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WO2016092559A1 - Dérivés de pyrazole substitués ayant une activité fongicide - Google Patents

Dérivés de pyrazole substitués ayant une activité fongicide Download PDF

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Publication number
WO2016092559A1
WO2016092559A1 PCT/IN2015/000443 IN2015000443W WO2016092559A1 WO 2016092559 A1 WO2016092559 A1 WO 2016092559A1 IN 2015000443 W IN2015000443 W IN 2015000443W WO 2016092559 A1 WO2016092559 A1 WO 2016092559A1
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Prior art keywords
substituted
compound
alkyl
unsubstituted
salt
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English (en)
Inventor
Tetsuya Imai
Surendra Kumar KUMAWAT
Manish Kumar SINGH
Ashish BHATT
Srinivas VENUVENKA
Vivek Kumar PANDEY
Dhuni Lal YADAV
Mahaveer Singh CHOUHAN
Jawed ASHRAF Md
Richu DHIR
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OAT and IIL India Laboratories Pvt Ltd
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OAT and IIL India Laboratories Pvt Ltd
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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
    • C07D401/12—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 chain containing hetero atoms as chain links
    • 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing three or more hetero rings

Definitions

  • the present invention relates to a novel hetero compound and use thereof.
  • Patent Literature (PTL) 1 discloses the compound represented by Formula (A) below. PTL 1 discloses that this compound exhibits insecticidal activity.
  • the present inventors conducted extensive research to achieve the above objects, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt thereof that has fungicidal activity.
  • the present inventors have conducted further research based on the above findings.
  • the present invention has thereby been accomplished.
  • the present invention includes the following embodiments:
  • a heterocyclic compound represented by Formula (1) is a heterocyclic compound represented by Formula (1) :
  • R 1 and R 4 are identical or different and each represents substituted or unsubstituted aryl, or a substituted or
  • R 2 represents substituted or unsubstituted C 1-4 alkyl
  • Y represents oxygen or sulfur
  • R 7 represents C 1-4 alkyl, C 1-4 alkylcarbonyl, or C 1-4 alkoxycarbonyl
  • the bond represented by: is a single bond o-r a double bond.
  • heterocyclic compound or a salt thereof according . ⁇ ' to Item 1 or 2, wherein R 3 represents substituted aryl.
  • heterocyclic compound or a salt thereof according to any one of Items 1 to 3, wherein R 4 represents a substituted or unsubstituted heter.oaryl group.
  • heterocyclic compound or a salt thereof according to any one of Items 1 to 4, wherein R 4 is substituted or
  • the heterocyclic compound or a salt thereof according to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the heterocyclic compound or a salt thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi.
  • the present invention is directed to a compound represented by Formula (1) :
  • compound (1) of the present invention or a salt thereof (hereinafter sometimes referred to as “compound (1) of the present invention” or “compound (1)”),
  • R 1 and R 4 are identical or different and each represents
  • X represents C(-Y), CR 5 R 6 , NH, or NR 7 ,
  • aryl examples include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
  • halogen examples include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.
  • C 1-4 haloalkyl examples include, but are not particularly limited to, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, trifluoromethyl, 1-fluoroethyl, 2- fluoroethyl, 2-chloroethyl, 2, 2, 2-trifluoroethyl,
  • C 2-4 alkynyl examples include, but are not particularly limited to, ethynyl, 1-propynyl, l-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.
  • C 3-8 cycloalkyl examples include, but are not particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C 1-4 alkoxycarbonyl examples include, but are not particularly limited to, methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl,
  • C 1-4 alkylcarbonyloxy examples include, but are not . particularly limited to, methylcarbonyloxy (acetyloxy) ,
  • C 1-4 haloalkoxy examples include, but are not particularly limited to, fluoromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2-fluoroethoxy, 2-chloroethoxy, 1-fluoroethoxy, pentafluoroethoxy, and like C 1-4 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 5, halogen atoms.
  • C 1-4 alkylthio examples include, but are not particularly limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, see-butylthio, tert- butylthio, and like C 1-4 straight-chain or branched-chain
  • C 1-4 alkylsulfonyl examples include, but are not particularly limited to, methylsulfonyl, ethylsulfonyl, n- propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl,
  • C 1-4 alkylsulfinyl examples include, but are not particularly limited to, methylsulfinyl, ethylsulfinyl, n- propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl,
  • aryloxy examples include, but are not particularly limited to, phenyloxy, 1-naphthyloxy, 2-naphthyloxy, and the like
  • arylthio examples include, but are not particularly limited to, phenylthio, 1-naphthylthio, 2-naphthylthio, and the like.
  • arylsulfonyl examples include, but are not particularly limited to, phenylsulfonyl, 1-naphthylsulfonyl, 2- naphthylsulfonyl, and the like.
  • arylsulfinyl examples include, but are not particularly limited to, phenylsulfinyl, 1-naphthylsulfinyl, 2- naphthylsulfinyl, and the like.
  • aryl C 1-4 alkyl examples include phenylmethyl, phenylethyl, phenyl-n-propyl, 1-naphthylmethyl, 2-naphthylmethyl, and the like.
  • the substituted aryl or substituted heteroaryl group refers to an aryl group or heteroaryl group mentioned above that is substituted with one or more substituents.
  • the number of substituents is preferably 1 to 5, and more preferably 1 to 3.
  • the substituted C 1-4 alkyl refers to a C 1-4 alkyl group mentioned above that is substituted with one or more substituents
  • the number of substituents is preferably 1 to 5, and more
  • substituted C 1-4 alkyl, substituted aryl, and substituted heteroaryl groups include, but are not particularly limited to, halogen, nitro, cyano, hydroxy (hydroxyl group), thiol, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy C 1-4 alkyl, C 1-4 haloalkoxy alkyl, C 2-4 alkenyl, C 2-4 alkynyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl alkyl, C 1-4
  • alkylcarbonyl C 1-4 alkoxycarbonyl, C 1-4 alkylcarbonyloxy, C 1-4 alkoxy, C 1-4 haloalkoxy, C 1-4 alkylthio, C 1-4 haloalkylthio, C 1-4 alkylsulfonyl, C 1-4 alkylsulfinyl, aryloxy, arylthio, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl C 1-4 alkyl, a substituted or unsubstituted heteroaryl group, and the like.
  • substituents are halogen, nitro, cyano, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy, haloalkoxy, C 1-4 alkylthio, and aryloxy, and more preferable substituents are chlorine, fluorine, bromine, nitro, cyano, methyl,
  • substituents for, in particular, substituted aryl or a substituted heteroaryl group represented by R 1 are halogen, C 1-4 haloalkyl, and C 1-4 alkoxy, and more preferable substituents therefor are chlorine, fluorine, bromine,
  • a preferable substituent for substituted alkyl represented by R 2 is halogen, and a more preferable substituent is fluorine.
  • the number of substituents is as mentioned above.
  • substituents for substituted aryl or substituted heteroaryl group are halogen, C 1-4 haloalkyl, C 1-4 alkoxy, C 1-4 haloalkoxy, C 1-4 alkylthio, and aryloxy, and more preferable substituents are chlorine, fluorine, trifluoromethyl, methoxy, trifluoromethoxy, methylthio, and phenoxy.
  • the number of substituents is as mentioned above.
  • substituents for substituted aryl or substituted heteroaryl group represented by R 4 are halogen, nitro-, ' cyano, C 1-4 alkyl, and C 1-4 haloalkyl, and more preferable
  • substituents are chlorine, fluorine, nitro, cyano, methyl, and trifluoromethyl.
  • the number of substituents is as mentioned above.
  • Y represents oxygen or sulfur, and preferably oxygen.
  • R 5 and R 6 are identical or different and each represents hydrogen, hydroxy, thiol, halogen, C 1-4 alkyl, C 1-4
  • haloalkyl C 1-4 alkoxy C 1-4 alkyl, C 1-4 haloalkoxy C 1-4 alkyl, C 2-4 aikenyl, C 2-4 alkynyl, C 3-8 cycloalkyl, C 3-8 cycloalkyl C 1-4 alkyl, C 1-4 alkylcarbonyl, C 1-4 alkylcarbonyloxy, C 1-4 alkoxy, C 1-4
  • haloalkoxy C 1-4 alkylthio, C 1-4 alkylsulfonyl, C 1-4 alkylsulfinyl, arylsulfonyl, arylsulfinyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl C 1-4 alkyl, or a substituted or unsubstituted heteroaryl group, preferably hydrogen, hydroxy, thiol, halogen, C 1-4 alkylcarbonyloxy, C 1-4 alkylthio, or C 1-4 alkylsulfonyl, and more preferably hydrogen, hydroxy, chlorine, methylcarbonyloxy, methylthio, ethylthio, or methylsulfonyl .
  • R 7 represents hydrogen, C 1-4 alkyl, substituted or unsubstituted C 1-4 alkoxy, substituted or unsubstituted aryl, C 1-4 alkylcarbonyl, or C 1-4 alkoxycarbonyl, and preferably hydrogen.
  • the dotted line is a single bond or a double bond.
  • the substituted aryl is preferably an aryl group having one to three haloge'n atoms, an aryl group having one to three nitro groups, an aryl group having one to three cyano groups, an aryl group having one to three C 1-4 alkyl groups, an aryl group having one to three C 1-4 haloalkyl groups, an aryl group having one to two halogen atoms and one to two C 1-4 haloalkyl groups, an aryl group having one to three aryloxy groups, an aryl group having one to three C 1-4 alkoxy groups, an aryl group having one to three C 1-4 haloalkoxy groups, or an aryl group having one to three C 1-4 alkylthio groups; more preferably an aryl group having one to three chlorine atoms, an aryl group having one to three bromine atoms, an aryl group having one to three fluorine atoms, an aryl group having one to two fluorine
  • the substituted heteroaryl group is preferably a heteroaryl group having one to three halogen atoms, a heteroaryl group having one to three nitro groups, a heteroaryl group having one to three cyano groups, a heteroaryl group having one to three C 1-4 alkyl groups, a heteroaryl group having one to three C 1-4 haloalkyl groups, a heteroaryl group having one to two halogen atoms and one to two C 1-4 haloalkyl groups, a heteroaryl group having one to three aryloxy groups, a heteroaryl group having one to three C 1-4 alkoxy groups, a heteroaryl group having one to three C 1-4 haloalkoxy groups, or a heteroaryl group having one to three C 1-4 alkylthio groups; and more preferably a heteroaryl group having one to three chlorine atoms, a heteroaryl group having one to three bromine atoms, a heteroaryl group having one to three fluorine atoms,
  • heteroaryl group having one to three methylthio groups.
  • the substituted or unsubstituted heteroaryl group is particularly preferably 2-pyridyl, 3-pyridyl, 4-pyridyl, 5- fluoro-2-pyridyl, 5-chloro-2-pyridyl, 3, 5-dichloro-2-pyridyl, 5- methy1-2-pyridyl, 3-methyl-2-pyridyl, 5-trifluoromethyl-2-pyridyl, 4-trifluoromethyl-2-pyridyl, 3-trifluoromethyl-2-pyridyl, 6- trifluoromethyl-2-pyridyl, 3-chloro-5-trifluoromethyl-2-pyridyl, 3-nitro-5-trifluoromethyl-2-pyridyl, 3-cyano-2-pyridyl, 5-chloro- 3-pyridyl, 5-trifluoromethyl-3-pyridyl, 2-fluoro-6- trifluoromethyl-3-pyridyl, 5-pyrimidinyl,
  • the salt of the heterocyclic compound represented by Formula (1) may be any type of salt as long as it is
  • salt examples include hydrochloride salt, sulfate salt, nitrate salt, and like inorganic acid salts; acetate salt, methanesulfonic acid salt, and like organic acid salts; sodium salt, potassium salt, and like alkali metal salts; magnesium salt, calcium salt, and like alkaline earth metal salts; dimethylammonium, triethylammonium, and like quaternary ammonium salts;* and the like.
  • Compound (1) of the present invention encompasses a pyrazole compound represented by the following Formula (1A) (hereinafter referred to as “compound 1A”) and a dihydropyrazole compound represented by Formula (IB) (hereinafter referred to as “compound IB”).
  • a preferable compound is a compound in which R l and R 4 are not simultaneously unsubstituted aryl.
  • a more preferable compound of the present invention is a compound or a salt thereof in which R 1 and R 4 are identical or different and each represents substituted aryl or a substituted or unsubstituted heteroaryl group,
  • R 2 represents substituted or unsubstituted C 1-4 alkyl
  • R 3 represents substituted aryl, or a substituted or unsubstituted heteroaryl group
  • X represents C(-O), CR*R 6 , NH, or NR 7 ,
  • R 9 and R 6 are identical or different and each represents hydrogen; hydroxy, thiol, halogen, C 1-4 alkyl, C 1-4 haloalkyl, C 1-4 alkoxy C 1-4 alkyl, C 1-4 haloalkoxy C 1-4 alkyl, C 2 .
  • R 7 represents hydrogen, C 1-4 alkylcarbonyl, or C 1-4 alkoxycarbonyl
  • a more particularly preferable compound of the present invention is a compound or a salt thereof in which
  • R 1 represents 2, 4-disubstituted aryl
  • R 2 represents substituted or unsubstituted C 1-4 alkyl
  • R 3 represents 2, 4-disubstituted aryl or 3-substituted aryl
  • R 4 represents substituted or .unsubstituted 3-pyridyl
  • R 5 and R 6 are identical or different and each represents hydrogen, hydroxy, thiol, halogen, C 1-4 alkylcarbonyloxy, C 1-4 alkylthio, or C 1-4 alkylsulfonyl, and
  • the bond represented by: is a single bond or a double bond.
  • compound (1) of the present invention has isomers such as optical isomers, stereoisomers, regioisomers, and the like
  • any of the isomers and mixtures thereof are included within the scope of compound (1) .
  • the optical isomer separated from a racemic mixture is also included within the scope of compound (1) .
  • Each of such isomers may be obtained as a single compound by known synthesis and separation means (e.g., concentration, solvent extraction, column chromatography, and recrystallization) .
  • the process for preparing compound (1) of the present invention is not particularly limited, and various processes, such as Reaction Scheme 1, Reaction Scheme 2, Reaction Scheme 3, Reaction Scheme 4, Reaction Scheme 5, and Reaction Scheme 6, may be used.
  • compound (lB-1) is prepared by reacting a hydrazide compound represented by Formula (2)
  • the proportions of these compounds used are not particularly limited, and may be suitably selected from a wide range.
  • the latter is usually used in an amount of about 1 to 5 moles per mole of the former, and preferably about an equimolar amount with respect to the latter.
  • reaction above is performed after a step (a chlorination step) in which compound (2) is chlorinated to produce a chloride of compound (2) .
  • a chlorination step the chloride of compound (2) is reacted with compound (3) to produce compound (lB-1) .
  • a chlorinating agent may be used.
  • a chlorinating agent include, but are not particularly limited to, chlorine, phosphorus oxychloride (P0C1 3 ), and the like. These chlorinating agents may be used alone or in a combination of two or more.
  • the chlorinating agent is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 8 moles, per mole of compound (2) .
  • the chlorinating agent is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 8 moles, per mole of compound (2) .
  • phosphorus oxychloride which can also function as a solvent, is used as a chlorinating agent, the excess of phosphorus
  • oxychloride after the completion of the chlorination step, may be removed under reduced pressure so as to be used in the
  • Examples of the base used in the step for reacting compound (2) or a chlorination product of compound (2) with compound (3) include, but are not particularly limited to, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, and like alkali metal carbonate salts; sodium
  • hydroxide, potassium hydroxide, and like alkali metal hydroxides sodium hydride, potassium hydride, and like alkali metal hydrides, and other inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and like alkali metal alkoxides; and triethylamine, pyridine, and other organic bases. These bases may be used alone, or in a combination of two or more.
  • the base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (2) .
  • the base is preferably used in an amount of 1 to 5 moles, and more pre-ferably 1 to 3 moles, per mole of compound (2) .
  • triethylamine, pyridine, or like organic base may be used in large excess to serve also as a reaction solvent.
  • the above reaction may be carried out in a suitable solvent or in the absence of a solvent.
  • usable solvents for the reaction are not limited insofar as they are inert to the reaction.
  • solvents include n-hexane, cyclohexane, n-heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, I, 2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, 1, 2-dimethoxyethane, and like ethers; N,N- dimethylformamide (DMF) , and like amides; dimethylsulfoxide, and like sulfoxides; and the like.
  • solvents include n-
  • the reaction temperature of the above reaction is usually in, although not limited, the range of -20°C to the boiling point of the solvent used.
  • the reaction is preferably performed under reflux of the solvent.
  • the reaction time varies according to, for example, the reaction temperature.
  • the reaction is usually completed in about 0.5 to about 24 hours.
  • a pyrazole compound represented by Formula (1A-2) or a salt thereof (hereinafter referred to as "compound (1A-2)"), or a compound (1B-2) is prepared by reducing compound (lA-1) in a solvent.
  • a reducing agent may be used.
  • a reducing agent include, but are not particularly limited to, boron compounds, and the like.
  • boron compounds include sodium borohydride, potassium borohydride, and like alkali metal borohydride compounds; sodium
  • reducing agents may be used alone or in a combination of two or more.
  • the reducing agent is used in an amount of preferably 1 to 3 moles, and more preferably 1.5 to 2.5 moles, per mole of compound (lB-1) or compound (lA-1) .
  • solvents include, but are not particularly limited to, methanol, ethanol, isopropanol, and like lower alcohols; diethyl ether, tetrahydrofuran, 1,4-dioxane, 1,2- dimethoxyethane, and like
  • ether-based solvents benzene, toluene, and like aromatic hydrocarbon-based solvents; and the like.
  • lower alcohols are preferable, and 2-propanol is more preferable.
  • These solvents may be used alone or in a combination of two or more.
  • the reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used.
  • the reaction is preferably performed at room temperature.
  • the reaction time varies according to, for example, the reaction temperature.
  • the reaction is usually completed in about 0.5 to about 24 hours.
  • compound (lA-1) is prepared by oxidizing compound (lB-1) in a solvent .
  • An oxidizing agent may be used for the oxidation above.
  • Examples of such an oxidizing agent include, but are not
  • lead compounds such as lead oxide (PbO 2 , Pb 3 O 4 ) , lead tetraacetate (Pb(OAc) 4 ), lead trifluoroacetate
  • oxidizing agents may be used alone or in a combination of two or more.
  • solvents examples include n-hexane, cyclohexane, n- heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, 1, 2-dichloroethane, chloroform, carbon
  • tetrachloride and like halogenated hydrocarbons
  • diethyl ether tetrahydrofuran (THF) , 1,4-dioxane, 1, 2-dimethoxyethane, and like ethers
  • ⁇ , ⁇ -dimethylfoirmamide (DMF) ⁇ , ⁇ -dimethylfoirmamide (DMF), and like amides
  • dimethylsulfoxide dimethylsulfoxide, .and like sulfoxides; and the like. These solvents may be used alone or in a combination of two or more.
  • compound ( ⁇ '-l) is prepared by reacting an amino compound represented by Formula (4) (hereinafter referred to as “compound (4)”) with a compound represented by Formula (5) (hereinafter referred to as “compound (5)”) in a solvent in the presence of a catalyst and a base. Reaction Scheme 5
  • R 1 , R 2 , R 3 , and R 4 are as defined above, and
  • Examples of the leaving group represented by Z include chlorine, bromine, iodine, and like halogen atoms;
  • compound (5) include substituted or unsubstituted aryl halide, substituted or unsubstituted heteroaryl halide, and the like, with substituted or
  • Compound (5) is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of compound (4) .
  • bases include, but are not particularly limited to, sodium carbonate, potassium carbonate, cesium
  • hydroxide and like alkali metal hydroxides
  • bases may be used alone or in a combination of two or more.
  • the base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (4) .
  • the base is preferably used in an amount of 1 to 5 moles, and more preferably 1 to 3 moles, per mole of compound (4)
  • the reaction may be performed in the presence of a catalyst.
  • a catalyst include metal catalysts (e.g., metal and metal salts), copper salt complexes (e.g., a copper salt complex of copper iodide with ⁇ , ⁇ '-dimethyl-ethylenediamine, proline, or bipyridyl) , palladium complexes (e.g.,
  • the amount of the catalyst used is not particularly limited.
  • the catalyst is usually used in an amount of 0.001 to 1 mole, preferably 0.01 to 0.5 moles, and more preferably 0.05 to 0.3 moles, per mole of compound (4) .
  • solvents include n-hexane, cyclohexane, n- heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, 1, 2-dichloroethane, chloroform, carbon tetrachloride, and like halogenated hydrocarbons; diethyl ether, tetrahydrofuran (THF) , 1, 4-dioxane, 1, 2-dimethoxyethane, and like ethers; N,N-dimethylformamide (DMF) , and like amides;
  • THF tetrahydrofuran
  • DMF N,N-dimethylformamide
  • dimethylsulfoxide and like sulfoxides may be used alone or in a combination of two or more.
  • the reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used.
  • the reaction is preferably performed under reflux.
  • the reaction time varies according to, for example, the reaction temperature.
  • the reaction is usually completed in about 0.5 to about 24 hours.
  • compound (1 ⁇ '-2) is prepared by reacting compound (IA'- ⁇ ) with a: compound represented by Formula (6) (hereinafter referred to as “compound (6)”) in a solvent, whether in the presence of a base or not.
  • R 1 , R 2 , R 3 , R 4 , and R 7 are as defined above, and
  • Z represents a leaving group
  • Examples of the leaving group represented by Z of compound (6) include chlorine, bromine, iodine, and like halogen atoms; and substituted or unsubstituted alkyl sulfonate,
  • compound (6) examples include methyl halide, ethyl halide, acetyl halide, methoxycarbonyl halide, and the like
  • Compound (6) is usually used in an amount of 1 mole or more, preferably 1 to 10 moles, and more preferably 1 to 5 moles, per mole of compound (1A'-1).
  • bases include, but are not particularly limited to, sodium carbonate, potassium carbonate, cesium
  • hydroxide and like alkali metal hydroxides
  • DBU 1,8- diazabicyclo[5.4.0]undec-7-ene
  • bases may be used alone or in a combination of two or more.
  • the base may be used in a stoichiometric amount or more than the stoichiometric amount, with respect to compound (1A'-1). Specifically, the base is preferably used in an amount of ⁇ to 5 moles, and more preferably 1 to 3 moles, per mole of compound (1A'-1) .
  • solvents examples include n-hexane, cyclohexane, n- heptane, and like aliphatic or alicyclic hydrocarbons; benzene, chlorobenzene, toluene, xylene, and like aromatic hydrocarbons; methylene chloride, 1, 2-dichloroethane, chloroform, carbon
  • tetrachloride and like halogenated hydrocarbons
  • diethyl ether tetrahydrofuran (THF) , 1,4-dioxane, 1, 2-dimethoxyethane, and like ethers
  • THF tetrahydrofuran
  • DMF ⁇ , ⁇ -dimethylformamide
  • dimethylsulfoxide and like sulfoxides may be used alone or in a combination of two or more.
  • the reaction temperature of the above reaction is usually in, although not limited, the range of -10°C to the boiling point of the solvent used.
  • the reaction is preferably performed under reflux.
  • the reaction time varies according to, for example, the reaction temperature.
  • the reaction is usually completed in about 0.5 to about 24 hours .
  • Each compound (1) obtained after the completion of the reactions shown in Reaction Scheme 1 to Reaction Scheme 6 may be easily isolated from the reaction mixture and purified by known isolation and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography.
  • each regioisomer may be separated by a usual separation step, such as silica gel chromatography.
  • Compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent.
  • pest- controlling agents include agents (fungicides or virucides) for controlling plant diseases that cause problems in the
  • agents for controlling pests, mites, nematode, or soil pests that all cause problems in the agricultural and
  • animal-ectoparasite-controlling agents e.g., pulicide, ixodicide, and pedivulicideon
  • animal-ectoparasite-controlling agents e.g., pulicide, ixodicide, and pedivulicideon
  • the compound as is with no additional components.
  • compositions such as oil solutions, emulsions, wettable powders, flowable preparations, granules, dusts, aerosols, fumigants, or the like, according to known preparation methods.
  • Compound (1) of the present invention is usually contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt%.
  • solid carriers usable in the formulations include solid carriers in a fine powder or granular form, such as clay (e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay, and acid clay) , talc, ceramic, other inorganic minerals (e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica), and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride); and the like.
  • clay e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay, and acid clay
  • talc ceramic
  • other inorganic minerals e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica
  • chemical fertilizers e.g., ammonium sulfate, ammonium phosphat
  • liquid carriers examples include water, alcohols (e.g., methanol and ethanol), ketones (e.g., acetone and
  • aromatic hydrocarbons e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene
  • aromatic hydrocarbons e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene
  • hydrocarbons e.g., hexane, cyclohexane, kerosene, and light oil
  • esters e.g., ethyl acetate and butyl acetate
  • nitriles e.g., acetonitrile and isobutyronitrile
  • ethers e.g., diisopropyl ether and dioxane
  • acid amides e.g., N, W-dimethylformamide and N,N-dimethylacetamide
  • halogenated hydrocarbons e.g.,
  • dichloromethane trichloroethane, and carbon tetrachloride
  • dimethylsulfoxide soybean oil, cottonseed oil, and like
  • gaseous carriers examples include butane gas, LPG (liquefied petroleum gas) , dimethyl ether, carbon dioxide gas, and the like.
  • surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl aryl ethers,
  • polyoxyethylene adducts thereof polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like.
  • adjuvants for pharmaceutical preparation include fixing agents, dispersants, stabilizers, and the like.
  • fixing agents and dispersants examples include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, and alginic acid), lignin derivatives, bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acids) .
  • stabilizers examples include PAP (acidic isopropyl phosphate), BHT (2, 6-di-tert-butyl-4-methylphenol) , BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol) , vegetable oils, mineral oils, fatty acids, and fatty acid esters, and the like.
  • PAP acidic isopropyl phosphate
  • BHT 2, 6-di-tert-butyl-4-methylphenol
  • BHA mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol
  • vegetable oils mineral oils, fatty acids, and fatty acid esters, and the like.
  • the pest-controlling agent of the present invention it is preferable to use compound (1) as is, or by diluting it with water or the like.
  • the pest-controlling agent of the present invention may be used by mixing with, for example, other pest- controlling agents, such as known insecticides, nematicides, acaricides, fungicides, herbicides, plant-growth-controlling agents, synergists, soil conditioners, animal feeds, and the like, or it may be used simultaneously with these agents without mixing.
  • the amount of the pest-controlling agent of the invention is not limited, and may be suitably selected from a wide range according to various conditions such as the
  • concentration of active ingredient the form of preparation, type of disease or pest to be treated, type of plant, severity of disease, time for application, method of application, chemicals to be used in combination (insecticide, nematicide, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), and amount and type of fertilizer.
  • compound (1) of the present invention When used as a fungicide, compound (1) of the present invention is usually used in an amount of 0.01 to 500 g/100 m 2 , and preferably 1 to 200 g/100 m 2 .
  • compound (1) of the present invention When used as a miticide, compound (1) of the present invention is usually used in an amount of 0.1 to 500 g/100 m 2 , and preferably 1 to 200 g/100 m 2 .
  • the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm.
  • the granules, dusts, or the like can be used as is without
  • the amount or concentration of application of the compound may be suitably increased or decreased according to the type of formulation, time of application, place of application, method of application, type of insect, severity of damage, and the like.
  • Compound (1) of the present invention is characterized by having a particularly excellent fungicidal activity and a broad spectrum of activity.
  • the compound may be used for
  • fungal pathogens include those that cause cucumber gray mold, rice plant blast, rice plant sheath blight, apple powdery mildew, apple Alternaria blotch, persimmon powdery mildew, grape powdery mildew, barley powdery mildew, wheat powdery mildew, cucumber powdery mildew, cucumber gray mold, tomato late blight, strawberry powdery mildew, tobacco powdery mildew, and the like.
  • Compound (1) of the present invention is effectively used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide. Specifically, compound (1) of the present invention is effective for controlling
  • aphids aphids; diamondback moths, cabbage armyworms, common cutworms, codling moths, bollworms, tobacco budworms, gypsy moths, rice leafrollers, smaller tea tortrix moths, Colorado potato beetles, cucurbit leaf beetles, boll weevils, plant hoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies/ scarabs, black cutworms, cutworms, ants, and agricultural pest insects; slugs, snails, and like gastropods; rat mite,
  • cockroaches houseflies, house mosquitoes, and like hygiene- harming insects
  • angoumois grain moths adzuki bean weevils, red flour beetles, mealworms, and like stored-grain insects
  • mites such as two-spotted spider mites, carmine spider mites, . citrus red mites, Kanzawa spider mites, European red mites, broad mites, pink citrus rust mites, bulb mites, and like plant- parasitic mites; Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei, and like house dust mites; and the like, and
  • soil pests such as root-knot nematodes, cyst nematodes, root- lesion nematodes, white-tip nematode, strawberry bud nematode, pine wood nematode, and like plant parasitic nematodes; pill bugs, sow bugs, and like isopods; and the like.
  • organophosphorus agents such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, and neonicotinoid agent.
  • Table 3 shows 1 H-NMR data of the thus obtained title compound 1B-71.
  • Table 3 shows 1 H-NMR data of the thus obtained title compound 1B-75.
  • dichloromethane (10 ml) was portionwise added lead tetraacetate (0.37 g, 0.84 mmol, 1.2 equiv.) at room temperature under nitrogen atmosphere.
  • the reaction mixture was then stirred at room temperature for 18 hrs and after that filtered through a celite bed.
  • the filtrate was then diluted with dichloromethane, and the organic layer was then washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to get a crude product.
  • the crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.22 g of the title compound 1A-77.
  • Table 1 shows 1 H-NMR data of the thus obtained title compound 1A-77.
  • the combined organic layer was washed with distilled water, dried over sodium sulfate, filtered, and concentrated under reduced pressure to get a crude product.
  • the crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.07 g of the title compound 1A-80.
  • Table 1 shows 1 H-NMR data of the thus obtained title compound 1A-80.
  • Table 3 shows 1 H-NMR data of the thus obtained title compound IB-72.
  • Table 3 shows 1 H-NMR data of the thus obtained title compound 1B-76.
  • Table 1 shows 1 H-NMR data of the thus obtained title compound 1A-78.
  • xanthphos (0.108 g, 0.0001 moles, 0.2 equiv.) was added under nitrogen atmosphere and again purged for 5 minutes. The reaction mixture was stirred at 100°C for about 8 hrs.
  • reaction solution was cooled and filtered through a celite bed.
  • the filtrate was evaporated under reduced pressure through an evaporator.
  • the resulting concentrate was diluted with water (10 ml) and extracted with ethyl acetate (3x10 ml) and the organic layer was washed with brine solution and dried over anhydrous sodium sulfate, filtered, and
  • the crude product was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane (40:60) as an eluent to obtain 0.23 g of the title compound lA'-89 as a white solid product.
  • Table 2 shows 1 H-NMR data of the thus obtained title compound 1A' -89.
  • Table 2 shows 1 H-NMR data of the thus obtained title compound 1A'-91.
  • Tables 1, 2 and 3 show MS and 1 H-NMR data of the thus obtained compounds of the present invention.
  • each compound of the invention was added to a mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of fine powder of synthetic hydrated silicon dioxide, and 54 parts of clay.
  • the mixtures were mixed by stirring with a juice mixer to give 20% wettable powders.
  • each compound of the invention was mixed with 20 parts of water containing 3 parts of polyoxyethylene tristyrylphenyl ether phosphoric acid ester triethanolamine and 0.2 parts of Rhodorsil 426R.
  • the mixtures were subjected to wet pulverization with a DYNO-Mill, and mixed with 60 parts of water ⁇ containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to give 20% suspensions in water.
  • Test Examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for fungicides .
  • a small amount of mycelia of Botrytis cinerea was collected from a culture tube, and aseptically transferred to a potato dextrose agar (PDA) plate.
  • PDA potato dextrose agar
  • the plate on which Botrytis cinerea was seeded was kept in the dark for five days, then under blacklight-blue (BLB) irradiation for four days, and finally in the dark at 20°C for four days.
  • BLB blacklight-blue
  • a YG (0.2% yeast extract + 1% glucose) solution was prepared using distilled water.
  • 20 ml " of the YG solution was poured into the culture plate, and the surface was scraped with a brush.
  • the obtained suspension was filtered through tissue paper.
  • the filtrate thus obtained was diluted with the YG solution to 1 x 10 6 cfu of spores per ml.
  • Preventive value ⁇ 1- (average radius of lesions in treated plant/average radius of lesions in untreated plant) ⁇ x100
  • the compounds that exhibited a disease control value of 50% or more at 500 ppm are as follows:
  • Test Example 2 Fungicidal test on cucumber powdery mildew
  • the preventive value was calculated by using the following equation, in comparison with the severity of disease in an untreated plant.
  • Preventive value ⁇ 1- (average radius of lesions in treated plant/average radius of lesions in untreated plant) ⁇ *100
  • the compounds that exhibited a disease control value of 80% or more at 500 ppm are as follows:

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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)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Un des objets de la présente invention est de pourvoir à un composé hétérocyclique ou à un sel de celui-ci capable de lutter contre un organisme nuisible. La présente invention concerne un composé hétérocyclique représenté par la Formule (1) : ou un sel de celui-ci, dans laquelle R1 et R4 sont identiques ou différents et représentent chacun un aryle substitué ou non, ou un groupe hétéroaryle substitué ou non, R2 représente un alkyle C1-4 substitué ou non, R3 représente un aryle substitué ou non, ou un groupe hétéroaryle substitué ou non, X représente C(=Y), CR5R6, NH, ou NR7, Y représente un atome d'oxygène ou de soufre, R5 et R6 sont identiques ou différents et représentent chacun un atome d'hydrogène, ou autre, R7 représente un alkyle C1-4, un alkylcarbonyle C1-4, ou un alcoxycarbonyle C1-4, et la liaison représentée par : est une liaison simple ou une liaison double.
PCT/IN2015/000443 2014-12-12 2015-12-07 Dérivés de pyrazole substitués ayant une activité fongicide Ceased WO2016092559A1 (fr)

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WO2020003219A1 (fr) * 2018-06-29 2020-01-02 Oat & Iil India Laboratories Private Limited Dérivés de pyrazole substitués à titre d'insecticides et de fongicides
CN116082238A (zh) * 2022-07-01 2023-05-09 福建农林大学 一种制备吡唑类衍生物的绿色三组分氧化环合方法
US11724982B2 (en) 2014-10-10 2023-08-15 The Research Foundation For The State University Of New York Trifluoromethoxylation of arenes via intramolecular trifluoromethoxy group migration

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Publication number Priority date Publication date Assignee Title
US11724982B2 (en) 2014-10-10 2023-08-15 The Research Foundation For The State University Of New York Trifluoromethoxylation of arenes via intramolecular trifluoromethoxy group migration
WO2020003219A1 (fr) * 2018-06-29 2020-01-02 Oat & Iil India Laboratories Private Limited Dérivés de pyrazole substitués à titre d'insecticides et de fongicides
CN116082238A (zh) * 2022-07-01 2023-05-09 福建农林大学 一种制备吡唑类衍生物的绿色三组分氧化环合方法

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