Cl and 125 I.
• Any asymmetric atom (e.g., carbon or the like) of the compound of formula (IV) or the compound disclosed herein can be present in racemic or enantiomerically enriched form, for example the (R) -, (S) -or (R, S) -configuration.
• Salts of the compound of formula (IV) or salts of the compound disclosed herein include those derived from alkali or alkaline earth metals and those derived from ammonia and amines.
• Preferred cations include sodium, potassium, magnesium, and ammonium cations of the formula N + (R 19 R 20 R 21 R 22 ) , wherein R 19 , R 20 , R 21 and R 22 are independently selected from hydrogen, C 1 -C 6 alkyl and C 1 -C 6 hydroxyalkyl.
• Salts of the compound of formula (IV) or salts of the compound disclosed herein can be prepared by treating the compound of chemical formula (IV) or the compound disclosed herein with metal hydroxides (such as sodium hydroxide) or amines (such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine) .
• metal hydroxides such as sodium hydroxide
• amines such as ammonia, trimethylamine, diethanolamine, 2-methylthiopropylamine, diallylamine, 2-butoxyethylamine, morpholine, cyclododecylamine or benzylamine
• acceptable salts can be formed from organic acids or inorganic acids, such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid, naphthalenesulfonic acid, benzenesulfonic acid, toluenesulfonic acid, camphorsulfonic acid, or similarly known acceptable acids.
• organic acids or inorganic acids such as acetic acid, propionic acid, lactic acid, citric acid, tartaric acid, succinic acid, fumaric acid, maleic acid, malonic acid, mandelic acid, malic acid, phthalic acid, hydrochloric acid, hydrobromic acid, phosphoric acid, nitric acid, sulfuric acid, methanesulfonic acid
• stereoisomers refers to compounds which have identical chemical constitution, but differ with regard to the arrangement of the atoms or groups in space. Stereoisomers include enantiomer, diastereomers, conformer (rotamer) , geometric (cis/trans) isomer, atropisomer, etc.
• Enantiomers refers to two stereoisomers of a compound which are non-superimposable mirror images of one another.
• Diastereomer refers to a stereoisomer with two or more centers of chirality and whose molecules are not mirror images of one another. Diastereomers have different physical properties, e.g. melting points, boling points, spectral properties or biological activities. Mixture of diastereomers may separate under high resolution analytical procedures such as electrophoresis and chromatography such as HPLC.
• optically active compounds Many organic compounds exist in optically active forms, i.e., they have the ability to rotate the plane of plane-polarized light.
• the prefixes D and L, or R and S are used to denote the absolute configuration of the molecule about its chiral center (s) .
• the prefixes d and l or (+) and (-) are employed to designate the sign of rotation of plane-polarized light by the compound, with (-) or l meaning that the compound is levorotatory.
• a compound prefixed with (+) or d is dextrorotatory.
• a specific stereoisomer may be referred to as an enantiomer, and a mixture of such stereoisomers is called an enantiomeric mixture.
• a 50: 50 mixture of enantiomers is referred to as a racemic mixture or a racemate, which may occur where there has been no stereoselection or stereospecificity in a chemical reaction or process.
• any asymmetric atom (e.g., carbon or the like) of the compound (s) disclosed herein can be present in racemic or enantiomerically enriched form, for example the (R) -, (S) -or (R, S) -configuration.
• each asymmetric atom has at least 50 %enantiomeric excess, at least 60 %enantiomeric excess, a t least 70 %enantiomeric excess, at least 80 %enantiomeric excess, at least 90 %enantiomeric excess, at least 95 %enantiomeric excess, or at least 99 %enantiomeric excess in the (R) -or (S) -configuration.
• the compounds can be present in the form of one of the possible stereoisomers or as mixtures thereof, such as racemates and diastereoisomer mixtures, depending on the number of asymmetric carbon atoms.
• Optically active (R) -and (S) -isomers may be prepared using chiral synthons or chiral reagents, or resolved using conventional techniques. If the compound contains a double bond, the substituent may be E or Z configuration. If the compound contains a disubstituted cycloalkyl, the cycloalkyl substituent may have a cis-or trans-configuration.
• Any resulting mixtures of stereoisomers can be separated on the basis of the physicochemical differences of the constituents, into the pure or substantially pure geometric isomers, enantiomers, diastereomers, for example, by chromatography and/or fractional crystallization.
• racemates of final products or intermediates can be resolved into the optical antipodes by methods known to those skilled in the art, e.g., by separation of the diastereomeric salts thereof.
• Racemic products can also be resolved by chiral chromatography, e.g., high performance liquid chromatography (HPLC) using a chiral adsorbent.
• HPLC high performance liquid chromatography
• enantiomers can be prepared by asymmetric synthesis.
• substituents of compounds disclosed herein are disclosed in groups or in ranges. It is specifically intended that the invention include each and every individual subcombination of the members of such groups and ranges.
• the term “C 1 -C 6 alkyl” or “C 1-6 alkyl” is specifically intended to individually disclose methyl, ethyl, C 3 alkyl, C 4 alkyl, C 5 alkyl, and C 6 alkyl.
• alkyl refers to a saturated linear or branched-chain monovalent hydrocarbon group of 1-20 carbon atoms. Unless otherwise stated, the alkyl group contains 1-20 carbon atoms. In some embodiments, the alkyl group contains 1-12 carbon atoms; in some embodiments, the alkyl group contains 1-8 carbon atoms; in other embodiments, the alkyl group contains 1-6 carbon atoms; in still other embodiments, the alkyl group contains 1-4 carbon atoms; in yet other embodiments, the alkyl group contains 1-3 carbon atoms.
• alkyl groups include, but are not limited to, methyl (Me, -CH 3 ) , ethyl (Et, -CH 2 CH 3 ) , n-propyl (n-Pr, -CH 2 CH 2 CH 3 ) , isopropyl (i-Pr) , -CH (CH 3 ) 2 ) , n-butyl (n-Bu, -CH 2 CH 2 CH 2 CH 3 ) , isobutyl (i-Bu, -CH 2 CH (CH 3 ) 2 ) , sec-butyl (s-Bu, -CH (CH 3 ) CH 2 CH 3 ) , tert-butyl (t-Bu, -C (CH 3 ) 3 ) , n-pentyl (-CH 2 CH 2 CH 2 CH 3 ) , 2-pentyl (-CH (CH 3 ) CH 2 CH 2 CH 3 ) , 3-pentyl (-CH (CH 2
• alkenyl refers to linear or branched-chain monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least one site of unsaturation, i.e., a carbon-carbon sp2 double bond, wherein, the alkenyl radical may be optionally substituted independently with one or more substituents described herein, and includes radicals having “cis” and “trans” orientations, or alternatively, “E” and “Z” orientations.
• the alkenyl contains 2 to 8 carbon atoms.
• the alkenyl contains 2 to 6 carbon atoms.
• the alkenyl contains 2 to 4 carbon atoms.
• alkynyl refers to a linear or branched monovalent hydrocarbon radical of 2 to 12 carbon atoms with at least a carbon-carbon, sp triple bond.
• alkoxy refers to an alkyl group, as defined herein, attached to the remainder of the molecule via an oxygen atom.
• alkoxy include, but are not limited to, methoxy (MeO, -OCH 3 ) , ethoxy (EtO, -OCH 2 CH 3 ) , 1-propoxy (n-PrO, n-propoxy, -OCH 2 CH 2 CH 3 ) , isopropoxy (i-PrO, i-propoxy, -OCH (CH 3 ) 2 ) , isobuty l (i-BuO, i-butoxy, CH (CH 3 ) 2 CH 2 O-) , isopentyloxy (CH (CH 3 ) 2 CH 2 CH 2 O-) and the like.
• alkenyloxy refers to an alkenyl group, as defined herein, attached to the remainder of the molecule via an oxygen atom.
• alkynyloxy refers to an alkynyl group, as defined herein, attached to the remainder of the molecule via an oxygen atom.
• alkylthio refers to the alkyl group, as defined herein, attached to the remainder of the molecule via a sulfur atom.
• alkylthio include, but are not limited to, -SCH 3 , -SCH 2 CH 3 , -SCH 2 CH 2 CH 3 , -SCH (CH 3 ) 2 , and the like.
• cycloalkyl refers to a monovalent or multivalent saturated monocyclic, bicyclic, or tricyclic ring system having 3 to 12 carbon atoms. In some embodiments, the cycloalkyl contains 3 to 10 carbon atoms. In other embodiments, the cycloalkyl contains 3 to 8 carbon atoms. In still other embodiments, the cycloalkyl contains 3 to 6 carbon atoms.
• the cycloalkyl is optionally substituted with one or more substituents described herein.
• Some examples include, but not limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclohendecyl and cyclododecyl, etc.
• haloalkyl refers to an alkyl group substituted with one or more halogen atoms, wherein the alkyl group is as defined herein.
• haloalkyl include -CH 2 F, -CHF 2 , -CH 2 Cl, -CH 2 Br, -CF 3 , -CH 2 CF 3 , -CH 2 CH 2 F, -CH 2 CH 2 Cl, -CH 2 CH 2 Br, -CH 2 CHF 2 , -CH 2 CH 2 CF 3 , -CH 2 CH 2 CH 2 F, -CH 2 CH 2 CH 2 Cl, -CH 2 CH 2 CH 2 Br, -CHFCH 2 CH 3 , -CHClCH 2 CH 3 , and the like.
• haloalkoxy refers to an alkoxy group substituted with one or more halogen atoms, wherein the alkoxy group is as defined herein.
• Some non-limiting examples of haloalkoxy include -OCH 2 F, -OCHF 2 , -OCH 2 Cl, -OCH 2 Br, -OCF 3 , -OCH 2 CF 3 , -OCH 2 CH 2 F, -OCH 2 CH 2 Cl, -OCH 2 CH 2 Br, -OCH 2 CHF 2 , -OCH 2 CH 2 CF 3 , -OCH 2 CH 2 CH 2 F, -OCH 2 CH 2 CH 2 Cl, -OCH 2 CH 2 CH 2 Br, -OCHFCH 2 CH 3 , -OCHClCH 2 CH 3 , and the like.
• haloalkylthio refers to an alkylthio group substituted with one or more halogen atoms, wherein the alkylthio group is as defined herein.
• the compound of the present invention can generally be used as fungicide active ingredients in compositions or formulations, and generally also include pesticidally acceptable surfactants and/or carriers.
• the above surfactants may be various surfactants well known in the field of pesticide formulations, and the present invention is preferably one or more of an emulsifier, a dispersant and a wetting agent.
• Other carriers other than the above surfactants may be various carriers well known in the field of pesticide formulations, including various silicates, carbonates, sulfates, oxides, phosphates, plant carriers, and synthetics. Specifically, for example, one or more of silica, kaolin, diatomaceous earth, clay, talc, organic bentonite, pumice, titanium dioxide, dextrin, cellulose powder, light calcium carbonate, soluble starch, corn starch, sawdust powder, urea, amine fertilizer, mixture of urea and amine fertilizer, glucose, maltose, sucrose, anhydrous potassium carbonate, anhydrous sodium carbonate, anhydrous potassium hydrogencarbonate, anhydrous sodium hydrogencarbonate, attapulgite, mixture of anhydrous potassium carbonate and anhydrous potassium hydrogencarbonate and mixture of anhydrous sodium carbonate and anhydrous sodium hydrogencarbonate.
• silica kaolin, diatomaceous earth, clay, talc, organic bentonite, pumic
• the above emulsifier may be various emulsifiers known in the field of pesticide formulations.
• the emulsifier may be one or more of calcium dodecylbenzenesulfonate, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether, alkylphenol ethoxylates, alkylphenol polyoxyethylene polyoxypropylene ethers, fatty amines, ethylene oxide adducts of fatty amides, fatty acid polyoxyethylene esters, rosin acid ethylene oxide adducts , polyol fatty acid ester and ethylene oxide adduct thereof, styryl phenyl polyoxyethylene ether, alkyl phenol formaldehyde resin polyoxyethylene ether, hydroxyl-terminated polyoxyethylene polyoxypropylene ether, styryl phenol formaldehyde resin polyoxyethylene polyoxypropylene ether and castor oil polyoxyethylene ether.
• the above dispersing agent may be various dispersing agents known in the field of agricultural pesticide formulations.
• the dispersing agent is one or more of acrylic acid homopolymer sodium salt, maleic acid disodium salt, naphthalenesulfonic acid formaldehyde condensate sodium salt, rosin block polyoxyethylene ether polyoxypropylene ether sulfonate, hydroxyl-terminated polyoxyethylene polyoxypropylene ether block copolymer, triphenylethylphenol polyoxyethylene ether phosphate, fatty alcohol polyoxyethylene ether phosphate and sodium p-hydroxyphenyl lignosulfonate.
• the above wetting agent may be various wetting agents known in the field of pesticide formulations.
• the wetting agent may be one or more of sodium lauryl sulfate, sodium secondary alkyl sulfate, sodium dodecylbenzenesulfonate, fatty alcohol polyoxyethylene ether, alkylnaphthalenesulfonate, alkylphenol resin polyoxyethylene ether sulfate.
• the fungicidal composition may further contain various auxiliaries for use in preparations conventionally used in the field of pesticide preparations.
• the auxiliary agent to be prepared may be one or more of solvents, co-solvents, thickeners, antifreezes, capsules, protectants, antifoaming agents, disintegrants, stabilizers, preservatives and binders.
• the above solvent can be known as various solvents in the field of pesticide formulations.
• the solvents can be one or more of organic solvents, vegetable oils, mineral oils, solvent oils and water.
• the organic solvent comprises one or more of N-methylpyrrolidone, tetrahydrofuran, dimethyl sulfoxide, N, N-dimethyldecanoamide, N, N-dimethylformamide, trimethylbenzene, tetramethylbenzene, xylene, toluene, octane, heptane, methanol, isopropanol, n-butanol, tetrahydrofurfury l alcohol, tributyl phosphate, 1, 4-dioxane and cyclohexanone.
• the vegetable oil includes one or more of methylated vegetable oil, rosin-based vegetable oil, turpentine oil, epoxidized soybean oil, soybean oil, peanut oil, rapeseed oil, castor oil, corn oil, and pine nut oil.
• the mineral oil includes one or more of liquid wax, engine oil, kerosene, and lubricating oil.
• the above solvent can also be used as a co-solvent.
• the above antifreeze agent may be various antifreeze agents known in the field of pesticide formulations, and the present invention is preferably one or more of ethylene glycol, propylene glycol, glycerin and urea.
• the above thickener may be various thickeners known in the field of pesticide formulations.
• the thickener may be one or more of xanthan gum, polyvinyl alcohol, polypropylene alcohol, polyethylene glycol, silica, diatomite, kaolin, clay, sodium alginate, aluminum magnesium silicate, sodium aluminum silicate, carboxymethyl cellulose, sodium hydroxypropyl cellulose, and organic bentonite.
• the above-mentioned capsules may be various kinds of capsules known in the field of pesticide formulations, and one or more of polyurethane, polyurea and urea-formaldehyde resins are preferred in the presen t invention.
• the above protective agent may be various protective agents known in the field of pesticide formulations, and the present invention is preferably polyvinyl alcohol and/or polyethylene glycol.
• the above antifoaming agent may be various antifoaming agents known in the field of pesticide formulations, and the present invention is preferably one or more of organosiloxane, tributyl phosphate and silicone.
• the above stabilizer is selected from one or more of triphenyl phosphite, epichlorohydrin and acetic anhydride.
• the above preservative is selected from one or more of benzoic acid, sodium benzoate, 1, 2-benzisothiazolin-3-one (abbreviated as BIT) , carson and potassium sorbate.
• the invention also provides a preparation prepared from the above fungicidal composition, wherein the dosage forms of the preparation are emulsifiable concentrate, water emulsion, microemulsion, soluble liquid agent, aqueous suspension, suspoemulsion, ultra low volume spray, oil suspension, microcapsule suspension agent, water surface film oil agent, wettable powder, water-dispersible granule, dry suspension agent, soluble powder, soluble granule, emulsifiable powder, emulsifiable granule, granule, solid microcapsule preparation, effervescent tablet, effervescent granule, water floating dispersion granule or seed coating agent.
• the above dosage forms can be prepared by conventional methods in the art.
• the preparation method of the above emulsifiable concentrate preparation may include, for example, mixing and stirring each active component, a solvent, a co-solvent, and an emulsifier to form a uniform transparent oil phase, thereby obtaining an emulsifiable concentrate preparation.
• the preparation method of the above aqueous emulsion may, for example, comprise mixing an active ingredient, an emulsifier, a co-solvent with a solvent to form a homogeneous oil phase; mixing water, a thickener, an antifreeze or the like to form a uniform aqueous phase. Under high shear, the aqueous phase is added to the oil phase or the oil phase is added to the aqueous phase to form a water emulsion with good dispersibility.
• the preparation method of the above microemulsion may be, for example, mixing and stirring an active ingredient, an emulsifier, and a solvent into a uniform transparent oil phase. Under agitation, water is gradually added to form a uniform transparent microemulsion.
• water or oil may be used as a medium, and an auxiliary agent such as an active component or a surfactant may be added to a sanding kettle, and after grinding to a certain particle size, the mixture may be filtered.
• the metered thickener is then added to the ground mother liquor, then the mixture is sheared and dispersed evenly. It is made into oil suspension or water suspension.
• the preparation method of the above water-dispersible granules and soluble granules for example, the active components, the dispersing agent, the wetting agent, the carrier, and the like may be uniformly mixed, and then pulverized to a certain particle diameter by a jet stream, and then kneaded by adding water. Finally, it is added to a granulator for granulation, and after drying, a water-dispersible granule or a soluble granule can be obtained.
• the preparation method of the above-mentioned soluble powder and wettable powder for example, the fillers of the respective active components, various auxiliary agents and other carriers may be thoroughly mixed and pulverized by an ultrafine pulverizer.
• the fungicidal composition of the present invention may be provided in the form of a finished preparation, that is, each substance in the composition has been mixed; it may also be provided in the form of a separate preparation, which is self-mixed in a bucket or a tank before use, and selectively diluted with water and diluted according to the concentration of the required active substance.
• the compounds of the invention are useful as plant disease control agents.
• the present invention therefore further comprises a method for controlling plant diseases caused by a phytopathogenic fungus, comprising applying to the plant or portion thereof to be protected, or to the plant seed to be protected, an effective amount of a compound of the invention or a fungicidal composition containing asid compound.
• the compound and/or composition of the present invention can provide control over diseases caused by a broad spectrum of phytopathogenic fungi in the Basidiomycete, Ascomycete, Oomycete, and Deuteromycete classes. They are effective in controlling a broad spectrum of plant diseases, especially foliar pathogens of ornamental crops, turf crops, vegetable crops, field crops, cereal crops and fruit crops.
• pathogens include: Oomycetes, including Phytophthora diseases such as Pathogenic Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici, Pythium diseases such as Pythium aphanidermatum, and diseases in the Peronosporaceae family such as Plasmopara viticola, Peronospora spp. diseases (including Peronospora tabacina and Peronospora parasitica) , Pseudoperonospora spp.
• Phytophthora diseases such as Pathogenic Phytophthora infestans, Phytophthora megasperma, Phytophthora parasitica, Phytophthora cinnamomi and Phytophthora capsici
• Pythium diseases such as Pythium aphanidermatum
• Botrytis diseases such as Botrytis cinerea, Monilinia fructicola, Sclerotinia diseases such as Sclerotinia sclerotiorum, Magnaporthe grisea, Phomopsis viticola, Helminthosporium diseases such as Helminthosporium tritici repentis, Pyrenophora teres, anthracnose diseases (such as Colletotrichum graminicola and Colletotrichum orbiculare) and Gaeumannomyces graminis; Basidiomycetes, including rust fungus caused by Puccinia spp.
• compositions or combinations also have resistance activity against bacteria such as Erwinia amylovora, Xanthomonas campestris, Pseudomonas syringae and other related species.
• the fungicidal composition of the present invention is simple to use, and is applied to crops and places where crops grow before or after the germination of plant diseases in a conventional manner, such as soil mixing, spraying, jetting, pouring, etc.
• the amount of application depends on the climatic conditions or the state of the crop. It is generally applied in an amount of 10-5000 g per acre and diluted to 10-400 mg/L (preferably 100-300 mg/L) for administration.
• the diluent is preferably water.
• the fungicidal effect of the fungicidal composition of the present invention is usually related to external factors such as climate, but the influence of the climate can be alleviated by using an appropriate dosage form.
• composition of the present invention can also be used in combination with other compounds having fungicidal, insecticidal or herbicidal properties, or with nematicides, acaricides, protectants, herbicide safeners, growth regulators, phytonutrients or soil conditioners, etc.
• the compounds of the invention can be prepared by the methods described herein.
• the raw materials, reagents and the like used in the preparation of the compounds of the present invention are all commercially available, raw materials or reagents are purchased from commodity suppliers such as Angie Chemical, Aladdin or Belling, etc. ; or raw materials, reagents can be prepared by conventional methods in the art.
• the chemical name of the compound doesn’t match the corresponding structure, the compound is characterized by the corresponding structure.
• the nuclear magnetic resonance spectrum of the present invention is tested under the conditions of a Bruker 400 MHz or 600 MHz nuclear magnetic instrument at room temperature, using CDC1 3 , d 6 -DMSO, CD 3 OD or d 6 -acetone as solutions (reported in ppm) , and using TMS (0 ppm) or chloroform (7.26 ppm) as the reference standard.
• peak multiplicities the following abbreviations are used: s (singlet) , d (doublet) , t (triplet) , q (quartet) , m (multiplet) , br (broadened) , dd (doublet of doublets) , dt (doublet of triplets) .
• the low resolution mass spectrometry (MS) data of the present invention is determined under the following conditions: Agilent 6120 Quadrupole HPLC-MS (column model: Zorbax SB-C18, 2.1 x 30 mm, 3.5 ⁇ m, 6 min, flow rate 0.6 mL/min, mobile phase : 5%-95% (CH 3 CN with 0.1%formic acid) in a ratio of (containing 0.1%formic acid in H 2 O) ) , UV detection at 210/254 nm, electrospray ionization mode (ESI) .
• Agilent 6120 Quadrupole HPLC-MS column model: Zorbax SB-C18, 2.1 x 30 mm, 3.5 ⁇ m, 6 min, flow rate 0.6 mL/min, mobile phase : 5%-95% (CH 3 CN with 0.1%formic acid) in a ratio of (containing 0.1%formic acid in H 2 O) )
• UV detection at 210/254 nm electros
• Target compound (c) disclosed herein can be prepared by the process illustrated in scheme 1.
• Compound (a) can be subjected to a nucleophilic substitution reaction with compound (b) under basic conditions (such as sodium hydroxide, sodium hydride, potassium carbonate, etc. ) to give a target compound (c) .
• basic conditions such as sodium hydroxide, sodium hydride, potassium carbonate, etc.
• Target compound (c-1) can be prepared by the process illustrated in scheme 2.
• Compound (a) can be subjected to a nucleophilic substitution reaction with compound (b-1) under basic conditions (such as sodium hydroxide, sodium hydride, potassium carbonate, etc. ) to give a target compound (c-1) .
• basic conditions such as sodium hydroxide, sodium hydride, potassium carbonate, etc.
• Target compound (c-2) can be prepared by the process illustrated in scheme 3.
• Compound (d) can be subjected to a nucleophilic substitution reaction with compound (e) under basic conditions (such as sodium hydroxide, sodium hydride, potassium carbonate, etc. ) to give a target compound (c-2) .
• each hal is independently chlorine, bromine or iodine
• R a and R b , R b and R c , R c and R d , or R d and R e form -O- (CH 2 ) w -O-, wherein w is 1 or 2;
• each of R f , R g , R f1 and R g1 is independently hydrogen, fluorine, clorine or C 1-6 alkyl;
• each of R 11 and R 12 is independently C 3-6 cycloalkyl.
• N 3 - (2-fluorobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.36 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (2, 5-difluorobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.38 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (3, 4-difluorobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.38 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (4-fluoro-3- (trifluoromethyl) benzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.43 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (4-bromo-2, 6-difluorobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.46 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 1 , N 1 -dimethyl-N 3 - ( (perfluorobenzyl) methyl) -1H-1, 2, 4-triazole-1, 3-disulfonamide (0.44 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromomethylcyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 1 , N 1 -dimethyl-N 3 - (3, 4, 5-trifluorobenzyl) -1H-1, 2, 4-triazole-1, 3-disulfonamide (0.40 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromomethylcyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 1 , N 1 -dimethyl-N 3 - (2, 3, 4, 5, 6-pentamethylbenzyl) -1H-1, 2, 4-triazole-1, 3-disulfonamide (0.42 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromomethylcyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (4- (trifluoromethyl) benzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.41 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 4) .
• N 3 - (4-iodobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.47 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (3- (trifluoromethyl) benzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.41 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (3- (trifluoromethoxy) benzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.43 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (2-iodobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.47 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N 3 - (3-cyanobenzyl) -N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.37 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• bromocyclopropane (0.24 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• N- (2-chlorobenzyl) -O-ethylhydroxylamine (0.37 g, 2.0 mmol)
• pyridine (0.32 g, 4.0 mol)
• tetrahydrofuran 10 mL
• 1- (N, N-Dimethylaminosulfonyl) -1H-1, 2, 4-triazole-3-sulfonyl chloride (0.55 g, 2.0 mmol) was slowly added to the reaction system.
• N- (2, 5-difluorobenzyl) -O-ethylhydroxylamine (0.37 g, 2.0 mmol)
• pyridine (0.32 g, 4.0 mol
• tetrahydrofuran 10 mL
• 1- (N, N-Dimethylaminosulfonyl) -1H-1, 2, 4-triazole-3-sulfonyl chloride (0.55 g, 2.0 mmol) was slowly added to the reaction system.
• N 1 , N 1 -dimethyl-N 3 - (3- (trifluoromethyl) phenyl) -1H-1, 2, 4-triazole-1, 3-disulfonamide (0.40 g, 1.0 mmol) and THF (30 mL) .
• NaH 60%, 0.48 g 12 mmol
• 2-methoxyethy l chloroformate (0.28 g, 2.0 mmol) was slowly added to the reaction system.
• N 3 -cyclopropyl-N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide (0.30 g, 1.0 mmol)
• potassium carbonate (0.28 g, 2.0 mmol)
• DMF 10 mL
• 2- (bromomethyl) benzonitrile (0.39 g, 2.0 mmol) was slowly added to the reaction system.
• the mixture was reacted for 8 h at 25 °C, quenched with water (20 mL) , extracted with ethyl acetate (15 mL ⁇ 3) .
• Example E (intermediate N 3 -cyclopropyl-N 1 , N 1 -dimethyl-1H-1, 2, 4-triazole-1, 3-disulfonamide) can reac t with compound (b) ( wherein R a , R b , R c , R d , R e , R f , R g and X have the meanings described herein) or compound (b-1) (wherein R a1 , R b1 , R c1 , R d1 , R e1 and X 1 have the meanings described herein) according to a similar preparation method of example 19 to give the target compounds of table 1.
• Test target pseudoperonospora cubensis
• Test treatment The compounds were dissolved in DMF to form 1%EC for use. The fungicidal activity of these compounds on pseudoperonospora cubensis at different doses was evaluated by live potting.
• a potted cucumber seedling with the same growth in leaf period was selected to dry naturally after spray treatment. After 24 h of treatment, the cucumber seedling was inoculated, and the fresh cucumber downy mildew leaves were picked up. The sporangia on the back of the diseased leaf was washed with distilled water using a brush, and formulated as a sporangia suspension ( (2-3) x 10 5 /mL) .
• the inoculation sprayer pressure 0.1 MPa was sprayed uniformly on the cucumber seedlings.
• the inoculated test material was moved to the artificial climate chamber to maintain the relative humidity of 100%and the temperature at about 21 °C. After 24 hours, the temperature was maintained at 21 °C, and the relative humidity was about 95%.
• the graded survey was conducted according to the incidence of the blank control after 5 days, and the control effect was calculated according to the disease index.
• Example Control effect (%) Example 1 100 Example 2 100 Example 4 100 Example 5 100 Example 6 100 Example 7 100 Example 8 100 Example 9 100 Example 10 100 Example 11 100 Example 12 100 Example 13 100 Example 14 100 Example 15 100 Example 16 100 Example 17 100 Example 19 100 Example 20 100 Example 21 100 Example 22 100 Example 23 100 Example 24 100 Example 25 100 Example 26 100 Example 27 100 Example 28 100 Example 29 100 Example 30 100 Example 31 100 Example 32 100 Example 33 100 Example 34 100 Example 35 100 Example 36 100 Example 37 100 Example 38 100 Example 39 100 Example 40 100 Example 41 100
• Example Control effect (%) Example 1 100 Example 2 100 Example 4 100 Example 5 100 Example 6 100 Example 7 100 Example 8 100 Example 9 100 Example 10 100 Example 11 100 Example 12 100 Example 13 100 Example 14 100 Example 15 100 Example 19 100 Example 20 100 Example 21 100 Example 22 100 Example 23 100 Example 24 100 Example 25 100 Example 26 100 Example 27 100 Example 28 100 Example 29 80 Example 31 100 Example 32 100 Example33 90 Example 34 100 Example 35 100 Example 36 100 Example 37 100 Example 38 100 Example39 100 Example40 100 Example41 100 Example 42 90
• Example Control effect (%) Example 1 100
• Example 2 100
• Example Control effect (%) Example 4 100
• Example 5 100
• Example 10 100
• Example 12 100
• Example 13 100
• Example 23 80 Example 28 100
• Tables A to D show that the compound of the present invention has significant control effects against cucumber downy mildew at different concentrations, and has a good development prospect.

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