WO2021120992A1 - Dérivés de triazole et leur utilisation - Google Patents

Dérivés de triazole et leur utilisation Download PDF

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WO2021120992A1
WO2021120992A1 PCT/CN2020/131020 CN2020131020W WO2021120992A1 WO 2021120992 A1 WO2021120992 A1 WO 2021120992A1 CN 2020131020 W CN2020131020 W CN 2020131020W WO 2021120992 A1 WO2021120992 A1 WO 2021120992A1
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alkyl
halogenated
alkoxy
alkylthio
alkoxycarbonyl
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PCT/CN2020/131020
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English (en)
Chinese (zh)
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周繁
冉兆晋
孙朝辉
毛志强
王芳
王志祥
崔顺艳
侯薪鑫
王宇
石凯强
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沈阳化工研究院有限公司
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • 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
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/06—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D411/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms
    • C07D411/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D411/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having oxygen and sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
    • Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture

Definitions

  • the invention belongs to the field of chemistry, specifically a triazole derivative, and the application of the derivative in plant growth regulation and fungicides.
  • Paclobutrazol is a plant growth regulator, which has the effects of delaying plant growth, inhibiting stem elongation, shortening internodes, promoting plant tillering, increasing plant resistance to stress, and increasing yield.
  • soil half-life is 0.5-1.0 years
  • the purpose of the present invention is a triazole derivative and its application.
  • a triazole derivative which is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, oxazolyl, isoxazole containing C, N, O or S substituted by 1-5 R 8 Heteroaryl groups such as thiazolyl, thiazolyl, isothiazolyl, oxadiazolyl or thiadiazolyl;
  • R 6 and R 7 which are the same or different are selected from hydrogen, hydroxyl, amino, C 1 -C 12 alkyl, halogenated C 1 -C 12 alkyl, C 1 -C 12 alkoxy or halogenated C 1- C 12 alkoxy, C 1 -C 12 alkylamino, halogenated C 1 -C 12 alkylamino;
  • R 6 , R 7 can also be connected to the N to form a three-membered, four-membered, five-membered, six-membered, seven-membered or eight-membered heterocycloalkane containing C, N, O or S;
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, oxazolyl, isoxazole containing C, N, O or S substituted by 1-5 R 8 Heteroaryl groups such as thiazolyl, thiazolyl, isothiazolyl, oxadiazolyl or thiadiazolyl;
  • R 2 is selected from H, halogen, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl , C 1 -C 6 alkoxy C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 alkylthio C 1 -C 6 alkyl , Halogenated C 1 -C 6 alkylthio C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxycarbonyl C 1- C 6 alkyl, C 1 -C 6 alkylthiocarbonyl C 1 -C 6 alkyl or halogenated C 1 -C 6 alkylthiocarbonyl C 1 -C 6 al
  • R 3 is selected from H, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl, C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy C 1 -C 6 alkyl, C 1 -C 6 alkylthio C 1 -C 6 alkyl, halogen C 1 -C 6 alkylthio C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxycarbonyl C 1 -C 6 Alkyl, C 1 -C 6 alkylthiocarbonyl C 1 -C 6 alkyl or halogenated C 1 -C 6 alkylthiocarbonyl C 1 -C 6 alkyl;
  • R 4 and R 5 are the same or different selected from H, halogen, hydroxy, amino, nitro, cyano, C 1 -C 6 alkyl, halogenated C 1 -C 6 alkyl, C 3 -C 6 cycloalkyl , C 2 -C 6 alkenyl, C 2 -C 6 alkynyl, C 1 -C 6 alkoxy C 1 -C 6 alkyl, halogenated C 1 -C 6 alkoxy C 1 -C 6 alkyl , C 1 -C 6 alkylthio C 1 -C 6 alkyl, halogenated C 1 -C 6 alkylthio C 1 -C 6 alkyl, C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkane Group, halogenated C 1 -C 6 alkoxycarbonyl C 1 -C 6 alkyl, C 1 -C 6 alkylthiocarbonyl C 1 -C 6 alkyl,
  • R 6 and R 7 that are the same or different are selected from hydrogen, hydroxyl, amino, C 1 -C 6 alkyl, halo C 1 -C 6 alkyl, C 1 -C 6 alkoxy or halo C 1- C 6 alkoxy, C 1 -C 6 alkylamino, halogenated C 1 -C 6 alkylamino;
  • R 6 , R 7 can also be connected to the N to form a three-membered, four-membered, five-membered, six-membered, seven-membered or eight-membered heterocycloalkane containing C, N, O or S;
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, oxazolyl, isoxazole containing C, N, O or S substituted by 1-5 R 8 Heteroaryl groups such as thiazolyl, thiazolyl, isothiazolyl, oxadiazolyl or thiadiazolyl;
  • R 2 is selected from H, halogen, C 1 -C 3 alkyl, halo C 1 -C 3 alkyl, C 3 -C 4 cycloalkyl;
  • R 3 is selected from H, C 1 -C 4 alkyl
  • R 4 and R 5 are the same or different and are selected from H, halogen, C 1 -C 3 alkyl;
  • R 6 and R 7 that are the same or different are selected from hydrogen and C 1 -C 3 alkyl groups
  • R 6 , R 7 can also be connected to the N to form a three-membered, four-membered, five-membered or six-membered heterocycloalkane containing C, N, O or S;
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from unsubstituted or substituted by 1-5 R 8 pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, 1, 2, 4-oxadiazole, 1,3,4-oxadiazole, 1,2,4-thiadiazole or 1,3,4-thiadiazole;
  • R 2 is selected from H, C 1 -C 3 alkyl
  • R 3 is selected from H, C 1 -C 4 alkyl
  • R 4 and R 5 are the same or different and are selected from H, halogen, C 1 -C 3 alkyl;
  • R 6 and R 7 that are the same or different are selected from hydrogen and C 1 -C 3 alkyl groups
  • R 6 , R 7 can also be connected to the N to form a three-membered, four-membered, five-membered or six-membered heterocycloalkane containing C, N, O or S;
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected unsubstituted or substituted with 1-5 R 8 5-pyridyl, 2-pyridyl, 5-pyrimidinyl, 2-pyrimidinyl, 2-pyrazinyl, 2-pyridazinyl, 5- Oxazolyl, 4-oxazolyl, 5-isoxazolyl, 3-isoxazolyl, 5-thiazolyl, 4-thiazolyl, 5-isothiazolyl, 3-isothiazolyl, 3-1, 2,4-oxadiazole, 5-1,2,4-oxadiazole, 5-1,3,4-oxadiazole, 3-1,2,4-thiadiazole, 5-1,2, 4-thiadiazole or 5-1,3,4-thiadiazole;
  • R 2 is selected from H, methyl
  • R 3 is selected from tert-butyl
  • R 4 and R 5 are the same or different and are selected from H and methyl;
  • R 8 is selected from H, halogen, nitro, cyano, methyl, trifluoromethyl, methoxy, trifluoromethoxy, dimethylamino, methylcarbonyl, methoxycarbonyl, methylcarbonyloxy , Trifluoromethylcarbonyloxy, methylsulfonyloxy, methoxyethoxy or ethoxyethoxy.
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from 2-R 8 -5-pyridyl, 5-R 8 -2-pyridyl, 2-R 8 -5-pyrimidinyl, 5-R 8 -2-pyrimidinyl, 2-R 8 -5 -Pyrazinyl, 2-R 8 -6-pyridazinyl, 2-R 8 -5-oxazolyl, 2-R 8 -4-oxazolyl, 3-R 8 -5-isoxazolyl, 5-R 8 -3-isothiazolyl, 2-R 8 -5-thiazolyl, 2-R 8 -4-thiazolyl, 3-R 8 -5-isothiazolyl, 5-R 8 -3- Isothiazolyl, 5-R 8 -3-1,2,4-oxadiazole, 3-R 8 -5-1,2,4-oxadiazole, 2-R 8 -5-1,3,4 -Oxadiazole, 5-R 8 -3-1,2,4-thiadiazole, 3-R 8 -5-1,2,4-
  • R 2 is selected from H
  • R 3 is selected from tert-butyl
  • R 4 and R 5 are selected from H;
  • R 8 is selected from halogen and methoxy.
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from 2-R 8 -5-pyridyl, 5-R 8 -2-pyridyl, 2-R 8 -5-pyrimidinyl, 2-R 8 -5-pyrazinyl, 2-R 8- 6-pyridazinyl or 2-R 8 -5-thiazolyl;
  • R 2 is selected from H
  • R 3 is selected from tert-butyl
  • R 4 and R 5 are selected from H;
  • R 8 is selected from chlorine, bromine and methoxy.
  • the triazole derivative is a compound represented by general formula I, its diastereomers, chiral isomers or salts thereof:
  • R 1 is selected from 2-R 8 -5-pyridyl
  • R 2 is selected from H
  • R 3 is selected from tert-butyl
  • R 4 and R 5 are selected from H;
  • R 8 is selected from chlorine, bromine and methoxy.
  • One of the triazole derivatives is used in the preparation of plant growth regulators or fungicides.
  • the triazole derivative as an active component in the preparation of plant growth regulators or fungicides; the weight percentage of the active component is 0.1-99%.
  • the use of the derivative of the present invention is as a plant growth control and fungicide.
  • a kind of triazole derivative represented by formula I as a salt can be hydrochloride, sulfate, hydrobromide, methanesulfonate, citrate, oxalate, succinate, maleate Acid salt, citrate, acetate, lactate, phosphate, hydroiodide, nitrate, tartrate, p-toluenesulfonate, etc.
  • Halogen refers to fluorine, chlorine, bromine or iodine.
  • Alkyl straight or branched chain alkyl, such as methyl, ethyl, propyl, isopropyl, n-butyl or tert-butyl.
  • Cycloalkyl A substituted or unsubstituted heteroatom-containing cyclic alkyl group, such as cyclopropyl, cyclopentyl or cyclohexyl. Substituents such as methyl, halogen and the like.
  • Heterocycloalkyl substituted or unsubstituted cyclic alkyl containing one or more N, O, S heteroatoms, such as tetrahydrofuranyl, cyclopentapiperidinyl. Substituents such as methyl, halogen and the like.
  • Halogenated alkyl groups straight or branched chain alkyl groups.
  • the hydrogen atoms on these alkyl groups can be partially or fully replaced by halogen atoms, for example, chloromethyl, dichloromethyl, trichloromethyl, fluoromethyl, dichloromethane, Fluoromethyl, trifluoromethyl, etc.
  • Alkoxy straight or branched chain alkyl, connected to the structure via an oxygen atom bond.
  • Halogenated alkoxy groups straight-chain or branched-chain alkoxy groups.
  • the hydrogen atoms on these alkoxy groups may be partially or completely replaced by halogen atoms.
  • halogen atoms for example, chloromethoxy, dichloromethoxy, trichloromethoxy, fluoromethoxy, difluoromethoxy, trifluoromethoxy, chlorofluoromethoxy, trifluoroethoxy and the like.
  • Alkoxyalkyl The alkoxy group is attached to the structure via the alkyl group. Such as -CH 2 OCH 3 , -CH 2 OCH 2 CH 3 .
  • Halogenated alkoxyalkyl The hydrogen atoms on the alkyl group of the alkoxyalkyl group may be partially or completely replaced by halogen atoms. Such as -CH 2 OCH 2 CH 2 Cl.
  • Alkylthio straight or branched chain alkyl, connected to the structure via a sulfur atom bond.
  • Halogenated alkylthio linear or branched alkylthio.
  • the hydrogen atoms on these alkyl groups may be partially or completely replaced by halogen atoms.
  • halogen atoms for example, chloromethylthio, dichloromethylthio, trichloromethylthio, fluoromethylthio, difluoromethylthio, trifluoromethylthio, chlorofluoromethylthio and the like.
  • Alkenyl straight or branched chain alkenes, such as vinyl, 1-propenyl, 2-propenyl and the different butenyl, pentenyl and hexenyl isomers. Alkenyl also includes polyenes such as 1,2-propadienyl and 2,4-hexadienyl.
  • Alkynyl linear or branched alkynes, such as ethynyl, 1-propynyl, 2-propynyl and the different butynyl, pentynyl and hexynyl isomers.
  • Alkynyl groups also include groups composed of multiple triple bonds, such as 2,5-hexadiynyl.
  • Alkenyloxy straight or branched chain alkenes, connected to the structure via an oxygen atom bond.
  • Halogenated alkenyloxy groups straight or branched chain alkenyloxy groups.
  • the hydrogen atoms on these alkenyloxy groups may be partially or completely replaced by halogen atoms.
  • Alkynoxy straight-chain or branched alkynes, connected to the structure via an oxygen atom bond.
  • Halogenated alkynyloxy groups straight or branched chain alkynyloxy groups.
  • the hydrogen atoms on these alkynyloxy groups may be partially or completely replaced by halogen atoms.
  • Alkylcarbonyl A straight or branched chain alkyl group is connected to the structure via a carbonyl group (-CO-), such as an acetyl group.
  • Halogenated alkylcarbonyl straight or branched chain alkylcarbonyl, the hydrogen atoms on the alkyl group can be partially or completely replaced by halogen atoms, such as trifluoroacetyl.
  • Alkoxycarbonyl The alkoxy is attached to the structure via the carbonyl group. Such as -COOCH 3 , -COOCH 2 CH 3 .
  • Halogenated alkoxycarbonyl The hydrogen atoms on the alkyl group of the alkoxycarbonyl group can be partially or completely replaced by halogen atoms, such as -COOCH 2 CF 3 , -COOCH 2 CH 2 Cl and so on.
  • Alkylsulfonyl straight or branched chain alkyl is connected to the structure via sulfonyl (-SO 2 -), such as methylsulfonyl.
  • Halogenated alkylsulfonyl linear or branched alkylsulfonyl, the hydrogen atoms on the alkyl group can be partially or completely replaced by halogen atoms.
  • Alkylsulfonyloxy alkyl-SO 2 -O-.
  • Halogenated alkylsulfonyloxy group The hydrogen atoms on the alkyl group of the alkylsulfonyloxy group may be partially or completely replaced by halogen atoms, such as CF 3 -SO 2 -O.
  • Alkoxycarbonylalkyl alkoxycarbonyl-alkyl-, for example CH 3 OCOCH 2 -.
  • Halogenated alkoxycarbonylalkyl The hydrogen atoms on the alkyl group of the alkoxycarbonylalkyl group may be partially or completely replaced by halogen atoms, such as CF 3 CH 2 OCOCH 2 -.
  • Alkylcarbonyloxy such as CH 3 COO- etc.
  • Halogenated alkylcarbonyloxy group The hydrogen atoms of the alkylcarbonyloxy group can be partially or completely replaced by halogen atoms, such as CF 3 COO- and so on.
  • Alkoxycarbonyloxy alkoxycarbonyl- oxy-, for example CH 3 OCOO-.
  • Halogenated alkoxycarbonyloxy The hydrogen atoms on the alkyl group of the alkoxycarbonyloxy group may be partially or completely replaced by halogen atoms, such as CF 3 OCOO-.
  • Alkylthiocarbonylalkyl alkylthiocarbonyl-alkyl-, for example CH 3 SCOCH 2 -.
  • Halogenated alkylthiocarbonylalkyl The hydrogen atoms on the alkyl group of the alkylthiocarbonylalkyl group may be partially or completely replaced by halogen atoms, such as CF 3 CH 2 SCOCH 2 -.
  • Alkoxyalkoxy such as CH 3 OCH 2 O- and the like.
  • Halogenated alkoxy alkoxy The hydrogen atoms on the alkoxy group can be partially or completely replaced by halogen atoms, such as CF 3 OCH 2 O-.
  • Alkylthioalkyl alkyl-S-alkyl-, for example CH 3 SCH 2 -.
  • Halogenated alkylthioalkyl The hydrogen atoms on the alkyl group of the alkylthioalkyl group can be partially or completely replaced by halogen atoms, such as ClCH 2 CH 2 SCH 2 -, CF 3 CH 2 SCH 2 -and so on.
  • Heteroaryl is a five-membered ring or six-membered ring containing one or more N, O, S heteroatoms.
  • furyl pyrazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl and the like.
  • heteroaryl moiety in heteroaryl and heteroarylalkyl, heteroaryloxy and heteroarylalkoxy refers to a five-membered ring or six-membered ring containing one or more N, O, S heteroatoms Yuan ring.
  • furyl pyrazolyl, thiazolyl, pyridyl, pyrimidinyl, pyrazinyl, pyridazinyl, triazinyl, quinolinyl, benzoxazolyl, indolyl and the like.
  • the compound represented by formula I and its diastereomers, chiral isomers and salts thereof can be used for plant growth control and fungicide applications.
  • the plant growth regulation function is used to improve crop characteristics, including but not limited to: emergence, crop yield, protein content, increased vigor, faster/delayed maturation, increased/delayed seed emergence speed, improved nutrient utilization Efficiency, improved nitrogen use efficiency, improved water use efficiency, improved oil content and/or quality, improved digestibility, faster/more uniform maturation, improved flavor, improved starch content, more developed root system (Improved root growth), improved adversity tolerance (eg drought, heat, salt, light, UV, moisture, cold), reduced ethylene (reduced production and/or suppression of acceptance), increased tillers, increased plant height , Larger leaves, fewer dead basal leaves, stronger tillers, greener leaf color, pigment content, photosynthetic activity, less input requirements (such as fertilizer or water), less seed requirements, more yield Tillers, earlier flowering, early grain maturity, less plant dumping (lodging), increased stem growth, increased plant vigor, increased plant density and early and better germination.
  • root system Improved root growth
  • improved plant growth and plant development better growth, more tillers, greener leaves, larger leaves, more biomass, better roots, improved plant stress tolerance, more Higher grain yield, more harvested biomass, improved harvest quality (content of fatty acids, metabolites, oil, etc.), more marketable products (e.g. improved size), improved processes (e.g. longer storage) Time limit, better extraction of the compound), improved seed quality (sown in the following season for seed production); or any other advantage familiar to those skilled in the art.
  • the derivative represented by formula I of the present invention has the functions of delaying plant growth, inhibiting stem elongation, shortening plant internodes, promoting flower bud differentiation, promoting leaf growth, improving plant resistance to stress, and increasing plant yield in plant growth regulation. It can be used to obtain traits beneficial to agricultural production, and other plant growth regulators prepared by mixing it with agriculturally acceptable auxiliary agents can have other functions of plant growth regulation.
  • the main plants include, but are not limited to, cereal crops (rice, wheat, barley, oats, corn, millet, sorghum, etc.), tuber crops (sweet potato, potato, cassava, etc.), legume crops (soybeans, broad beans, peas, mung beans, etc.) , Adzuki beans, snow peas, etc.) and fiber crops (cotton, hemp, sericulture, etc.), oil crops (peanuts, rapeseed, sesame, soybeans, sunflowers, etc.), sugar crops (beet, sugar cane, etc.), beverage crops (tea, coffee, etc.) , Cocoa, etc.), favorite crops (tobacco, etc.), medicinal crops (ginseng, fritillary, etc.), tropical crops (rubber, coconut, oil palm, sisal, etc.), melons (watermelon, melon, cantaloupe, papaya, etc.) , And fruits, sericulture, vegetables (tomatoes, pepper
  • Oomycetes diseases such as downy mildew (cucumber downy mildew, rape downy mildew, soybean downy mildew, beet downy mildew, sugarcane) Downy mildew, tobacco downy mildew, pea downy mildew, loofah downy mildew, wax gourd downy mildew, melon downy mildew, cabbage downy mildew, spinach downy mildew, radish downy mildew, grape downy mildew, Onion downy mildew), white rust fungus (canola white rust, cabbage white rust), damping-off (rapeseed damping-off, tobacco damping-off, tomato damping-off, pepper damping-off, eggplant damping-off, cucumber Damping-off, cotton seedling damping-off), cotton rot (pepper spongy rot, loof
  • the derivatives of the present invention can be used to prevent and treat the following major viruses, including but not limited to: tobacco mosaic virus, tobacco rattle virus, tobacco leaf curl virus, tobacco ringspot virus, tobacco etch virus, sweet potato feathery mottle virus, potato Y virus , Potato Leaf Roll Virus, Potato X Virus, Potato S Virus, Potato A Virus, Potato Spindle Tuber Virus, Sugarcane Mosaic Virus, Sugarcane Streak Mosaic Virus, Cucumber Mosaic Virus, Melon Mosaic Virus, Pumpkin Mosaic Virus, Tomato spot wilt virus, tomato infertility virus, beet curly top virus, alfalfa mosaic virus, banana bunchy top virus, banana streak virus, citrus decay virus, wheat yellow mosaic virus, wheat soil-borne mosaic virus, wheat spindle streak pattern Leaf virus, barley yellow dwarf virus, grain mosaic virus, rice dwarf virus, rice tumour dwarf virus, rice cluster dwarf virus, rice black streaked dwarf virus, rice tooth dwarf virus, rice stripe leaf blight virus, rice white leaf
  • the derivative represented by formula I of the present invention has a fungicide function, and its mixed preparation with agriculturally acceptable auxiliary agents and other medicaments can have other functions related to agricultural production.
  • the compound synthesized by the present invention and its diastereomers, chiral isomers and their salts can be used as active ingredients of plant growth regulators and fungicides. They can be used alone or in combination with other plant growth regulators and fungicides. use.
  • the heteroaryl group of R 1 is shown in Table 1 below, but it does not limit the present invention.
  • R 2 substituents are shown in Table 2 below, but do not limit the present invention.
  • R 3 substituents are shown in Table 3 below, but they do not limit the present invention.
  • R 4 and R 5 are the same or different as shown in Table 4 below, but they do not limit the present invention.
  • R 8 substituents are shown in Table 5 below, but do not limit the present invention.
  • R 2 is H
  • R 3 is C(CH 3 ) 3
  • R 4 is H
  • R 5 is H
  • R 1 is shown in Table 6 below, and the number is 6-1------6-560:
  • X is halogen, chlorine, bromine or iodine.
  • the step 1 reaction is carried out in a suitable solvent, and the suitable solvent can be selected from ethyl acetate, dichloromethane, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide , Dimethyl sulfoxide, etc.
  • the suitable solvent can be selected from ethyl acetate, dichloromethane, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide , Dimethyl sulfoxide, etc.
  • step 1 the reaction is carried out with the participation of a suitable base, which can be selected from sodium tert-butoxide, potassium tert-butoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate, triethylamine, diisopropylethylamine, etc.
  • a suitable base which can be selected from sodium tert-butoxide, potassium tert-butoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, sodium carbonate, Potassium carbonate, triethylamine, diisopropylethylamine, etc.
  • the reaction temperature can be between room temperature and the boiling point of the solvent, usually 20-150°C.
  • the reaction time is 1 hour to 12 hours, usually 1-6 hours.
  • the reaction is carried out in a suitable solvent, which can be selected from ethyl acetate, dichloromethane, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide , Dimethyl sulfoxide, etc.
  • a suitable solvent which can be selected from ethyl acetate, dichloromethane, tetrahydrofuran, acetonitrile, toluene, xylene, benzene, N,N-dimethylformamide , Dimethyl sulfoxide, etc.
  • the reaction can be carried out with the participation of a suitable base, which can be selected from sodium tert-butoxide, potassium tert-butoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, and sodium carbonate , Potassium carbonate, triethylamine, diisopropylethylamine, etc.
  • a suitable base which can be selected from sodium tert-butoxide, potassium tert-butoxide, sodium hydride, sodium amide, sodium hydroxide, potassium hydroxide, and sodium carbonate , Potassium carbonate, triethylamine, diisopropylethylamine, etc.
  • the reaction temperature can be between room temperature and the boiling point of the solvent, usually 20-120°C.
  • the reaction time is 1 hour to 12 hours, usually 2-8 hours.
  • the reaction is carried out in a suitable solvent, which can be selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, water and the like.
  • a suitable solvent which can be selected from methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, tert-butanol, water and the like.
  • the reaction can be carried out with the participation of a suitable reducing agent, which can be selected from sodium borohydride, potassium borohydride, and combinations of reducing agents such as hydrogen, hydrazine hydrate, and precious metals such as palladium, platinum, etc. .
  • a suitable reducing agent which can be selected from sodium borohydride, potassium borohydride, and combinations of reducing agents such as hydrogen, hydrazine hydrate, and precious metals such as palladium, platinum, etc.
  • the reaction temperature can be between zero and the boiling point of the solvent, usually 0-100°C.
  • the reaction time is 1 hour to 24 hours, usually 2-8 hours.
  • the compound of general formula I of the present invention has excellent plant growth regulating activities and fungicidal activities such as delaying plant growth, inhibiting stem elongation, shortening plant nodes, etc., and has a shorter metabolic residue time, is easier to decompose, and is more effective for subsequent crops. The impact is even smaller.
  • the compound of general formula I is expected to play a role in the field of agricultural production.
  • the compound of general formula I of the present invention has excellent activity in inhibiting crop stem elongation, dwarfing plants, and preventing lodging, and its metabolic time in the soil is shorter than that of current market drugs, reducing The possibility of phytotoxicity occurred.
  • the compound of general formula I of the present invention reduces the height of rice plants and has a smaller impact on rice yield.
  • the compound of general formula I of the present invention also has a significant function of promoting early flowering of crops. In addition, due to its rapid degradation performance, it can minimize phytotoxicity for subsequent fruit growth.
  • Fig. 1 is a standard curve of paclobutrazol provided by an embodiment of the present invention.
  • Figure 2 is a standard curve of compound 6-375 provided by an embodiment of the present invention.
  • Figure 3 is a graph showing the dynamic trend of paclobutrazol degradation in soil provided by an embodiment of the present invention.
  • Figure 4 is a graph showing the degradation dynamics of compound No. 6-375 in soil provided by an embodiment of the present invention.
  • Figure 5 is a diagram of cucumber growth and development 21 days after drug addition provided by an embodiment of the present invention.
  • the characterization data of some compounds are as follows:
  • A is an intermediate for preparing the corresponding compound.
  • the above-obtained compound is reacted with an acid in a conventional manner to obtain the corresponding salt.
  • a certain concentration of medicinal solution is mixed with the melted agar medium, and the sprouting rice seeds are spotted on the surface of the medium and cultivated for one week to measure the physiological plant height of the rice.
  • the rice variety is Jijing 83, the rice plant height is used as the inhibition index, the treatment without compound added is the blank control, and the paclobutrazol is the positive control.
  • the inhibitory rate of compound 6-55 on rice plant height was greater than 30%, and the inhibitory rate of the positive drug paclobutrazol on rice plant height was greater than 30%.
  • a certain concentration of compound 6-55 and paclobutrazol were sprayed on the soil.
  • the original adhesion amounts of compound 6-55 and paclobutrazol in the soil were 1.2 mg/kg and 1.1 mg/kg, respectively.
  • the half-life is less than 2 days, while the half-life of paclobutrazol is greater than 3 days.
  • the determination method is as follows: a high-throughput screening method is adopted, that is, the sample of the compound to be tested is dissolved in a suitable solvent (the type of solvent is acetone, methanol, DMF, etc., and is selected according to its ability to dissolve the sample) to prepare the desired concentration The liquid to be tested.
  • a suitable solvent the type of solvent is acetone, methanol, DMF, etc., and is selected according to its ability to dissolve the sample
  • the test solution to the microwells of the 96-well culture plate, and then add the rape sclerotium pathogen propagule suspension (for the preparation method, refer to the journal article: Fujian Agriculture and Forestry Science and Technology, 1997, third issue, 15 Page) is added to it, and the treated culture plate is placed in a constant temperature incubator for culture. The investigation was conducted 24 hours later.
  • the germination or growth of the pathogen propagules was visually inspected, and the antibacterial activity of the compound was evaluated according to the germination or growth of the control treatment.
  • the aqueous solution of the solvent with the same concentration of the test compound sample was used as the CK control.
  • a certain concentration of the test compound sample is mixed with the melted agar, and the rice seed of the sprouting variety Yanfeng 47 is spotted on the surface of the agar containing the test compound, and cultivated for one week to measure the physiological plant height of the rice.
  • the rice plant height was used as the inhibition index, the treatment without compound was used as the blank control, and the paclobutrazol was used as the positive control.
  • compound 6-18, compound 6-47, compound 6-55, compound 6-59, compound 6-166, compound 6-375 inhibited rice plant height by more than 30%.
  • the positive drug paclobutrazol on rice The inhibition rate of plant height is greater than 30%.
  • the experimental crop rice the variety is Yanfeng 47. Soak the rice seeds for 24 hours, and evenly spread them in the seedling tray (54cm ⁇ 27cm ⁇ 6cm). After the rice seedlings grow to three leaves, select them and transplant them into a planting box (24cm ⁇ 15cm ⁇ 15cm). Each treatment 3 boxes, each box planted 6 holes of rice, 5 plants in each hole, the soil is field soil.
  • the test agents were paclobutrazol, uniconazole, compound 6-375 and B1, and a blank control was set at the same time.
  • Each agent is set at the concentration of 10 -4 g/mL, 10 -5 g/mL, and 10 -6 g/mL, and the application rate is 133.4 g/mu, 13.34 g/mu and 1.334 g/mu per hole.
  • the amount of medicine is calculated based on the amount of medicine added and the amount of soil in the box.
  • the soil sample containing paclobutrazol is added to 25ml acetonitrile at a liquid-to-mass ratio of 5:1, and the soil sample containing compound 6-375 is extracted by The liquid-to-mass ratio is 3:1.
  • the soil is added to 15ml of acetonitrile for extraction. After vortexing for 1 min, ultrasonic extraction for 30 min, low temperature quick freezing at -20°C for 10 min, centrifugation at 10,000 rpm/min for 5 min, the supernatant was recovered and passed through a 0.22 ⁇ m organic filter membrane for testing.
  • the test crop was cucumber. Cucumber seeds were placed in an incubator at 25°C for accelerating germination. After the sprouts grew to 1cm, they were sown in planting pots (upper diameter 12cm, lower diameter 9cm, height 11.5cm). The soil was turf soil. After a true leaf grows, apply compound fertilizer (the ratio of nitrogen, phosphorus and potassium is 15-15-15). The experiment set up blank control, test agent group, and positive control group.
  • test agents were compound 6-375 and B1, and the positive control agents were paclobutrazol and uniconazole, respectively 10 -4 g/mL (each pot equivalent to 4kg/hm 2), 10 -5 g / mL ( equivalent to application rates per pot 0.4kg / hm 2), 10 -6 g / mL ( equivalent to application rates per pot 0.04kg / hm 2), according to an amount equivalent to administration and dosage Calculation of pot soil volume.
  • the blank control CK was sprayed with water. The dosage of the medicine is calculated according to the soil volume of the planting pot.
  • the compound of general formula I synthesized by the present invention and its diastereomers, chiral isomers and their salts can be used alone, or mixed with agriculturally acceptable additives and other pharmaceutical agents. Plant growth regulation, sterilization and other functions.
  • the compound of general formula I synthesized by the present invention and its diastereomers, chiral isomers and their salts can be used as active ingredients of plant growth regulators and fungicides, and can be used alone or in combination with other plant growth regulators and Fungicides are used in combination.

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  • Organic Chemistry (AREA)
  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth 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)
  • Plural Heterocyclic Compounds (AREA)

Abstract

L'invention relève du domaine de la chimie. L'invention concerne en particulier des dérivés de triazole, et une utilisation des dérivés dans la régulation de la croissance des plantes et des fongicides. Les dérivés de triazole sont des composés représentés par la formule générale I, des diastéréomères et des isomères chiraux de ceux-ci, ou des sels de ceux-ci. Les définitions de chaque substituant dans la formule sont décrites dans la spécification. Les composés selon la présente invention peuvent être utilisés pour la régulation de la croissance des plantes et des applications fongicides.
PCT/CN2020/131020 2019-12-19 2020-11-24 Dérivés de triazole et leur utilisation WO2021120992A1 (fr)

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CN114957215B (zh) * 2022-01-13 2023-03-21 渤海大学 亚甲基桥连喹啉和1,2,3-三唑双杂环化合物及其制备方法与应用

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