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WO2020003219A1 - Substituted pyrazole derivatives as insecticides and fungicides - Google Patents

Substituted pyrazole derivatives as insecticides and fungicides Download PDF

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Publication number
WO2020003219A1
WO2020003219A1 PCT/IB2019/055483 IB2019055483W WO2020003219A1 WO 2020003219 A1 WO2020003219 A1 WO 2020003219A1 IB 2019055483 W IB2019055483 W IB 2019055483W WO 2020003219 A1 WO2020003219 A1 WO 2020003219A1
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Prior art keywords
substituted
unsubstituted
alkyl
salt
pyrazole compound
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PCT/IB2019/055483
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French (fr)
Inventor
Surendra Kumar KUMAWAT
Saurabh Arun KHOLE
Kiran Sadashiv BABAR
Manish Kumar YADAV
Ravi Kumar Sharma
Nand Kishor ARORA
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Oat & Iil India Laboratories Private Limited
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Publication of WO2020003219A1 publication Critical patent/WO2020003219A1/en

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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
    • 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
    • A01N43/90—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having two or more relevant hetero rings, condensed among themselves or with a common carbocyclic ring system
    • 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
    • C07D401/04—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 directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/04—Ortho-condensed systems

Definitions

  • the present disclosure relates to novel pyrazole compounds and the process for preparing the said compounds. Furthermore, the disclosure provides an agriculture and horticulture insecticide and fungicide composition comprising the compounds of the present disclosure .
  • Patent Literature (PTL) 1 disclosed quinoline derivatives having fungicidal activity but there was no description for insecticidal activity.
  • WO 2006/013896 Patent Literature (PTL) 2
  • JP 2008-110953 Patent Literature (PTL) 3
  • JP 2633377 Patent Literature (PTL) 4
  • US 4168311 Patent Literature (PTL) 5
  • Patent Literature (PTL) 5 disclosed quinoline derivatives having an insecticidal activity.
  • PTL 1 and PTL 2 disclosed the compound represented by the following formula (A) :
  • Z represents an oxygen atom, a sulfur atom, SO, S0 2 , CO or Q, etc., where Q is a C1-4 alkylene group (the Ci- 4 alkylene group may be substituted with a halogen atom or a cyano group) ;
  • Ri, R 2 , and R 3 represent hydrogen, C 1-4 alkyl group, C 1-4 haloalkyl group, C 1-4 alkyloxy group, C 1-4 haloalkoxy group, alkyloxycarbonyl group, nitro group, cyano group, formyl group, acetyl group, acetylethoxy group, etc.;
  • R 2 and R 3 together represent one (CH 2 ) m , wherein m represents 3 or
  • Xi, X 2 , and X 3 each independently represent a hydrogen atom, a halogen atom, a Ci_ 4 alkyl group which may be substituted with a halogen atom or a Ci_ 4 alkyloxy group, a Ci_ 4 alkyloxycarbonyl group, a C 1-4 alkyloxy group which may be substituted with a halogen atom, or a C 1-4 alkyloxycarbonyl group which may be substituted by a halogen atom, with the proviso that X 2 , X 2 , and X 3 do not simultaneously represent hydrogen atoms;
  • Wi represents a nitrogen atom or CY 2 ,
  • W 2 represents a nitrogen atom or CY 2 .
  • W 3 represents a nitrogen atom or CY 3 ,
  • W 2 and W 3 represent CY 2 and CY 3 , respectively, when W 2 represents a nitrogen atom, Wi and W 3 represent CY 2 and CY 3 , respectively, and when W 3 represents a nitrogen atom, W 2 and W 2 represent CY 2 and CY 2 , respectively;
  • Yi, Y 2 and Y 3 each independently represent a hydrogen atom, A, or
  • A represents a Ci-s alkyl group, Ci-s alkyloxy group, C 2- s alkenyl group, C 2-8 alkenyloxy group, Ci-s alkyloxycarbonyl group, C 2-8 alkenylthio group, C 1-8 alkylsulfinyl group, C 2- s alkenylsulfinyl group, C 1-8 alkylsulfonyl group, C 2-8 alkenylsulfonyl group, phenyl group, or phenoxy group, wherein all these substituents may further be substituted with various groups, such as halogen, C 1-4 alkyl group, etc., and
  • B represents a halogen atom, or a C 1-4 alkyl group.
  • the present disclosure provides novel substituted pyrazole compounds or salts thereof which exhibit high insecticidal and fungicidal activity against drug resistant insects and fungi as well as drug sensitive insects and fungi.
  • the present disclosure also provides a process for preparing the said novel substituted pyrazole compounds or salts thereof.
  • the present disclosure further provides a new type of agriculture and horticulture composition
  • a substituted pyrazole compound or a salt thereof as an active ingredient, which exhibits a remarkable insecticidal and fungicidal effect against chemical-resistant as well as chemical-sensitive insects and fungi.
  • the present inventors conducted extensive research, and succeeded in synthesizing a compound represented by the following formula (1) or a salt thereof that has shown excellent insecticidal and fungicidal activities.
  • the present inventors have conducted further research based on the above findings.
  • the present disclosure relates to novel substituted pyrazole compounds or salts thereof represented by the following general formula (1) .
  • the present disclosure includes the following embodiments:
  • Embodiment A1 is a diagrammatic representation of Embodiment A1 :
  • a substituted pyrazole compound represented by formula (1) A substituted pyrazole compound represented by formula (1) :
  • Q represents an oxygen atom, a sulfur atom, CR. 6 R 7 or direct bond.
  • R 6 and R 7 each independently represent hydrogen, halogen, cyano, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 cyanoalkoxy, C 1 -C 12 alkylthio, C 1 -C 12 haloalkylthio, C 1 -C 12 alkoxy, C 1 -C 12 alkyl, C 1 -C 12 haloalkoxy, C 2 -Ci 2 alkenyl, C 2 -Ci 2 haloalkenyl, C 2 -Ci 2 alkenyloxy, C 2 -Ci 2 haloalkenyloxy, C 2 -Ci 2 alkynyl, C 2 -Ci 2 haloalkynyl, C 2 -Ci 2
  • R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryl Ci-Ci 2 alkyl, substituted or unsubstituted heteroaryl Ci-Ci 2 alkyl, Ci-Ci 2 alkyl, Ci-Ci 2 haloalkyl, Ci-Ci 2 cyanoalkyl, Ci-Ci 2 alkoxy Ci-Ci 2 alkyl, Ci-Ci 2 alkylthio Ci-Ci 2 alkyl, Ci-Ci 2 haloalkoxy Ci-Ci 2 alkyl, C 2 -Ci 2 alkenyl, C 2 -Ci 2 alkynyl, C 2 -Ci 2 haloalkenyl, C 2 -Ci 2 haloalkynyl, Ci-Ci 2 alkylsulfinyl, Ci-Ci 2 alkylsulfonyl, Ci-Ci 2 haloal
  • Ri represents hydrogen, substituted or unsubstituted Ci-Ci 2 alkyl, substituted or unsubstituted C 2 -Ci 2 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted C 3 -Ci 2 cycloalkyl, substituted or unsubstituted aryl Ci-Ci 2 alkyl, substituted or unsubstituted Ci-Ci 2 alkylcarbonyl, substituted or unsubstituted Ci-Ci 2 haloalkylcarbonyl, substituted or unsubstituted Ci-Ci 2 haloalkoxycarbonyl, substituted or unsubstituted C 2 -C 12 alkenylcarbonyl , substituted or unsubstituted C 2 - C 12 alkynylcarbonyl , substituted or unsubstituted C 3 - C 12 cycloalkylcarbonyl , substitute
  • R 2 represents hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 haloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, or substituted or unsubstituted C 1 -C 12 haloalkoxy;
  • R 3 represents hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 haloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 haloalkoxy, substituted or unsubstituted C 2 -C 12 alkenyl, substituted or unsubstituted C 2 -C 12 alkynyl, substituted or unsubstituted C 3 - C 12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclic;
  • R 4 and R 5 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 haloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 alkylthio, or substituted or unsubstituted aryl;
  • Xi represents C-Rs or N
  • X 2 represents C-R 9 or N
  • X 3 represents C-R 10 or N
  • Re , R 9 and Rio each independently represent hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 haloalkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 haloalkoxy, substituted or unsubstituted C 1 -C 12 alkylthio, substituted or unsubstituted C 1 -C 12 haloalkylthio, substituted or unsubstituted C 1 -C 12 alkoxycarbonyl, substituted or unsubstituted C 1 -C 12 haloalkoxycarbonyl , cyano, nitro or substituted or unsubstituted amino .
  • Embodiment A2 is a diagrammatic representation of Embodiment A2 :
  • Embodiment A3 is a diagrammatic representation of Embodiment A3 :
  • substituted pyrazole compound or a salt thereof according to any one of embodiments A1 or A2, wherein R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or C 1 -C 12 alkyl.
  • Embodiment A4 is a diagrammatic representation of Embodiment A4 :
  • substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A3, wherein Ri represents hydrogen, substituted or unsubstituted C 2 -C 12 alkenyl, substituted or unsubstituted C 2 -C 12 alkynyl, substituted or unsubstituted C 1 -C 12 alkylcarbonyl , substituted or unsubstituted C 3 -C 12 cycloalkylcarbonyl , substituted or unsubstituted C 1 -C 12 alkoxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted C 1 -C 12 alkylsulfinyl, substituted or unsubstituted C 1 -C 12 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, or substituted or unsubsti
  • R 2 represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, or substituted or unsubstituted Ci-Ci 2 haloalkyl.
  • Embodiment A6 is a diagrammatic representation of Embodiment A6 :
  • R 3 represents substituted or unsubstituted Ci-Ci 2 alkyl, or substituted or unsubstituted Ci-Ci 2 haloalkyl .
  • Embodiment A7
  • R 4 and R5 each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, or substituted or unsubstituted Ci-Ci 2 haloalkyl .
  • Embodiment A8 is a diagrammatic representation of Embodiment A8 :
  • substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A7, wherein X 2 represents C-Rs, X 2 represents C-Rg, and X3 represents C-R10, wherein Rg, R9 and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, substituted or unsubstituted Ci-Ci 2 haloalkyl, or substituted or unsubstituted Ci-Ci 2 alkoxy.
  • Embodiment A9
  • a pest controlling agent comprising the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 as an active ingredient.
  • Embodiment A10
  • Embodiment All A method for controlling pests, which comprises applying the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 to a plant or its vicinity, or soil where a plant is cultivated.
  • Embodiment A12 is a diagrammatic representation of Embodiment A12
  • a method for controlling pests which comprises applying an effective amount of the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 to pests, a habitat of a pests, or a place where inhabitation is predicted.
  • the present disclosure includes the following embodiments:
  • Embodiment 1 is a diagrammatic representation of Embodiment 1 :
  • a substituted pyrazole compound represented by formula (1) A substituted pyrazole compound represented by formula (1) :
  • Q represents an oxygen atom, a sulfur atom, CR. 6 R 7 or direct bond;
  • R 3 ⁇ 4 and R 7 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 alkylthio, substituted or unsubstituted C 2 -Ci 2 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkenyloxy, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted C 2 -Ci 2 alkynyloxy, substituted or unsubstituted Ci-Ci 2 alkylsulfinyl, substituted or unsubstituted Ci-Ci 2 alkylsulfonyl, substituted or unsubstituted C 3 -C
  • R represents hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 2 -C 12 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted C 1 -C 12 alkylsulfinyl, substituted or unsubstituted C 1 -C 12 alkylsulfonyl, substituted or unsubstituted C 1 -C 12 alkylcarbonyl , substituted or unsubstituted C 1 -C 12 alkoxycarbonyl , substituted or unsubstituted C 3 -C 12 cycloalkyl, or substituted or unsubstituted saturated heterocyclic;
  • Ri represents hydrogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 2 -Ci 2 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted C 1 -C 12 alkylcarbonyl, substituted or unsubstituted C 2 -Ci 2 alkenylcarbonyl , substituted or unsubstituted C 2 -Ci 2 alkynylcarbonyl , substituted or unsubstituted C 3 -C 12 cycloalkylcarbonyl , substituted or unsubstituted C 1 -C 12 alkoxycarbonyl, substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted heteroaryloxycarbonyl , substituted or unsubstituted
  • R 2 and R 3 each independently represents hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 2 -C 12 alkenyl, substituted or unsubstituted C 2 -C 12 alkynyl, substituted or unsubstituted C 3 -C 12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclic;
  • R 4 and R 5 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C 1 -C 12 alkyl, substituted or unsubstituted C 1 -C 12 alkoxy, substituted or unsubstituted C 1 -C 12 alkylthio or substituted or unsubstituted aryl;
  • Xi represents C-Rs or N
  • X 2 represents C-R 9 or N
  • X 3 represents C-Rio or N
  • R 9 and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, substituted or unsubstituted Ci-Ci 2 alkoxy, substituted or unsubstituted Ci-Ci 2 alkylthio, substituted or unsubstituted Ci-Ci 2 alkoxycarbonyl , cyano, nitro, or substituted or unsubstituted amino.
  • Ci-Ci 2 alkyl is selected from the group consisting of Ci-Ci 2 alkyl, Ci-Ci 2 haloalkyl, Ci-Ci 2 alkoxy Ci-Ci 2 alkyl, and Ci-Ci 2 haloalkoxy Ci-Ci 2 alkyl;
  • Ci-Ci 2 alkoxy is selected from the group consisting of Ci-Ci 2 alkoxy, Ci-Ci 2 haloalkoxy, and Ci-Ci 2 cyanoalkoxy;
  • said substituted or unsubstituted Ci-Ci 2 alkylthio is selected from the group consisting of Ci-Ci 2 alkylthio and Ci-Ci 2 haloalkylthio ; said substituted or unsubstituted C 2 -Ci 2 alkenyl is selected from the group consisting of C 2 -Ci 2 alkenyl and C 2 -Ci 2 haloalkenyl; said substituted or unsubstituted C 2 -Ci 2 alkenyloxy is selected from the group consisting of C 2 -Ci 2 alkenyloxy and C 2 -Ci 2 haloalkenyloxy; said substituted or unsubstituted C 2 -Ci 2 alkynyl is selected from the group consisting of C 2 -Ci 2 alkynyl and C 2 -Ci 2 haloalkynyl; said substituted or unsubstituted C 2 -Ci 2 alkynyloxy is selected from
  • Ci-Ci 2 alkylsulfonyl is selected from the group consisting of Ci-Ci 2 alkylsulfonyl and Ci-Ci 2 haloalkyl sulfonyl ;
  • said substituted or unsubstituted C 3 -Ci 2 cycloalkyl is C 3 -Ci 2 cycloalkyl ;
  • said substituted or unsubstituted C 1 -C 12 alkylcarbonyl is selected from the group consisting of C 1 -C 12 alkylcarbonyl and C 1 -C 12 haloalkylcarbonyl ;
  • said substituted or unsubstituted C 1 -C 12 alkoxycarbonyl is selected from the group consisting of C 1 -C 12 alkoxycarbonyl and C 1 -C 12 haloalkoxycarbonyl ;
  • said substituted or unsubstituted C 1 -C 12 alkylcarbonylamino is C 1 -C 12 alkylcarbonylamino
  • said substituted or unsubstituted C 1 -C 12 alkylsulfonyloxy is C 1 -C 12 alkylsulfonyloxy;
  • said substituted or unsubstituted C 1 -C 12 alkylsulfinyloxy is C 1 -C 12 alkylsulfinyloxy .
  • said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 cyanoalkyl, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 alkylthio C 1 -C 12 alkyl, C 1 -C 12 haloalkoxy C 1 -C 12 alkyl, substituted or unsubstituted aryl C 1 -C 12 alkyl, and substituted or unsubstituted hetroaryl aryl C 1 -C 12 alkyl; said substituted or unsubstituted C 2 -Ci 2 alkenyl is selected from the group consisting of C 2 -Ci 2 alkenyl and C 2 -Ci 2 haloalkenyl; said substituted or unsubstituted C 2 -Ci 2 alkynyl is
  • Ci-Ci 2 alkylsulfonyl is selected from the group consisting of Ci-Ci 2 alkylsulfonyl and Ci-Ci 2 haloalkyl sulfonyl ;
  • Ci-Ci 2 alkylcarbonyl is selected from the group consisting of Ci-Ci 2 alkylcarbonyl Ci-Ci 2 haloalkylcarbonyl ;
  • Ci-Ci 2 alkoxycarbonyl is selected from the group consisting of Ci-Ci 2 alkoxycarbonyl and Ci-Ci 2 haloalkoxycarbonyl; and/or
  • substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in Ri, said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl and substituted or unsubstituted aryl C 1 -C 12 alkyl;
  • said substituted or unsubstituted C 1 -C 12 alkylcarbonyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkylcarbonyl, substituted or unsubstituted C 1 -C 12 haloalkylcarbonyl , substituted or unsubstituted aryl C 1 -C 12 alkylcarbonyl, substituted or unsubstituted heteroaryl C 1 -C 12 alkylcarbonyl, substituted or unsubstituted heterocycle C 1 -C 12 alkylcarbonyl, and substituted or unsubstituted C 3- Ci 2 cycloalkyl C 1 -C 12 alkylcarbonyl;
  • said substituted or unsubstituted C 1 -C 12 alkoxycarbonyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkoxycarbonyl, substituted or unsubstituted aryl C 1 -C 12 alkoxycarbonyl, and substituted or unsubstituted heteroaryl C 1 -C 12 alkoxycarbonyl ;
  • substituted or unsubstituted C 1 -C 12 alkylsulfinyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkylsulfinyl, and substituted or unsubstituted C 1 -C 12 haloalkylsulfinyl ; and/or
  • said substituted or unsubstituted C 1 -C 12 alkylsulfonyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkylsulfonyl, and C 1 -C 12 haloalkylsulfonyl ;
  • Ri can also be further substituted by various substituents groups, such as F, Cl, Br, I, CN, N0 2 , CH 3 , C(CH 3 ) 3 , OCH 3 , C0 2 CH 3 , C0 2 CH 2 CH 3 , S0 2 CH 3 , OCH 2 CF 3 , CF 3 , or OCF 3 .
  • substituents groups such as F, Cl, Br, I, CN, N0 2 , CH 3 , C(CH 3 ) 3 , OCH 3 , C0 2 CH 3 , C0 2 CH 2 CH 3 , S0 2 CH 3 , OCH 2 CF 3 , CF 3 , or OCF 3 .
  • substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R 2 , said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl, and substituted or unsubstituted C 1 -C 12 haloalkyl; and/or
  • said substituted or unsubstituted C 1 -C 12 alkoxy is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkoxy, and substituted or unsubstituted C 1 -C 12 haloalkoxy.
  • said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl, and substituted or unsubstituted C 1 -C 12 haloalkyl; and/or
  • said substituted or unsubstituted C 1 -C 12 alkoxy is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkoxy, and substituted or unsubstituted C 1 -C 12 haloalkoxy.
  • substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R 4 and R 5 , said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl, and substituted or unsubstituted C 1 -C 12 haloalkyl.
  • substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R 8 , R 9 and Rio, said substituted or unsubstituted C 1 -C 12 alkyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkyl, and substituted or unsubstituted C 1 -C 12 haloalkyl;
  • said substituted or unsubstituted C 1 -C 12 alkoxy is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkoxy, and substituted or unsubstituted C 1 -C 12 haloalkoxy;
  • substituted or unsubstituted C 1 -C 12 alkylthio is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkylthio, and substituted or unsubstituted C 1 -C 12 haloalkylthio ; and/or
  • said substituted or unsubstituted C 1 -C 12 alkoxycarbonyl is selected from the group consisting of substituted or unsubstituted C 1 -C 12 alkoxycarbonyl, and substituted or unsubstituted C 1 -C 12 haloalkoxycarbonyl .
  • Q represents an oxygen atom or a sulfur atom
  • R represents substituted or unsubstituted aryl, substituted or unsubstituted C 1 -C 12 alkyl,
  • Ri represents hydrogen, substituted or unsubstituted C 2 -Ci 2 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted Ci-Ci 2 alkylcarbonyl , substituted or unsubstituted C 3 -Ci 2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci 2 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted arylcarbonyl , or substituted or unsubstituted Ci-Ci 2 alkylsulfonyl ;
  • R 2 represents hydrogen, or substituted or unsubstituted Ci-Ci 2 alkyl
  • R 3 represents substituted or unsubstituted Ci-Ci 2 alkyl
  • R 4 and R 5 each independently represent hydrogen, substituted or unsubstituted Ci-Ci 2 alkyl
  • Xi represents C-R 3 or N
  • X 2 represents C-Rg
  • X 3 represents C-R 10 .
  • R 8 , Rg and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, or substituted or unsubstituted Ci-Ci 2 alkoxy.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1 :
  • Embodiment 3 is a diagrammatic representation of Embodiment 3 :
  • R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted Ci-Ci 2 alkyl.
  • Embodiment 4 The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R represents substituted or unsubstituted C 6 -C 10 aryl, or unsubstituted C 1 -C 12 alkyl .
  • Embodiment 5
  • Embodiment 6 is a diagrammatic representation of Embodiment 6 :
  • R 2 represents hydrogen, substituted or unsubstituted C 2 -C 22 alkenyl, unsubstituted C 2 -Ci 2 alkynyl, unsubstituted Ci-Ci 2 alkylcarbonyl, unsubstituted C 3 -Ci 2 cycloalkylcarbonyl, unsubstituted Ci-Ci 2 alkoxycarbonyl, substituted or unsubstituted C 6 -C 10 arylcarbonyl, unsubstituted C 6 -C 10 aryloxycarbonyl, or unsubstituted C 6 -C 10 arylsulfonyl .
  • Embodiment 7
  • R 2 represents hydrogen, halogen, or substituted or unsubstituted Ci-Ci 2 alkyl.
  • Embodiment 8
  • R 2 represents hydrogen, or unsubstituted Ci-Ci 2 alkyl.
  • Embodiment 9 The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R 3 represents substituted or unsubstituted C 1 -C 12 alkyl.
  • Embodiment 10 is a diagrammatic representation of Embodiment 10:
  • R 4 and R 5 each independently represent hydrogen, halogen, or substituted or unsubstituted C 1 -C 12 alkyl.
  • Embodiment 11 is a diagrammatic representation of Embodiment 11:
  • R 4 and R 5 each independently represent hydrogen, or unsubstituted C 1 -C 12 alkyl.
  • Embodiment 12 is a diagrammatic representation of Embodiment 12
  • X 4 represents C-R 8
  • X 2 represents C-R 9
  • X 3 represents C-R 10
  • R 8 , R 9 and Ri 0 are independently of each other hydrogen, halogen, substituted or unsubstituted C 1 -C 12 alkyl, or substituted or unsubstituted C 1 -C 12 alkoxy .
  • Embodiment 13 is a diagrammatic representation of Embodiment 13:
  • X 4 represents C-R 8
  • X 2 represents C-Rg
  • X 3 represents C-R 10
  • R 8 , Rg and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, or unsubstituted Ci-Ci 2 alkoxy.
  • Embodiment 14 is a diagrammatic representation of Embodiment 14:
  • Embodiment 15 is a diagrammatic representation of Embodiment 15:
  • Embodiment 17 is a diagrammatic representation of Embodiment 17:
  • Embodiment 18 is a diagrammatic representation of Embodiment 18:
  • Embodiment 19 is a diagrammatic representation of Embodiment 19:
  • R 4 and R5 each independently represent hydrogen, or unsubstituted C1-C6 alkyl.
  • Embodiment 20 is a diagrammatic representation of Embodiment 20.
  • Xi represents C-Rs
  • X 2 represents C-Rg
  • X 3 represents C-R10
  • Rs, R 9 and Rio are, independently of each other, hydrogen, halogen, unsubstituted C1-C6 alkyl, or unsubstituted C1-C6 alkoxy.
  • Embodiment 21 is a diagrammatic representation of Embodiment 21.
  • a pest controlling agent comprising the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments as an active ingredient.
  • Embodiment 22 is a diagrammatic representation of Embodiment 22.
  • Embodiment 23 A method for using the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments for controlling pests.
  • a method for controlling pests which comprises applying the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments to a plant or its vicinity, or soil where a plant is cultivated.
  • Embodiment 24 is a diagrammatic representation of Embodiment 24.
  • a method for controlling pests which comprises applying an effective amount of substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments to pests, a habitat of a pests, or a place where inhabitation is predicted.
  • a novel substituted pyrazole compound or a salt thereof according to the present disclosure achieves an excellent insecticidal and fungicidal effect. Additionally, the pyrazole compound or a salt thereof according to the present disclosure is useful as a new type of insecticide and fungicide that exhibit excellent insecticidal and fungicidal effect not only against chemical-sensitive fungi, but also against chemical-resistant fungi .
  • the present disclosure is directed to a compound represented by Formula ( 1 ) :
  • R, Ri, R 2 , R 3 , R 4 , R 5 , Xi, X 2 , X 3 , and Q are as defined above.
  • the number of substituents of a group defined by "substituted” is not particularly limited if it is substitutable, and is one or plural .
  • the description for each group is also applied when the group is one part of or a substituent on other groups.
  • Ci-Ci 2 alkyl means a linear or branched, saturated hydrocarbon group having one to twelve carbon atoms.
  • C 1 -C 6 alkyl or “C 1 -C 3 alkyl” means a linear or branched, saturated hydrocarbon group having one to six or one to three carbon atoms, respectively.
  • C 2 -Ci 2 alkenyl means a linear or branched, unsaturated hydrocarbon group having two to twelve carbon atoms and containing one to three double bonds.
  • C 2 -Ci 2 alkynyl means a linear or branched, unsaturated hydrocarbon group having two to twelve carbon atoms and containing one triple bond.
  • C 3 -Ci 2 cycloalkyl means a cyclic alkyl having three to twelve carbon atoms, and includes those cyclic alkyl having a partially bridged structure.
  • C 3 -C 6 cycloalkyl means a cyclic alkyl having three to six carbon atoms.
  • C 1 -C 12 alkoxy refers to a "C 1 -C 12 alkyloxy group", wherein the "C 1 -C 12 alkyl” moiety is defined the same as the above-described "C 1 -C 12 alkyl”.
  • Aryl means a monocyclic or polycyclic aromatic hydrocarbon.
  • C 6 -C 10 aryl means an aryl group, as defined herein, having six to ten carbon atoms.
  • C 6 aryl means an aryl group, as defined herein, having six carbon atoms.
  • Heterocyclic means a saturated, unsaturated, or aromatic heterocyclic group which has at least one of nitrogen, oxygen, phosphorus and/or sulfur atoms in the ring and may be bonded at any substitutable position.
  • Heterocyclic may be referred to as “heterocycle” or “heterocyclyl " .
  • Heteroaryl means an aromatic heterocyclic group which has at least one of nitrogen, oxygen, and/or sulfur atoms in the ring and may be bonded at any substitutable position, wherein the ring member atoms of the heteroaryl besides carbon atoms include 1, 2, 3 or 4 heteroatoms selected from N, 0 and S .
  • halogen examples include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.
  • C 1 -C 12 alkyl examples include, but are not particularly limited to, C 1 -C 12 straight-chain or branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1, 1-dimethylpropan-l-yl, n-hexyl, 1-ethylpentyl, 2-ethylhexyl , and the like.
  • C 1 -C 12 straight-chain or branched-chain alkyl such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1, 1-di
  • C 1 -C 12 haloalkyl examples include, but are not particularly limited to, C 1 -C 12 straight-chain or branched-chain alkyl substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethyl , chloromethyl , bromomethyl, iodomethyl, difluoromethyl, 2, 2-difluoroethyl, trifluoromethyl,
  • C1-C12 alkoxy examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy,
  • C1-C12 haloalkoxy examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, 2 , 2-difluoroethoxy, trifluoromethoxy,
  • C1-C12 alkoxy C1-C12 alkyl examples include, but are not particularly limited to, alkoxyalkyl in which the C1-C12 straight-chain or branched-chain alkyl is substituted with a C1-C12 straight-chain or branched-chain alkoxy, such as methoxymethyl , ethoxymethyl , n-propoxymethyl , isopropoxymethyl , n-butoxymethyl , isobutoxymethyl , sec-butoxymethyl , tert-butoxymethyl , methoxyethyl , ethoxyethyl, methoxy-n-propyl , methoxy-n-butyl , and the like.
  • C1-C12 haloalkoxy C1-C12 alkyl examples include, but are not particularly limited to, straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethoxymethyl , chloromethoxymethyl , bromomethoxymethyl , iodomethoxymethyl , difluoromethoxymethyl, trifluoromethoxymethyl, 2, 2, 2-trifluoroethoxymethyl, and the like .
  • C3-C12 cycloalkyl examples include, but are not particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C3-C12 cycloalkylcarbonyl examples include, but are not particularly limited to, cyclopropylcarbonyl , cyclobutylcarbonyl , cyclopentylcarbonyl , cyclohexylcarbonyl and the like.
  • C1-C12 alkylcarbonyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylcarbonyl groups, such as methylcarbonyl (acetyl), ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl), isopropylcarbonyl ( isobutyryl ) , n-butylcarbonyl (valeryl), isobutylcarbonyl ( isovaleryl ) , sec-butylcarbonyl , tert-butylcarbonyl , n-pentylcarbonyl , isopentylcarbonyl , neopentylcarbonyl , (1, 1-dimethylpropan-l-yl ) carbonyl,
  • C1-C12 haloalkylcarbonyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylcarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylcarbonyl , chloromethylcarbonyl , bromomethylcarbonyl , iodomethylcarbonyl , dichloromethylcarbonyl , trichloromethylcarbonyl, difluoromethylcarbonyl , trifluoromethylcarbonyl, chiorodifluoromethylcarbonyl , bromodifluoromethylcarbonyl , dichlorofluoromethylcarbonyl , 2,2, 2-trichloroethylcarbonyl , 2,2, 2-trifluoroethylcarbonyl , pentafluoroethylcarbonyl , and the like.
  • halogen atoms such as fluoromethylcarbonyl , chloromethylcarbonyl
  • C1-C12 alkoxycarbonyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxycarbonyl, such as methoxycarbonyl , ethoxycarbonyl , n-propoxycarbonyl , isopropoxycarbonyl , n-butoxycarbonyl , isobutoxycarbonyl , sec-butoxycarbonyl , tert-butoxycarbonyl , n-pentyloxycarbonyl , isopentyloxycarbonyl , neopentyloxycarbonyl , (1, 1-dimethylpropan-l-yloxy) carbonyl, n-hexyloxycarbonyl ,
  • Ci-Ci 2 haloalkoxycarbonyl examples include, but are not particularly limited to, Ci-Ci 2 straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl , chloromethoxycarbonyl , bromomethoxycarbonyl , iodomethoxycarbonyl , dichioromethoxycarbonyl, trichloromethoxycarbonyl , difluoromethoxycarbonyl , trifluoromethoxycarbonyl ,
  • C1-C12 cyanoalkyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkyl substituted with a cyano group, such as cyanomethyl, cyanoethyl, cyano-n-propyl , cyano-isopropyl , cyano-n-butyl , cyano-isobutyl , cyano-sec-butyl , cyano-tert-butyl , cyano-n-hexyl , and the like.
  • a cyano group such as cyanomethyl, cyanoethyl, cyano-n-propyl , cyano-isopropyl , cyano-n-butyl , cyano-isobutyl , cyano-sec-butyl , cyano-tert-butyl , cyano-n-hexyl , and the like.
  • C1-C12 cyanoalkoxy examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy substituted with a cyano group, such as cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano-hexyloxy, and the like.
  • a cyano group such as cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano-hexyloxy, and the like.
  • C 2 -Ci 2 alkenyl examples include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, and the like.
  • C 2 -Ci 2 haloalkenyl examples include, but are not particularly limited to, 2 , 2-dichlorovinyl , 2 , 2-dibromovinyl , 2, 2-difluorovinyl, 3, 3-difluoro-2-allyl, 4, 4-difluoro-3-butenyl ,
  • C 2 -Ci 2 alkynyl examples include, but are not particularly limited to, ethynyl, 2-propynyl (propargyl), l-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.
  • C 2 -Ci 2 haloalkynyl examples include, but are not particularly limited to, fluoroethynyl , bromoethynyl , chloroethynyl , iodoethynyl, 3, 3, 3-trifluoro-l-propynyl, and the like .
  • C1-C12 alkylsulfinyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, and the like .
  • C1-C12 alkylsulfinyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-but
  • C1-C12 haloalkylsulfinyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfinyl, chloromethylsulfinyl, bromomethylsulfinyl , iodomethylsulfinyl , dichloromethylsulfinyl , trichloromethylsulfinyl, difluoromethylsulfinyl , trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl , dichlorofluoromethylsulfinyl , 2,2, 2-trichloroethylsulfinyl , 2,2, 2-trifluoroethylsulfinyl, pentafluor
  • C1-C12 alkylsulfonyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, and the like .
  • C1-C12 haloalkylsulfonyl examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfonyl, chloromethylsulfonyl, bromomethylsulfonyl , iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl, difluoromethylsulfonyl , trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl , dichlorofluoromethylsulfonyl , 2,2, 2-trichloroethylsulfonyl , 2,2, 2-trifluoroethylsulfonyl, pentafluor
  • C1-C12 alkylthio examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylthio, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, and the like.
  • C1-C12 haloalkylthio examples include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylthio substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio, dichloromethylthio, trichloromethylthio, difluoromethylthio, trifluoromethylthio, chiorodifluoromethylthio, bromodifluoromethylthio, dichlorofluoromethylthio, 2,2, 2-trichloroethylthio,
  • C 2 -Ci 2 alkenyloxy examples include, but are not particularly limited to, vinyloxy, 1-propenyloxy, isopropenyloxy, allyloxy,
  • C 2 -Ci 2 haloalkenyloxy examples include, but are not particularly limited to, 2 , 2-dichlorovinyloxy,
  • C 2 -Ci 2 alkynyloxy examples include, but are not particularly limited to, ethynyloxy, 2-propynyloxy, l-methyl-2-propynyloxy,
  • C 2 -Ci 2 haloalkynyloxy examples include, but are not particularly limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3, 3, 3-trifluoro-l-propynyloxy, and the like.
  • Ci-Ci 2 alkylsulfonyloxy examples include, but are not particularly limited to, Ci-Ci 2 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and the like.
  • C 1 -C 12 alkylsulfinyloxy examples include, but are not particularly limited to, C 1 -C 12 straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and the like.
  • C 1 -C 12 alkylsulfinyloxy examples include, but are not particularly limited to, C 1 -C 12 straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfin
  • substituted or unsubstituted amino include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino, and the like.
  • alkyl include C 1 -C 12 alkyl mentioned above, and the like.
  • acyl include C 1 -C 12 alkoxycarbonyl , haloalkoxycarbonyl , arylcarbonyl mentioned above, and the like.
  • aryl examples include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
  • aryl C 1 -C 12 alkyl examples include, but are not particularly limited to, benzyl, phenylethyl, phenyl-n-propyl and the like. These aryl C 1 -C 12 alkyl can be further substituted at the alkyl part or the aryl part, or both.
  • aryloxy examples include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.
  • aryl C 1 -C 12 alkoxy examples include, but are not particularly limited to, benzyloxy, phenylethoxy, phenyl-n-propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and the like .
  • heteroaryloxy examples include, but are not particularly limited to, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, and the like .
  • heteroaryl C 1 -C 12 alkoxy examples include, but are not particularly limited to, pyridinylmethoxy, pyridinylethoxy, pyrimidinylethoxy, pyrazolylmethoxy, 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.
  • heteroaryl examples include, but are not particularly limited to, thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl , triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, isoindolyl, indazolyl, quinazolinyl , carbazolyl, benzoxazolyl , benzisoxazolyl , benzothiazolyl , benzisothiazolyl , benzimidazolyl , quinolinyl, isoquinolinyl , pyridoindolyl , cinnolinyl,
  • All the Aryls and Heteroaryls mentioned above may optionally be further substituted.
  • Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
  • heterocyclic group examples include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl, dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl , oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl , isoxazolinyl , thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl , isothiazolinyl , pyrazolyl, pyrazolidinyl , imidazolyl, imidazolinyl , imidazolidinyl , oxadiazolyl, oxadiazolinyl , thiadiazolinyl , triazolyl, triazolinyl, triazolidinyl , tetrazolyl, tetrazoliny
  • heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group.
  • heterocyclics mentioned above may optionally be further substituted.
  • substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
  • substituents in "substituted” include: but are not particularly limited to, halogen, nitro, cyano, hydroxyl, formyl, C 1 -C 12 alkyl, C 1 -C 12 haloalkyl, C 1 -C 12 alkoxy, C 1 -C 12 haloalkoxy, C 1 -C 12 alkoxy C 1 -C 12 alkyl, C 1 -C 12 haloalkoxy C 1 -C 12 alkyl, C 3 -C 12 cycloalkyl, C 3 -C 12 cycloalkyl C 1 -C 12 alkyl, C 1 -C 12 alkylcarbonyl , C 1 -C 12 haloalkylcarbonyl , arylcarbonyl , aryloxycarbonyl , C 1 -C 12 alkoxycarbonyl , C 1 -C 12 haloalkoxycarbonyl , C 1 -C 12 cyan
  • substituents are halogen, nitro, cyano, Ci-Ci 2 alkyl, 0 2 -0i 2 haloalkyl, 0 2 -0i 2 alkoxy, 0 2 -0i 2 haloalkoxy, 0 2 -0i 2 alkylsulfonyl, Ci-Ci 2 alkoxycarbonyl , Ci-Ci 2 haloalkylsulfonyl, Ci-Ci 2 alkylsulfinyl, 0 2 -0i 2 haloalkylsulfinyl, 0 2 -0i 2 alkylthio, Ci-Ci 2 haloalkylthio, substituted or unsubstituted amino, aryl, and heterocyclic, and more preferable substituents are fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, C(CH 3 ) 3 trifluoromethyl
  • Preferable substituted aryl groups are halogen-substituted aryl, dihalogen-substituted aryl, Ci-Ci 2 alkyl-substituted aryl, Ci-Ci 2 haloalkyl-substituted aryl, halogen and Ci-Ci 2 haloalkyl-substituted aryl, Ci-Ci 2 alkoxy-substituted aryl, Ci-Ci 2 haloalkoxy-substituted aryl, and Ci-Ci 2 alkylthio-substituted aryl .
  • More preferable substituted aryl groups are chlorine-substituted aryl, dichlorine-substituted aryl, fluorine-substituted aryl, difluorine-substituted aryl, trifluoromethyl-substituted aryl, methyl-substituted aryl, chlorine- and trifluoromethyl-substituted aryl, trifluoromethoxy-substituted aryl, methoxy-substituted aryl, trifluoromethoxy-substituted aryl, and methylthio-substituted aryl.
  • Preferable substituted heteroaryl groups are halogen-substituted heteroaryl, Ci-Ci 2 alkyl-substituted heteroaryl, Ci-Ci 2 haloalkyl-substituted heteroaryl, halogen and Ci-Ci 2 haloalkyl-substituted heteroaryl, Ci-Ci 2 alkoxy-substituted heteroaryl, Ci-Ci 2 haloalkoxy-substituted heteroaryl, and Ci-Ci 2 alkylthio-substituted heteroaryl.
  • More preferable substituted heteroaryl groups are chlorine-substituted heteroaryl, fluorine-substituted heteroaryl, trifluoromethyl-substituted heteroaryl, chlorine- and trifluoromethyl-substituted heteroaryl, trifluoromethoxy-substituted heteroaryl, and methoxy-substituted heteroaryl, and methylthio-substituted heteroaryl.
  • Preferable substituted heterocyclic groups are halogen-substituted heterocyclic, C 1 -C 12 alkyl-substituted heterocyclic, C 1 -C 12 haloalkyl-substituted heterocyclic, C 1 -C 12 alkoxy-substituted heterocyclic, C 1 -C 12 haloalkoxy-substituted heterocyclic, and C 1 -C 12 alkylthio-substituted heterocyclic.
  • More preferable substituted heterocyclic groups are chlorine-substituted heterocyclic, fluorine-substituted heterocyclic, trifluoromethyl-substituted heterocyclic, trifluoromethoxy-substituted heterocyclic, methoxy-substituted heterocyclic, and methylthio-substituted heterocyclic.
  • the salts of the compounds represented by Formula (1) may be any type of salts as long as they are agriculturally acceptable.
  • the salts include inorganic acid salts, such as a hydrochloride salt, a sulfate salt, a nitrate salt, and the like; organic acid salts, such as an acetate salt, a methanesulfonic acid salt, and the like; alkali metal salts, such as a sodium salt, a potassium salt, and the like; alkaline earth metal salts, such as a magnesium salt, a calcium salt, and the like; quaternary ammonium salts, such as dimethylammonium, triethylammonium, and the like; and the like.
  • Xi represents C-Rs or N
  • X 2 represents C-R 9 or N
  • X 3 represents C-R 10 or N.
  • Xi represents a nitrogen atom
  • X 2 and X 3 represent C-R 9 and C-R 10 , respectively
  • X 2 represents a nitrogen atom
  • Xi and X 3 represent C-Rs and C-R 10 , respectively
  • X 3 represents a nitrogen atom
  • X 2 and X 2 represent C-Rs and C-Rg, respectively .
  • a preferable compound is a compound in which Q represents an oxygen atom, or a sulfur atom
  • a more preferable compound (1) is a compound in which Q represents an oxygen atom
  • a preferable compound is a compound in which R. 6 and R 7 each independently represent hydrogen, halogen, or C1-C12 alkyl, and a more preferable compound (1) is a compound in which R 6 and R 7 each independently represent hydrogen, chlorine, or methyl.
  • a preferable compound is a compound in which R represents substituted or unsubstituted aryl or C1-C12 alkyl
  • a more preferable compound (1) is a compound in which R represents halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy-substituted aryl, unsubstituted aryl or methyl .
  • a preferable compound is a compound in which R 2 represents hydrogen, substituted or unsubstituted C 2 -Ci 2 alkenyl, substituted or unsubstituted C 2 -Ci 2 alkynyl, substituted or unsubstituted Ci-Ci 2 alkylcarbonyl , substituted or unsubstituted C 3 -Ci 2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci 2 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl , and a more preferable compound (1) is a compound in which Ri represents hydrogen, unsubstituted C 2 -Ci 2 alkenyl, unsubstituted C 2 -Ci 2 alkynyl, unsubstituted Ci-Ci 2 alkylcarbonyl, unsubstituted C
  • a preferable compound is a compound in which R 2 represents hydrogen, substituted or unsubstituted Ci-Ci 2 alkyl, and a more preferable compound (1) is a compound in which R 2 represents hydrogen, methyl or ethyl.
  • a preferable compound is a compound in which R 3 represents substituted or unsubstituted Ci-Ci 2 alkyl, and a more preferable compound (1) is a compound in which R 3 represents methyl, ethyl or tri fluoromethyl .
  • a preferable compound is a compound in which R 4 and R 5 each independently represent hydrogen, substituted or unsubstituted C 1 -C 12 alkyl, and a more preferable compound (1) is a compound in which R 4 and R 5 each independently represent hydrogen or methyl .
  • a preferable compound is a compound in which X lf X 2 and X 3 each independently represent C-R 8 , C-Rg , C-R 10 , or N
  • a more preferable compound (1) is a compound in which X 4 , X 2 and X 3 each independently represent C-R 8 , C-Rg , and C-R 10 .
  • X 4 represents a nitrogen atom
  • X 2 and X 3 represent C-Rg and C-R 10 , respectively.
  • X 4 and X 3 represent C-Rs and C-R 10 , respectively.
  • X 3 represents a nitrogen atom
  • X 4 and X 2 represent C-Rs and C-Rg , respectively .
  • a preferable compound is a compound in which R 8 , Rg and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci 2 alkyl, and a more preferable compound (1) is a compound in which Re , Rg and Rio represent independently of each other hydrogen, chloro, methyl or ethyl .
  • a more preferable compound of the present disclosure is a compound or a salt thereof in which
  • Q represents an oxygen atom
  • R is halogen-, alkyl-, haloalkyl-, alkoxy-, or haloalkoxy-substituted aryl; unsubstituted aryl; or methyl;
  • Ri is hydrogen, unsubstituted C 2 -Ci 2 alkenyl, unsubstituted C 2 -Ci 2 alkynyl, unsubstituted Ci-Ci 2 alkylcarbonyl , unsubstituted C 3 -Ci 2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci 2 alkoxycarbonyl , unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl ;
  • R 2 is hydrogen, or substituted or unsubstituted Ci-Ci 2 alkyl
  • R 3 is substituted or unsubstituted Ci-Ci 2 alkyl
  • R 4 is hydrogen, or substituted or unsubstituted Ci-Ci 2 alkyl
  • R 5 is hydrogen or methyl
  • Xi represents C-R 8 or N
  • X 2 represents C-Rg ;
  • X 3 represents C-Rio;
  • Rs is hydrogen, C 1 -C 12 alkyl or halogen
  • R 9 is hydrogen, C 1 -C 12 alkyl or halogen
  • Rio is hydrogen, C 1 -C 12 alkyl or halogen.
  • a particularly preferable compound of the present disclosure is a compound or a salt thereof in which
  • Q represents an oxygen atom
  • Rg is hydrogen
  • R 7 is hydrogen
  • R is substituted or unsubstituted aryl, or C 1 -C 12 alkyl
  • Ri is hydrogen, unsubstituted C 2 -Ci 2 alkenyl, unsubstituted C 2 -Ci 2 alkynyl, unsubstituted Ci-Ci 2 alkylcarbonyl , unsubstituted C 3 -Ci 2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci 2 alkoxycarbonyl , unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl;
  • R 2 is hydrogen, methyl or ethyl
  • R 3 is methyl, ethyl or trifluoromethyl ;
  • R 4 is hydrogen or methyl
  • R 5 is hydrogen, or substituted or unsubstituted Ci-Ci 2 alkyl
  • X 2 represents C-R 3 or N
  • X 2 represents C-R 9 ;
  • X 3 represents C-Rio
  • R is hydrogen, chloro, methyl or ethyl
  • R 9 is hydrogen, chloro, methyl or ethyl
  • Rio is hydrogen, chloro, methyl or ethyl.
  • Another more preferable compound of the present disclosure is a compound or a salt thereof in which
  • Q represents an oxygen atom or a sulfur atom, preferably an oxygen atom
  • R is Cg aryl substituted with halogen, Ci-Cg alkyl, Ci-Cg haloalkyl, Ci-Cg alkoxy, Ci-Cg haloalkoxy, and/or Ci-Cg haloalkylsulfonyl ;
  • Ri is hydrogen, unsubstituted Ci-Cg alkoxycarbonyl, unsubstituted Ci-Cg alkylcarbonyl, unsubstituted Ci-Cg haloalkylcarbonyl , unsubstituted C 3 -Cg cycloalkylcarbonyl, or unsubstituted Cg arylcarbonyl, or Ci-Cg haloalkyl-substituted Cg arylcarbonyl;
  • R 2 is Ci-C 3 alkyl
  • R 3 is hydrogen or Ci-C 3 alkyl
  • R. 4 is hydrogen or C 1 -C 3 alkyl
  • R 5 is hydrogen or C 1 -C 3 alkyl
  • Xi represents C-Rs
  • X 2 represents C-Rg
  • X 3 represents C-Ri 0 ;
  • R 8 is hydrogen, C 1 -C 3 alkyl, or fluorine
  • Rg is hydrogen or C 1 -C 3 alkyl
  • Rio is hydrogen or C 1 -C 3 alkyl.
  • a particularly preferable compound of the present disclosure is a compound or a salt thereof in which
  • Q represents an oxygen atom or a sulfur atom, preferably an oxygen atom
  • R is Ce aryl substituted with fluorine, chlorine, bromine, C 1 -C 3 alkyl, C 1 -C 3 haloalkyl, and/or C 1 -C 3 haloalkoxy;
  • Ri is hydrogen, unsubstituted Ci-C 6 alkoxycarbonyl , unsubstituted Ci-C 6 alkylcarbonyl , unsubstituted Ci-C 6 haloalkylcarbonyl , or unsubstituted cyclopropylcarbonyl ;
  • R 2 is methyl
  • R 3 is ethyl
  • R 4 is hydrogen, methyl, or ethyl
  • R 5 is hydrogen, methyl, or ethyl
  • Xi represents C-Rs
  • X 2 represents C-Rg
  • X 3 represents C-R 10 ;
  • Rs is hydrogen, methyl, or ethyl
  • Rg is methyl
  • the present disclosure also incorporates preparation of the said novel substituted pyrazole compounds or a salt thereof as represented by formula (1) .
  • preparation of the compounds of the present disclosure There are various known synthesis procedures for the preparation of the compounds of the present disclosure. Hereinafter, the synthesis procedure for one type of compounds of the present disclosure will be described and shown in Scheme- 1 . However, the preparation of the novel substituted pyrazole compounds or a salt thereof is not limited to this method.
  • R, Ri, R 2 , R3, Xi, X 2 , X3 and Q are as defined above while LG and LGi are any of known leaving groups.
  • This step provides a method of preparing compound (III) by the reaction of compound with compound (II)
  • R is as defined above.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: fatty acid or alicyclic hydrocarbon-based solvents, such as n-hexane, cyclohexane, n-heptane, and the like; aromatic hydrocarbon-based solvents, such as benzene, chlorobenzene, toluene, xylene, and the like; halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ester solvents, such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and the like; amide-based solvents, such as acetonitrile; A/,A/-
  • the amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound (I) .
  • the amount of compound (II) to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 1.5 mol, per 1 mol of the compound (I) .
  • the reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 60 minutes to 10 hours.
  • R is as defined above.
  • Formylation can be done by any known procedures. Some examples of the formylation include, but are not limited to, using POCI 3 -DMF system or using hexamethylenetetramine.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • a solvent examples include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF), 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and trifluoroacetic acid, dimethyl sulfoxide, sulfolane, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichlor
  • the amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (III) .
  • the amount of phosphorous oxychloride to be used is usually 1.0 to 20.0 mol , preferably 1.0 to 10.0 mol , per 1 mol of the compound
  • the amount of hexamethylenetetramine to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (III) .
  • the reaction temperature varies depending on the starting compound, the reaction reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 50 to 120°C.
  • the reaction time varies depending on the compound, the reaction reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 1 to 10 hours.
  • This step consists of two phases.
  • R and Q is as defined above.
  • any known peracid can be used, examples include but are not limited to, m-chloroperbenzoic acid, hydrogen peroxide, peracetic acid, etc.
  • the amount of the peracid is usually 1.0 to 20.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (IV) .
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and dimethyl sulfoxide and sulfolane. Any one of these solvents
  • the amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (IV) .
  • the hydrolysis of the intermediate can be done by any known procedure, examples include, but are not limited to, using an acid in protic solvents, or using a base in appropriate solvent.
  • any well-known acid like hydrochloric acid, sulfuric acid, etc. can be used while in basic conditions, any known base, such as organic bases like triethylamine or inorganic bases like sodium hydroxide can be used.
  • the amount of the acid or base to be used is usually 1.0 to 20.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (IV) .
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; dimethyl sulfoxide or sulfolane; and protic solvents like
  • the amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (IV) .
  • the reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 6 hours to 18 hours.
  • This step consists of reactions between compound (V) and compound (VI) in the presence of a base and solvent to produce the compound (VII) .
  • LG represents any suitable leaving group, such as halogen, O-mesylates, O-sulfonates, O-tosylates, etc.
  • the base used for the above mentioned reaction is not particularly limited.
  • any conventionally known base can widely be used, and examples of the base include: alkali metal carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases including alkali metal hydrides, such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases, such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine pyridine, piperidine, and the like. Any separate one of these bases or a combination of two or more types thereof can be used.
  • the amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 1.5 mol, per 1 mol of the compound (V) .
  • the aforementioned reaction is performed in an appropriate solvent. No limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • a solvent examples include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; amide-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane; acetonitrile; N, N-dimethylformamide (DMF) , N, N-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and dimethyl sulfoxide, sulfolane, and protic solvents, such as methanol, ethanol, water, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • halogenated hydrocarbon-based solvents such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like
  • amide-based solvents such
  • the amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (V) .
  • the reaction temperature varies depending on the starting compound, the reaction reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 60 minutes to 12 hours.
  • This step involves the reduction of nitro group (N0 2 ) present in the compound (VII) to produce amino group (NH 2 ) of the compound (VIII) .
  • R, Xi, X 2 , X3 and Q are as defined above.
  • the reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 90°C.
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 5 minutes to 48 hours, preferably from 60 minutes to 6 hours.
  • This step is a method of preparing the compound (X) from the reactions of compound (VIII) and compound (IX) in the presence of a catalyst and a suitable solvent.
  • R, R 2 , R 3 , Xi, X 2 , X 3 and Q are as defined above.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: benzene, chlorobenzene, toluene, xylene, 1 , 2-dichloroethane, diphenyl ether, acetonitrile, A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone, polyphosphoric acid Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • the amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound represented by formula (VIII) .
  • the aforementioned reaction can be performed under the presence of a catalyst.
  • a catalyst there are various conventional catalysts which can be used for this reaction and some examples of these catalysts include: trifluoroacetic acid; hydrochloric acid; sulfuric acid; p-toluene sulfonic acid; boron trifluoride etherate (BF 3 -Et 2 0) ; aluminium chloride (AICI 3 ) ; iron chloride (FeCls); titanium chloride (T ⁇ 01 4 ) ; tin chloride (SnCl 4 ) .
  • the amount of the acid to be used is usually 1.0 to 5 mol, preferably 0.05 mol, per 1.5 mol of the compound (VIII) .
  • the amount of the acetoacetate (IX) to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol of the compound (VIII) .
  • the reaction temperature varies depending on the type of the starting compound, the reagent, and the solvent and generally from 0°C to 200 0 C .
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 2 hours to 16 hours.
  • This step produces the compound ( 1 ) by the treatment of compound (X) with compound (XI) .
  • R, Ri, R 2 , R 3 , Rg, Rio, Xi, X 2 , X 3 and Q are as defined above.
  • LGi represents any suitable leaving group, such as halogen, O-mesylates, O-sulfonates, O-tosylates, etc.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: aromatic hydrocarbon-based solvents, such as benzene, chlorobenzene, toluene, xylene, and the like; halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like s; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) ,
  • aromatic hydrocarbon-based solvents such as benzene, chlorobenzene, toluene, xylene, and the like
  • A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like and ketone-based solvents, such as acetone, methyl ethyl ketone, cyclohexanone, and the like; and dimethyl sulfoxide. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • the amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound represented by formula (X) .
  • a base used for the above mentioned reaction is not particularly limited.
  • a conventionally known base can widely be used, and examples of the base include: alkali metal carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; metal hydroxides, such as sodium hydroxide, potassium hydroxide, and the like alkali; inorganic bases including alkali metal hydrides, such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases, such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine pyridine, piperidine, and the like; and preferably pyridine. Any separate one of these bases or a combination of two or more types
  • the amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 1.1 mol, per 1 mol of the compound (X) , sometimes, when an organic base is used it can serve as a solvent also.
  • the amount of compound (XI) to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (X) .
  • the reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is generally from — 10 ° C to boiling point of the solvent.
  • the reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 1 hour to 12 hours.
  • Each compound represented in Scheme- 1 after the completion of the reaction can be easily isolated from the reaction mixtures and purified by known isolations and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography.
  • Compound (1) of the present disclosure may be used as an active ingredient of a pest-controlling agent.
  • pest-controlling agents include agents (agricultural and horticultural insecticide, miticides, nematicides, or soil insecticides) for controlling pests , mites, nematode, or soil pests that all cause problems in the agricultural and horticultural fields; animal-ectoparasite-controlling agents (e.g., pulicide, ixodicide, and pedivulicide) , and the like.
  • compound (1) of the present disclosure For use as an active ingredient of a pest-controlling agent, it is possible to use compound (1) of the present disclosure as is with no additional components. However, it is usually preferable to use the compound by it combining with a solid carrier, liquid carrier, or gaseous carrier (propellant) , and optionally with a surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms, such as oil solutions, emulsions, wettable powders, flowable preparations, granules, dusts, aerosols, fumigants, or the like, according to known preparation methods.
  • a solid carrier liquid carrier, or gaseous carrier (propellant)
  • surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms, 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 disclosure is usually contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt% .
  • solid carrier examples include mineral carriers, such as pyrophyllite clay, kaolin clay, silicastone clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, active clay, Attapulgus clay, vermiculite, perlite, pumice, white carbon (e.g., mineral carriers, such as pyrophyllite clay, kaolin clay, silicastone clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, active clay, Attapulgus clay, vermiculite, perlite, pumice, white carbon (e.g.
  • mineral carriers such as pyrophyllite clay, kaolin clay, silicastone clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, active clay, Attapulgus clay, vermiculite, perlite, pumice, white carbon (e.g.
  • synthetic silicic acid or synthetic silicate titanium dioxide and the like
  • vegetable carriers such as wood flour, corn culm, walnut shell, fruit stone, rice hull, sawdust, wheat bran, soybean flour, powder cellulose, starch, dextrin, saccharide and the like
  • inorganic salt carriers such as calcium carbonate, ammonium sulfate, sodium sulfate, potassium chloride and the like
  • polymer carriers such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, urea-aldehyde resin and the like.
  • liquid carrier examples include monohydric alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and the like; polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, glycerine and the like; polyhydric alcohol derivatives, such as propylene type glycol ether and the like; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone and the like; ethers, such as ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether, tetrahydrofuran and the like; aliphatic hydrocarbons, such as normal paraffin, naphthene, isoparaffin, ali
  • the surfactant preferably gels or swells in water.
  • non-ionic surfactants such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether-formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkyl amine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyethylene fatty acid bisphenyl ether, polyalkylene
  • dialkyldiaminoethylbetaine or alkyldimethylbenzylbetaine amino acid type (e.g. dialkylaminoethylglycine or alkyldimethylbenzylglycine ) and the like .
  • binder and the tackifier examples include carboxymethyl cellulose or a salt thereof, dextrin, water-soluble starch, xanthane gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol having an average molecular weight of 6, 000 to 20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and natural phospholipid (e.g. cephalinic acid or lecithin) .
  • phospholipid e.g. cephalinic acid or lecithin
  • examples include water-soluble polymers, such as xanthan gum, guar gum, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, polysaccharide and the like; and inorganic fine powders, such as high-purity bentonite, white carbon and the like.
  • water-soluble polymers such as xanthan gum, guar gum, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, polysaccharide and the like
  • inorganic fine powders such as high-purity bentonite, white carbon and the like.
  • examples include, inorganic pigments, such as iron oxide, titanium oxide, Prussian Blue and the like; and organic dyes, such as Alizarine dye, azo dye, metal phthalocyanine dye and the like.
  • examples include silicone-based surfactant, cellulose powder, dextrin, processed starch, polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrene, methacrylic acid copolymer, half ester between polyhydric alcohol polymer and dicarboxylic acid anhydride, and water-soluble salt of polystyrenesulfonic acid.
  • examples include surfactant (e.g. sodium dialkylsulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, or polyoxyethylene fatty acid ester) , paraffin, terpene, polyamide resin, polyacrylic acid salt, polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol-formalin condensate, and synthetic resin emulsion.
  • surfactant e.g. sodium dialkylsulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, or polyoxyethylene fatty acid ester
  • paraffin terpene
  • polyamide resin polyacrylic acid salt
  • polyoxyethylene wax
  • polyvinyl alkyl ether polyvinyl alkyl ether
  • alkylphenol-formalin condensate alkylphenol-formalin condensate
  • examples include polyhydric alcohol (e.g. ethylene glycol, diethylene glycol, propylene glycol, or glycerine) .
  • polyhydric alcohol e.g. ethylene glycol, diethylene glycol, propylene glycol, or glycerine
  • examples include polysaccharide (e.g. starch, alginic acid, mannonse or galactose), polyvinylpyrrolidone, white carbon, ester gum and petroleum resin.
  • polysaccharide e.g. starch, alginic acid, mannonse or galactose
  • polyvinylpyrrolidone e.g. white carbon, ester gum and petroleum resin.
  • examples include sodium tripolyphosphate, sodium hexametaphosphate, stearic acid metal salt, cellulose powder, dextrin, methacrylic acid ester copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene-isobutylene-maleic anhydride copolymer, and starchpolyacrylonitrile graft copolymer.
  • examples include, desiccants, such as zeolite, quick lime, magnesium oxide and the like; antioxidants, such as phenol type, amine type, sulfur type, phosphoric acid type and the like; and ultraviolet absorbents, such as salicylic acid type, benzophenone type and the like.
  • the present pest control agent contains the above-mentioned additive components
  • their contents based on mass are selected in a range of ordinarily 5 to 95%, preferably 20 to 90% in the case of carrier (e.g. solid carrier or liquid carrier), ordinarily 0.1 to 30%, preferably 0.5 to 10% in the case of surfactant, and ordinarily 0.1 to 30%, preferably 0.5 to 10% in the case of other additives .
  • the present pest control agent is used in any formulation selected from dust formulation, dust-granule mixture, granule, wettable powder, water-soluble concentrate, water-dispersible granule, tablet, Jumbo, emulsifiable concentrate, oil formulation, solution, flowable concentrate, emulsion, microemulsion, suspoemulsion, ultra-low volume formulation, microcapsule, smoking agent, aerosol, baiting agent, paste, etc.
  • the formulation can be used per se or after dilution with a diluent (e.g. water) in a given concentration.
  • a diluent e.g. water
  • the application of the formulation containing the present compound or its dilution product can be conducted by a method ordinarily used, such as dispersion (e.g. spraying, misting, atomizing, powder dispersion, granule dispersion, on-water-surface dispersion, or inbox dispersion) , in-soil application (e.g. mixing or drenching), on-surface application (e.g. coating, dust coating or covering), immersion, poison bait, smoking and the like.
  • dispersion e.g. spraying, misting, atomizing, powder dispersion, granule dispersion, on-water-surface dispersion, or inbox dispersion
  • in-soil application e.g. mixing or drenching
  • on-surface application e.g. coating
  • the proportion (mass %) of the active ingredient in the present pest control agent is appropriately selected so as to meet the necessity.
  • the active ingredient is appropriately selected, for example, in the following ranges:
  • dust-granule mixture, etc. 0.01 to 20%, preferably 0.05 to 10%.
  • granule, etc. 0.1 to 30%, preferably 0.5 to 20%.
  • the formulation is sprayed after dilution in an appropriate concentration, or applied directly.
  • the concentration of active ingredient is generally 0.1 to 5, 000 ppm.
  • the application amount thereof per unit area is 0.1 to 5,000 g per 1 ha in terms of active ingredient compound; however, the application amount is not restricted thereto.
  • the present pest control agent is sufficiently effective when using the present compound alone as an active ingredient.
  • the present pest control agent may be mixed or used in combination, as necessary, with fertilizers and agricultural chemicals, such as insecticide, miticide, nematocide, synergist, fungicide, antiviral agent, attractant, herbicide, plant growth-controlling agent and the like. In this case, a higher effect is exhibited.
  • Compound (1) of the present disclosure is effectively used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide.
  • compound (1) of the present disclosure is effective for controlling pests: for example, aphids, such as green peach aphids, cotton aphids, and the like; diamondback moths, Spodoptera litura, 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; gastropods, such as slugs, snails, and the like; hygiene-harming insects, such as rat mit
  • Compound (1) of the present disclosure is characterized by having a particularly excellent fungicidal activity and a broad spectrum of activity.
  • the compound may be used for controlling plant diseases ascribed to various fungal pathogens or resistant fungal pathogens.
  • fungal pathogens include those that cause cucumber gray mold, rice plant blast (Pyricularia grisea, millet) , 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.
  • m-Chloroperbenzoic acid (8.34 g, 48.36 mmol, 0.9 equiv.) was added to a solution of 1- (p-tolyl ) -lff-pyrazole-4-carbaldehyde (10.0 g, 53.74 mmol, 1.0 equiv.) in chloroform (500 mL) at room temperature under nitrogen atmosphere. The resulting mixture was refluxed for 4h.
  • reaction mixture was then cooled to room temperature, diluted with DCM (100 mL) , washed with sodium bicarbonate solution (3 x 100 mL) followed by distilled water (3 x 100 mL) , dried over sodium sulfate, filtered and concentrated under reduced pressure to give a crude product .
  • the pH of the reaction mixture was then made neutral by adding sodium bicarbonate solution and extracted with ethyl acetate (3 x 100 mL) .
  • CCbMe methoxycarbonyl , C0 2 Et: ethoxycarbonyl , CC ⁇ Ph: phenoxycarbonyl , Cy-pr: cyclopropyl, Cy-pent : cyclopentyl, F 2 -Ph: difluorophenyl, Cl 2 -Ph: dichlorophenyl , Cl 3 -Ph: trichlorophenyl , S0 2 Me: methylsulfonyl, SC ⁇ Et: ethylsulfonyl, SO 2 CF 3 : trifluoromethylsulfonyl, CN : cyano, N0 2 : nitro.
  • each compound of the present disclosure 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 blending in a juice mixer to give 20% wettable powders.
  • each compound of the present disclosure 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.
  • Compound A, Compound B and Flometoquin are the representative compounds mentioned in the specification of W02006/013896A1, W02007/088978A1.
  • Test Example 1 (Aphicidal test on Cotton aphid)
  • Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid.
  • a cucumber leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric.
  • Another cucumber leaf with cotton aphid (about 30 aphid samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25 ⁇ 2°C and a humidity of 40% for overnight. Next morning the top leaf was removed as aphid population has already moved to lower leaf.
  • Insecticidal formulations containing the compound of the present disclosure were prepared by adding an aqueous solution (100 ppm) of Sorpol 355 (manufactured by TOHO Chemical Industry Co., Ltd.) to a methanol solution of the compound of the present disclosure.
  • Insecticidal formulations were sprayed onto the leaves, and the leaves were air-dried and placed in a thermostatic chamber (25 ⁇ 2°C and a humidity of 50%) .
  • the mortality rate of the cotton aphid was calculated after 3 days.
  • Insecticidal formulations containing the compound of the present disclosure prepared in the same manner as in test example 1. These Insecticidal formulations were sprayed onto the castor leaves (4 x 4 cm) , leaves were air-dried and placed in a plastic cup over moist paper . 4 days old Spodoptera larvae (12-15 Nos.) were released, and cup is closed and placed in a thermostatic chamber (25 ⁇ 2°C and a humidity of 50%) . The mortality rate of the spodoptera was calculated after 3 days.
  • Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid.
  • a kidney bean leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric.
  • Another kidney bean leaf with two-spotted spider mites (about 30 mite samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25 ⁇ 2°C and a humidity of 40% overnight. Next morning the top leaf was removed as the mite population had already moved to the lower leaf.
  • Miticidal formulations containing the compound of the present disclosure prepared in the same manner as in test example 1. These miticidal formulations were sprayed onto the leaves, and the leaves were air-dried and placed in a thermostatic chamber (25 ⁇ 2°C and a humidity of 50%) . The mortality rate of the two-spotted spider mites was calculated after 2 days.
  • Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Twenty female adults of two-spotted spider mite were placed on the top of the leaf, and the fabric and leaf were placed in a thermostatic chamber having a temperature of 25 ⁇ 2°C and a humidity of 40% and 16L8D.
  • Miticidal formulations containing the compound of the present disclosure 500 ppm and 100 ppm prepared in the same manner as in test example 1 was sprayed onto the leaf, and the leaf was air-dried and placed in a thermostatic chamber (25 ⁇ 2°C and a humidity of 50%) .
  • the ovicidal rate of the two-spotted spider mites was calculated 6 days after the spraying of the miticidal formulation.
  • Compounds IB-38, IB-39, IB-41, IB-46, IB-47, IB-59, IB-61, IB-62, IB-63 , IB-64 , IB-66, IB-69, IB-70, IB-73, IB-75, IB-78 and IB-83 showed 80% or more mortality at 100 ppm whereas the reference compounds Compound A showed 40% mortality at 500 ppm and 0% mortality at 100 ppm, and the reference Compound B and Flometoquin each showed less than 30% mortality at 500 ppm.
  • Test example 5 Fungicidal test on Pyricularia grisea, millet
  • the small bit of mycelium of Pyricularia grisea was taken from culture tube and transferred on mathur media plate aseptically .
  • the inoculated plate was kept for 7 days at 25°C.
  • plates were incubated at 25°C for 5 days under the exposure to black light blue, 16L8D.
  • After five days the plates were fully covered with spores of fungus.
  • the spores were washed from plate with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain 2 x 10 5 cfu spore per ml .
  • the solution of the compound of the present disclosure (500 ppm) prepared in the same manner as in test example 1 was sprayed on fresh healthy two weeks old millet plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension.
  • the inoculated plants were then placed in a dew chamber (25°C and a humidity of 100%) .
  • One day after inoculation the plants were shifted to thermostatic chamber (25°C, a humidity of 80% , andl6L8D) .
  • the percent disease control was assessed after 5-7 days from leaf disease area compared to control.
  • Compounds 1A-276, 1A-325, IB-7 and IB-33 showed 80% or more control whereas the reference compounds (Compound A, Compound B and Flometoquin) showed less than 50%, less than 30%, and less than 30% control at 500 ppm, respectively.
  • Test example 6 Fungicidal test on Sphaerotheca fullglnea , cucumber
  • Sphaerotheca fuliginea was cultured on intact cucumber plants . Infected leaves with spores were washed with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain 2 x 10 5 cfu spore per ml .
  • the solution of the compound of the present disclosure (500 ppm) prepared in the same manner as in test example 1 was sprayed on fresh healthy two weeks old cucumber plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension.
  • the inoculated plants were then placed in green house (25°C, a humidity of 60% and 16L8D) .
  • the percent disease control was assessed after 12 days from leaf disease area compared to control.
  • Compounds 1A-172 , 1A-181, 1A-254 , 1A-262, 1A-264, 1A-266, 1A-325, 1A-431, IB-33, IB-57, IB-60, IB-66 and lC-10 showed 80% or more control whereas the reference Compound A showed such a strong phytotoxicity on cucumber at 500 ppm that evaluation was impossible, and the reference Compound B and Flometoquin showed 100% and less than 70% control at 500 ppm, respectively.
  • the substituted pyrazole compounds or a salt thereof of the present disclosure shows an excellent controlling effect against a wide range of pests, such as aphids, spodoptera, mites, etc. and are useful as a pesticide agent for agricultural and horticultural use .

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Abstract

An object of the present disclosure is to provide a novel substituted pyrazole compound or a salt thereof as represented by formula (1) that controls pests: wherein, Q represents an oxygen atom or a sulfur atom, or the like; R represents substituted or unsubstituted aryl, C1-C12alkyl, or the like; Represents hydrogen, substituted or unsubstituted C1- C12alkylcarbonyl, substituted or unsubstituted C1-C12alkoxycarbonyl or the like; R2and R3each independently represent hydrogen, substituted or unsubstituted C1-C12alkyl, or the like; R4and R5each independently represent hydrogen, substituted or unsubstituted C1- C12alkyl, or the like; andX1, X2and X3grepresent C-R8, C-Rg and C-R|0, respectively, wherein R8, R9and Rjgeach independently represent hydrogen, halogen, methyl, ethyl or the like. The compounds of formula (1) are useful as insecticides and fungicides.

Description

DESCRIPTION
SUBSTITUTED PYRAZOLE DERIVATIVES AS INSECTICIDES AND FUNGICIDES
Technical Field
The present disclosure relates to novel pyrazole compounds and the process for preparing the said compounds. Furthermore, the disclosure provides an agriculture and horticulture insecticide and fungicide composition comprising the compounds of the present disclosure .
Background of the invention
In recent years, it has been observed that due to long term and heavy use of conventional insecticides and fungicides, various insects and fungi have acquired resistance thereto. Therefore, these known pesticides are now incapable of controlling these pests effectively. To overcome this situation, there is a constant demand for the development of new types of pesticides that can control various chemical-sensitive as well as chemical-resistant insects and fungi .
Various compounds bearing pest control activity have been previously developed. For example, WO 2007/088978 (Patent Literature (PTL) 1) disclosed quinoline derivatives having fungicidal activity but there was no description for insecticidal activity. Furthermore, WO 2006/013896 (Patent Literature (PTL) 2), JP 2008-110953 (Patent Literature (PTL) 3), JP 2633377 (Patent Literature (PTL) 4) and US 4168311 (Patent Literature (PTL) 5) disclosed quinoline derivatives having an insecticidal activity.
PTL 1 and PTL 2 disclosed the compound represented by the following formula (A) :
Figure imgf000002_0001
wherein,
Z represents an oxygen atom, a sulfur atom, SO, S02, CO or Q, etc., where Q is a C1-4 alkylene group (the Ci-4 alkylene group may be substituted with a halogen atom or a cyano group) ;
Ri, R2, and R3 represent hydrogen, C1-4 alkyl group, C1-4 haloalkyl group, C1-4 alkyloxy group, C1-4 haloalkoxy group, alkyloxycarbonyl group, nitro group, cyano group, formyl group, acetyl group, acetylethoxy group, etc.;
R2 and R3 together represent one (CH2)m, wherein m represents 3 or
4;
Xi, X2, and X3 each independently represent a hydrogen atom, a halogen atom, a Ci_4 alkyl group which may be substituted with a halogen atom or a Ci_4 alkyloxy group, a Ci_4 alkyloxycarbonyl group, a C1-4 alkyloxy group which may be substituted with a halogen atom, or a C1-4 alkyloxycarbonyl group which may be substituted by a halogen atom, with the proviso that X2, X2, and X3 do not simultaneously represent hydrogen atoms;
Wi represents a nitrogen atom or CY2,
W2 represents a nitrogen atom or CY2, and
W3 represents a nitrogen atom or CY3,
with the proviso that, when W2 represents a nitrogen atom, W2 and W3 represent CY2 and CY3, respectively, when W2 represents a nitrogen atom, Wi and W3 represent CY2 and CY3, respectively, and when W3 represents a nitrogen atom, W2 and W2 represent CY2 and CY2, respectively; and
Yi, Y2 and Y3 each independently represent a hydrogen atom, A, or
B,
wherein A represents a Ci-s alkyl group, Ci-s alkyloxy group, C2-s alkenyl group, C2-8 alkenyloxy group, Ci-s alkyloxycarbonyl group, C2-8 alkenylthio group, C1-8 alkylsulfinyl group, C2-s alkenylsulfinyl group, C1-8 alkylsulfonyl group, C2-8 alkenylsulfonyl group, phenyl group, or phenoxy group, wherein all these substituents may further be substituted with various groups, such as halogen, C1-4 alkyl group, etc., and
B represents a halogen atom, or a C1-4 alkyl group.
The publications also mentioned that the compounds represented by the formula (A) are useful as fungicide and insecticide to control pests for agriculture and horticulture purposes. However, these publications nowhere, include the compounds of the present disclosure .
Citation List Patent Literature
PTL 1: WO 2007/088978A1
PTL 2: WO 2006/013896A1
PTL 3: JP 2008-110953
PTL 4: JP 2633377
PTL 5: US 4168311
Summary of the Invention
Solution to Problem
The present disclosure provides novel substituted pyrazole compounds or salts thereof which exhibit high insecticidal and fungicidal activity against drug resistant insects and fungi as well as drug sensitive insects and fungi.
The present disclosure also provides a process for preparing the said novel substituted pyrazole compounds or salts thereof.
The present disclosure further provides a new type of agriculture and horticulture composition comprising a substituted pyrazole compound or a salt thereof as an active ingredient, which exhibits a remarkable insecticidal and fungicidal effect against chemical-resistant as well as chemical-sensitive insects and fungi.
Specifically, the present inventors conducted extensive research, and succeeded in synthesizing a compound represented by the following formula (1) or a salt thereof that has shown excellent insecticidal and fungicidal activities. The present inventors have conducted further research based on the above findings.
As a result of extensive research, the present inventors have found that a compound represented by the following general formula (1) or a salt thereof exhibits excellent insecticidal and fungicidal activity .
Thus, the present disclosure relates to novel substituted pyrazole compounds or salts thereof represented by the following general formula (1) .
More specifically, the present disclosure includes the following embodiments:
Embodiment A1 :
A substituted pyrazole compound represented by formula (1) :
Figure imgf000005_0001
or a salt thereof,
wherein,
Q represents an oxygen atom, a sulfur atom, CR.6R7 or direct bond. R6 and R7 each independently represent hydrogen, halogen, cyano, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 haloalkoxy, C1-C12 cyanoalkoxy, C1-C12 alkylthio, C1-C12 haloalkylthio, C1-C12 alkoxy, C1-C12 alkyl, C1-C12 haloalkoxy, C2-Ci2 alkenyl, C2-Ci2 haloalkenyl, C2-Ci2 alkenyloxy, C2-Ci2 haloalkenyloxy, C2-Ci2 alkynyl, C2-Ci2 haloalkynyl, C2-Ci2 alkynyloxy, C2-Ci2 haloalkynyloxy, Ci-Ci2 alkylsulfinyl, Ci-Ci2 alkylsulfonyl, Ci-Ci2 haloalkylsulfinyl, Ci-Ci2 haloalkylsulfonyl, C3-Ci2 cycloalkyl, Ci-Ci2 alkylcarbonyl , Ci-Ci2 alkoxycarbonyl , Ci-Ci2 haloalkylcarbonyl , Ci-Ci2 haloalkoxycarbonyl , Ci-Ci2 alkylcarbonylamino, Ci-Ci2 alkylsulfonyloxy, Ci-Ci2 alkylsulfinyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted saturated heterocyclic;
R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted aryl Ci-Ci2 alkyl, substituted or unsubstituted heteroaryl Ci-Ci2 alkyl, Ci-Ci2 alkyl, Ci-Ci2 haloalkyl, Ci-Ci2 cyanoalkyl, Ci-Ci2 alkoxy Ci-Ci2 alkyl, Ci-Ci2 alkylthio Ci-Ci2 alkyl, Ci-Ci2 haloalkoxy Ci-Ci2 alkyl, C2-Ci2 alkenyl, C2-Ci2 alkynyl, C2-Ci2 haloalkenyl, C2-Ci2 haloalkynyl, Ci-Ci2 alkylsulfinyl, Ci-Ci2 alkylsulfonyl, Ci-Ci2 haloalkylsulfinyl, Ci-Ci2 haloalkylsulfonyl, Ci-Ci2 alkylcarbonyl, Ci-Ci2 haloalkylcarbonyl, Ci-Ci2 alkoxycarbonyl, Ci-Ci2 haloalkoxycarbonyl, C3-Ci2 cycloalkyl, or saturated heterocyclic;
Ri represents hydrogen, substituted or unsubstituted Ci-Ci2 alkyl, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C3-Ci2 cycloalkyl, substituted or unsubstituted aryl Ci-Ci2 alkyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl, substituted or unsubstituted Ci-Ci2 haloalkylcarbonyl, substituted or unsubstituted Ci-Ci2 haloalkoxycarbonyl, substituted or unsubstituted C2-C12 alkenylcarbonyl , substituted or unsubstituted C2 - C12 alkynylcarbonyl , substituted or unsubstituted C3- C12 cycloalkylcarbonyl , substituted or unsubstituted C1-C12 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted aryl C1-C12 alkoxycarbonyl, substituted or unsubstituted heteroaryloxycarbonyl , substituted or unsubstituted heteroaryl C1-C12 alkoxycarbonyl, substituted or unsubstituted arylcarbonyl , substituted or unsubstituted aryl C1- C12 alkylcarbonyl , substituted or unsubstituted heteroarylcarbonyl , substituted or unsubstituted heteroaryl C1- C12 alkylcarbonyl, substituted or unsubstituted heterocyclecarbonyl , substituted or unsubstituted heterocycle C 1- C12 alkylcarbonyl, substituted or unsubstituted C3- C12 cycloalkyl C1- C12 alkylcarbonyl, substituted or unsubstituted C1- C12 alkylsulfinyl, substituted or unsubstituted C1- C12 alkylsulfonyl, substituted or unsubstituted C1-C12 haloalkylsulfinyl, substituted or unsubstituted C1-C12 haloalkylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted heteroarylsulfinyl, substituted or unsubstituted arylsulfonyl, or substituted or unsubstituted heteroarylsul tony1 ;
R2 represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 haloalkyl, substituted or unsubstituted C1-C12 alkoxy, or substituted or unsubstituted C1-C12 haloalkoxy;
R3 represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 haloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 haloalkoxy, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C3- C12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclic;
R4 and R5 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 haloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, or substituted or unsubstituted aryl;
Xi represents C-Rs or N,
X2 represents C-R9 or N, and X3 represents C-R10 or N,
with the proviso that, when Xi represents a nitrogen atom, X2 and X3 represent C-R9 and C-R10 , respectively, when X2 represents a nitrogen atom, Xi and X3 represent C-Rs and C-R10 , respectively, and when X3 represents a nitrogen atom, Xi and X2 represent C-Rs and C-Rg, respectively;
Re , R9 and Rio each independently represent hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 haloalkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 haloalkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C1-C12 haloalkylthio, substituted or unsubstituted C1-C12 alkoxycarbonyl, substituted or unsubstituted C1-C12 haloalkoxycarbonyl , cyano, nitro or substituted or unsubstituted amino .
Embodiment A2 :
The substituted pyrazole compound or a salt thereof according to embodiment Al, wherein Q represents an oxygen atom, or a sulfur atom.
Embodiment A3 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 or A2, wherein R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or C1-C12 alkyl.
Embodiment A4 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A3, wherein Ri represents hydrogen, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C1-C12 alkylcarbonyl , substituted or unsubstituted C3-C12 cycloalkylcarbonyl , substituted or unsubstituted C1-C12 alkoxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted C1-C12 alkylsulfinyl, substituted or unsubstituted C1-C12 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, or substituted or unsubstituted arylsulfonyl . Embodiment A5 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A4, wherein R2 represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, or substituted or unsubstituted Ci-Ci2 haloalkyl.
Embodiment A6 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A5, wherein R3 represents substituted or unsubstituted Ci-Ci2 alkyl, or substituted or unsubstituted Ci-Ci2 haloalkyl .
Embodiment A7 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A6, wherein R4 and R5 each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, or substituted or unsubstituted Ci-Ci2 haloalkyl .
Embodiment A8 :
The substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A7, wherein X2 represents C-Rs, X2 represents C-Rg, and X3 represents C-R10, wherein Rg, R9 and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, substituted or unsubstituted Ci-Ci2 haloalkyl, or substituted or unsubstituted Ci-Ci2 alkoxy.
Embodiment A9 :
A pest controlling agent comprising the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 as an active ingredient.
Embodiment A10:
A method for using the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 for controlling pests .
Embodiment All: A method for controlling pests, which comprises applying the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 to a plant or its vicinity, or soil where a plant is cultivated.
Embodiment A12:
A method for controlling pests, which comprises applying an effective amount of the substituted pyrazole compound or a salt thereof according to any one of embodiments A1 to A8 to pests, a habitat of a pests, or a place where inhabitation is predicted.
Furthermore specifically, the present disclosure includes the following embodiments:
Embodiment 1 :
A substituted pyrazole compound represented by formula (1) :
Figure imgf000009_0001
or a salt thereof,
wherein,
Q represents an oxygen atom, a sulfur atom, CR.6R7 or direct bond; R¾ and R7 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkenyloxy, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C2-Ci2 alkynyloxy, substituted or unsubstituted Ci-Ci2 alkylsulfinyl, substituted or unsubstituted Ci-Ci2 alkylsulfonyl, substituted or unsubstituted C3-Ci2 cycloalkyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , substituted or unsubstituted Ci-Ci2 alkylcarbonylamino, substituted or unsubstituted Ci-Ci2 alkylsulfonyloxy, substituted or unsubstituted Ci-Ci2 alkylsulfinyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted saturated heterocyclic;
R represents hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C1-C12 alkylsulfinyl, substituted or unsubstituted C1-C12 alkylsulfonyl, substituted or unsubstituted C1-C12 alkylcarbonyl , substituted or unsubstituted C1-C12 alkoxycarbonyl , substituted or unsubstituted C3-C12 cycloalkyl, or substituted or unsubstituted saturated heterocyclic;
Ri represents hydrogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted C1-C12 alkylcarbonyl, substituted or unsubstituted C2-Ci2 alkenylcarbonyl , substituted or unsubstituted C2-Ci2 alkynylcarbonyl , substituted or unsubstituted C3-C12 cycloalkylcarbonyl , substituted or unsubstituted C1-C12 alkoxycarbonyl, substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted heteroaryloxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted heteroarylcarbonyl , substituted or unsubstituted heterocyclecarbonyl , substituted or unsubstituted C1-C12 alkylsulfinyl, substituted or unsubstituted C1-C12 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted heteroarylsulfinyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted heteroarylsulfonyl ;
R2 and R3 each independently represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C2-C12 alkenyl, substituted or unsubstituted C2-C12 alkynyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclic;
R4 and R5 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio or substituted or unsubstituted aryl;
Xi represents C-Rs or N,
X2 represents C-R9 or N, and X3 represents C-Rio or N,
with the proviso that, when Xi represents a nitrogen atom, X2 and X3 represent C-R9 and C-R10, respectively, when X2 represents a nitrogen atom, X2 and X3 represent C-Rs and C-R10, respectively, and when X3 represents a nitrogen atom, X2 and X2 represent C-R3 and C-Rg, respectively; and
Re, R9 and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, substituted or unsubstituted Ci-Ci2 alkoxy, substituted or unsubstituted Ci-Ci2 alkylthio, substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , cyano, nitro, or substituted or unsubstituted amino.
Embodiment la:
The substituted pyrazole compound or a salt thereof according to embodiment 1, wherein, in R6 and R7,
said substituted or unsubstituted Ci-Ci2 alkyl is selected from the group consisting of Ci-Ci2 alkyl, Ci-Ci2 haloalkyl, Ci-Ci2 alkoxy Ci-Ci2 alkyl, and Ci-Ci2 haloalkoxy Ci-Ci2 alkyl;
said substituted or unsubstituted Ci-Ci2 alkoxy is selected from the group consisting of Ci-Ci2 alkoxy, Ci-Ci2 haloalkoxy, and Ci-Ci2 cyanoalkoxy;
said substituted or unsubstituted Ci-Ci2 alkylthio is selected from the group consisting of Ci-Ci2 alkylthio and Ci-Ci2 haloalkylthio ; said substituted or unsubstituted C2-Ci2 alkenyl is selected from the group consisting of C2-Ci2 alkenyl and C2-Ci2 haloalkenyl; said substituted or unsubstituted C2-Ci2 alkenyloxy is selected from the group consisting of C2-Ci2 alkenyloxy and C2-Ci2 haloalkenyloxy; said substituted or unsubstituted C2-Ci2 alkynyl is selected from the group consisting of C2-Ci2 alkynyl and C2-Ci2 haloalkynyl; said substituted or unsubstituted C2-Ci2 alkynyloxy is selected from the group consisting of C2-Ci2 alkynyloxy and C2-Ci2 haloalkynyloxy; said substituted or unsubstituted Ci-Ci2 alkylsulfinyl is selected from the group consisting of Ci-Ci2 alkylsulfinyl and Ci-Ci2 haloalkyl sulfinyl ;
said substituted or unsubstituted Ci-Ci2 alkylsulfonyl is selected from the group consisting of Ci-Ci2 alkylsulfonyl and Ci-Ci2 haloalkyl sulfonyl ;
said substituted or unsubstituted C3-Ci2 cycloalkyl is C3-Ci2 cycloalkyl ; said substituted or unsubstituted C1-C12 alkylcarbonyl is selected from the group consisting of C1-C12 alkylcarbonyl and C1-C12 haloalkylcarbonyl ;
said substituted or unsubstituted C1-C12 alkoxycarbonyl is selected from the group consisting of C1-C12 alkoxycarbonyl and C1-C12 haloalkoxycarbonyl ;
said substituted or unsubstituted C1-C12 alkylcarbonylamino is C1-C12 alkylcarbonylamino;
said substituted or unsubstituted C1-C12 alkylsulfonyloxy is C1-C12 alkylsulfonyloxy; and/or
said substituted or unsubstituted C1-C12 alkylsulfinyloxy is C1-C12 alkylsulfinyloxy .
Embodiment lb:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R,
said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 cyanoalkyl, C1-C12 alkoxy C1-C12 alkyl, C1-C12 alkylthio C1-C12 alkyl, C1-C12 haloalkoxy C1-C12 alkyl, substituted or unsubstituted aryl C1-C12 alkyl, and substituted or unsubstituted hetroaryl aryl C1-C12 alkyl; said substituted or unsubstituted C2-Ci2 alkenyl is selected from the group consisting of C2-Ci2 alkenyl and C2-Ci2 haloalkenyl; said substituted or unsubstituted C2-Ci2 alkynyl is selected from the group consisting of C2-Ci2 alkynyl and C2-Ci2 haloalkynyl; said substituted or unsubstituted Ci-Ci2 alkylsulfinyl is selected from the group consisting of Ci-Ci2 alkylsulfinyl and Ci-Ci2 haloalkyl sulfinyl ;
said substituted or unsubstituted Ci-Ci2 alkylsulfonyl is selected from the group consisting of Ci-Ci2 alkylsulfonyl and Ci-Ci2 haloalkyl sulfonyl ;
said substituted or unsubstituted Ci-Ci2 alkylcarbonyl is selected from the group consisting of Ci-Ci2 alkylcarbonyl Ci-Ci2 haloalkylcarbonyl ;
said substituted or unsubstituted Ci-Ci2 alkoxycarbonyl is selected from the group consisting of Ci-Ci2 alkoxycarbonyl and Ci-Ci2 haloalkoxycarbonyl; and/or
said substituted or unsubstituted saturated heterocyclic is saturated heterocyclic. Embodiment lc:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in Ri, said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkyl and substituted or unsubstituted aryl C1-C12 alkyl;
said substituted or unsubstituted C1-C12 alkylcarbonyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkylcarbonyl, substituted or unsubstituted C1-C12 haloalkylcarbonyl , substituted or unsubstituted aryl C1-C12 alkylcarbonyl, substituted or unsubstituted heteroaryl C1-C12 alkylcarbonyl, substituted or unsubstituted heterocycle C1-C12 alkylcarbonyl, and substituted or unsubstituted C3-Ci2 cycloalkyl C1-C12 alkylcarbonyl;
said substituted or unsubstituted C1-C12 alkoxycarbonyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkoxycarbonyl, substituted or unsubstituted aryl C1-C12 alkoxycarbonyl, and substituted or unsubstituted heteroaryl C1-C12 alkoxycarbonyl ;
said substituted or unsubstituted C1-C12 alkylsulfinyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkylsulfinyl, and substituted or unsubstituted C1-C12 haloalkylsulfinyl ; and/or
said substituted or unsubstituted C1-C12 alkylsulfonyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkylsulfonyl, and C1-C12 haloalkylsulfonyl ; and
the groups mentioned as Ri can also be further substituted by various substituents groups, such as F, Cl, Br, I, CN, N02, CH3, C(CH3)3, OCH3, C02CH3, C02CH2CH3, S02CH3, OCH2CF3, CF3, or OCF3.
Embodiment Id:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R2, said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkyl, and substituted or unsubstituted C1-C12 haloalkyl; and/or
said substituted or unsubstituted C1-C12 alkoxy is selected from the group consisting of substituted or unsubstituted C1-C12 alkoxy, and substituted or unsubstituted C1-C12 haloalkoxy.
Embodiment le:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R3,
said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkyl, and substituted or unsubstituted C1-C12 haloalkyl; and/or
said substituted or unsubstituted C1-C12 alkoxy is selected from the group consisting of substituted or unsubstituted C1-C12 alkoxy, and substituted or unsubstituted C1-C12 haloalkoxy.
Embodiment If:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R4 and R5, said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkyl, and substituted or unsubstituted C1-C12 haloalkyl.
Embodiment lg:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein, in R8, R9 and Rio, said substituted or unsubstituted C1-C12 alkyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkyl, and substituted or unsubstituted C1-C12 haloalkyl;
said substituted or unsubstituted C1-C12 alkoxy is selected from the group consisting of substituted or unsubstituted C1-C12 alkoxy, and substituted or unsubstituted C1-C12 haloalkoxy;
said substituted or unsubstituted C1-C12 alkylthio is selected from the group consisting of substituted or unsubstituted C1-C12 alkylthio, and substituted or unsubstituted C1-C12 haloalkylthio ; and/or
said substituted or unsubstituted C1-C12 alkoxycarbonyl is selected from the group consisting of substituted or unsubstituted C1-C12 alkoxycarbonyl, and substituted or unsubstituted C1-C12 haloalkoxycarbonyl .
Embodiment lh:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein
Q represents an oxygen atom or a sulfur atom;
R represents substituted or unsubstituted aryl, substituted or unsubstituted C1-C12 alkyl,
Ri represents hydrogen, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted arylcarbonyl , or substituted or unsubstituted Ci-Ci2 alkylsulfonyl ;
R2 represents hydrogen, or substituted or unsubstituted Ci-Ci2 alkyl; R3 represents substituted or unsubstituted Ci-Ci2 alkyl;
R4 and R5 each independently represent hydrogen, substituted or unsubstituted Ci-Ci2 alkyl;
Xi represents C-R3 or N,
X2 represents C-Rg, and
X3 represents C-R10,
with the proviso that, when X2 represents a nitrogen atom, X2 and X3 represent C-Rg and C-R10, respectively, when X2 represents a nitrogen atom, X2 and X3 represent C-R3 and C-R10, respectively, and when X3 represents a nitrogen atom, X2 and X2 represent C-R3 and C-Rg, respectively; and
R8, Rg and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, or substituted or unsubstituted Ci-Ci2 alkoxy.
Embodiment 2 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein Q represents an oxygen atom, or a sulfur atom.
Embodiment 3 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted Ci-Ci2 alkyl.
Embodiment 4 : The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R represents substituted or unsubstituted C6-C10 aryl, or unsubstituted C1-C12 alkyl .
Embodiment 5 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein Ri represents hydrogen, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted Ci-Ci2 alkylsulfinyl, substituted or unsubstituted Ci-Ci2 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, or substituted or unsubstituted arylsulfonyl .
Embodiment 6 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R2 represents hydrogen, substituted or unsubstituted C2-C22 alkenyl, unsubstituted C2-Ci2 alkynyl, unsubstituted Ci-Ci2 alkylcarbonyl, unsubstituted C3-Ci2 cycloalkylcarbonyl, unsubstituted Ci-Ci2 alkoxycarbonyl, substituted or unsubstituted C6-C10 arylcarbonyl, unsubstituted C6-C10 aryloxycarbonyl, or unsubstituted C6-C10 arylsulfonyl .
Embodiment 7 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R2 represents hydrogen, halogen, or substituted or unsubstituted Ci-Ci2 alkyl.
Embodiment 8 :
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R2 represents hydrogen, or unsubstituted Ci-Ci2 alkyl.
Embodiment 9 : The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R3 represents substituted or unsubstituted C1-C12 alkyl.
Embodiment 10:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R4 and R5 each independently represent hydrogen, halogen, or substituted or unsubstituted C1-C12 alkyl.
Embodiment 11:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R4 and R5 each independently represent hydrogen, or unsubstituted C1-C12 alkyl.
Embodiment 12:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein X4 represents C-R8, X2 represents C-R9, X3 represents C-R10, and R8, R9 and Ri0 are independently of each other hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, or substituted or unsubstituted C1-C12 alkoxy .
Embodiment 13:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein X4 represents C-R8, X2 represents C-Rg, X3 represents C-R10, and R8, Rg and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, or unsubstituted Ci-Ci2 alkoxy.
Embodiment 14:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein Q represents an oxygen atom.
Embodiment 15:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R represents substituted or unsubstituted Oe aryl. Embodiment 16:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein Ri represents hydrogen, unsubstituted C1-C12 alkylcarbonyl , unsubstituted C3-C12 cycloalkylcarbonyl , unsubstituted C1-C12 alkoxycarbonyl , or substituted or unsubstituted C6 arylcarbonyl .
Embodiment 17:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R2 represents unsubstituted Ci-C6 alkyl.
Embodiment 18:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R3 represents unsubstituted Ci-C6 alkyl.
Embodiment 19:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein R4 and R5 each independently represent hydrogen, or unsubstituted C1-C6 alkyl.
Embodiment 20:
The substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments, wherein Xi represents C-Rs, X2 represents C-Rg, X3 represents C-R10, and Rs, R9 and Rio are, independently of each other, hydrogen, halogen, unsubstituted C1-C6 alkyl, or unsubstituted C1-C6 alkoxy.
Embodiment 21:
A pest controlling agent comprising the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments as an active ingredient.
Embodiment 22:
A method for using the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments for controlling pests. Embodiment 23:
A method for controlling pests, which comprises applying the substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments to a plant or its vicinity, or soil where a plant is cultivated.
Embodiment 24:
A method for controlling pests, which comprises applying an effective amount of substituted pyrazole compound or a salt thereof according to any one of the preceding embodiments to pests, a habitat of a pests, or a place where inhabitation is predicted.
Advantageous Effects of Invention
A novel substituted pyrazole compound or a salt thereof according to the present disclosure achieves an excellent insecticidal and fungicidal effect. Additionally, the pyrazole compound or a salt thereof according to the present disclosure is useful as a new type of insecticide and fungicide that exhibit excellent insecticidal and fungicidal effect not only against chemical-sensitive fungi, but also against chemical-resistant fungi .
Description of Embodiments
The present disclosure is described hereinafter. Throughout the entire specification, a singular expression should be understood as encompassing the concept thereof in the plural form unless specifically noted otherwise . Thus, singular articles (e.g., "a", "an", "the" and the like in case of English) should also be understood as encompassing the concept thereof in the plural form unless specifically noted otherwise . Further, the terms used herein should be understood as being used in the meaning that is commonly used in the art, unless specifically noted otherwise. Thus, unless defined otherwise, all terminologies and scientific technical terms that are used herein have the same meaning as the terms commonly understood by those skilled in the art to which the present disclosure pertains. In case of a contradiction, the present specification (including the definitions) takes precedence. 1. Substituted pyrazole compound or a salt thereof
The present disclosure is directed to a compound represented by Formula ( 1 ) :
Figure imgf000020_0001
or a salt thereof (hereinafter sometimes referred to as "compound (1) of the present disclosure" or "compound (1)"),
wherein R, Ri, R2, R3, R4, R5, Xi, X2, X3, and Q are as defined above.
Next, the terms in the present specification are described below .
In the present specification, the number of substituents of a group defined by "substituted" is not particularly limited if it is substitutable, and is one or plural . In addition, unless otherwise indicated, the description for each group is also applied when the group is one part of or a substituent on other groups.
"Ci-Ci2 alkyl" means a linear or branched, saturated hydrocarbon group having one to twelve carbon atoms. "C1-C6 alkyl" or "C1-C3 alkyl" means a linear or branched, saturated hydrocarbon group having one to six or one to three carbon atoms, respectively.
"C2-Ci2 alkenyl" means a linear or branched, unsaturated hydrocarbon group having two to twelve carbon atoms and containing one to three double bonds.
"C2-Ci2 alkynyl" means a linear or branched, unsaturated hydrocarbon group having two to twelve carbon atoms and containing one triple bond.
"C3-Ci2 cycloalkyl" means a cyclic alkyl having three to twelve carbon atoms, and includes those cyclic alkyl having a partially bridged structure. "C3-C6 cycloalkyl" means a cyclic alkyl having three to six carbon atoms. "C1-C12 alkoxy" refers to a "C1-C12 alkyloxy group", wherein the "C1-C12 alkyl" moiety is defined the same as the above-described "C1-C12 alkyl".
"Aryl" means a monocyclic or polycyclic aromatic hydrocarbon.
"C6-C10 aryl" means an aryl group, as defined herein, having six to ten carbon atoms. "C6 aryl" means an aryl group, as defined herein, having six carbon atoms.
"Heterocyclic" means a saturated, unsaturated, or aromatic heterocyclic group which has at least one of nitrogen, oxygen, phosphorus and/or sulfur atoms in the ring and may be bonded at any substitutable position. "Heterocyclic" may be referred to as "heterocycle" or "heterocyclyl " .
"Heteroaryl" means an aromatic heterocyclic group which has at least one of nitrogen, oxygen, and/or sulfur atoms in the ring and may be bonded at any substitutable position, wherein the ring member atoms of the heteroaryl besides carbon atoms include 1, 2, 3 or 4 heteroatoms selected from N, 0 and S .
The following shows specific examples of each group as used in this specification.
Examples of halogen include, but are not particularly limited to, fluorine, chlorine, bromine, iodine, and the like.
Examples of C1-C12 alkyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, neopentyl, 1, 1-dimethylpropan-l-yl, n-hexyl, 1-ethylpentyl, 2-ethylhexyl , and the like.
Examples of C1-C12 haloalkyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkyl substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethyl , chloromethyl , bromomethyl, iodomethyl, difluoromethyl, 2, 2-difluoroethyl, trifluoromethyl,
2.2.2-trifluoroethyl, pentafluoroethyl, 3, 3, 3-trifluoropropyl, heptafluoroisopropyl , 4,4, 4-trifluorobutyl, heptafluoroisobutyl , and the like.
Examples of C1-C12 alkoxy include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, n-pentyloxy, isopentyloxy, neopentyloxy,
1 , 1-dimethylpropan-l-yloxy, n-hexyloxy, 1-ethylpentyloxy,
2-ethylhexyloxy, and the like.
Examples of C1-C12 haloalkoxy include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, 2 , 2-difluoroethoxy, trifluoromethoxy,
2.2.2-trifluoroethoxy, pentafluoroethoxy, 3, 3, 3-trifluoropropoxy, heptafluoroisopropoxy, 4,4, 4-trifluorobutoxy, heptafluoroisobutoxy, and the like.
Examples of C1-C12 alkoxy C1-C12 alkyl include, but are not particularly limited to, alkoxyalkyl in which the C1-C12 straight-chain or branched-chain alkyl is substituted with a C1-C12 straight-chain or branched-chain alkoxy, such as methoxymethyl , ethoxymethyl , n-propoxymethyl , isopropoxymethyl , n-butoxymethyl , isobutoxymethyl , sec-butoxymethyl , tert-butoxymethyl , methoxyethyl , ethoxyethyl, methoxy-n-propyl , methoxy-n-butyl , and the like.
Examples of C1-C12 haloalkoxy C1-C12 alkyl include, but are not particularly limited to, straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 8, halogen atoms, such as fluoromethoxymethyl , chloromethoxymethyl , bromomethoxymethyl , iodomethoxymethyl , difluoromethoxymethyl, trifluoromethoxymethyl, 2, 2, 2-trifluoroethoxymethyl, and the like . Examples of C3-C12 cycloalkyl include, but are not particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
Examples of C3-C12 cycloalkylcarbonyl , include, but are not particularly limited to, cyclopropylcarbonyl , cyclobutylcarbonyl , cyclopentylcarbonyl , cyclohexylcarbonyl and the like.
Examples of C1-C12 alkylcarbonyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylcarbonyl groups, such as methylcarbonyl (acetyl), ethylcarbonyl (propionyl), n-propylcarbonyl (butyryl), isopropylcarbonyl ( isobutyryl ) , n-butylcarbonyl (valeryl), isobutylcarbonyl ( isovaleryl ) , sec-butylcarbonyl , tert-butylcarbonyl , n-pentylcarbonyl , isopentylcarbonyl , neopentylcarbonyl , (1, 1-dimethylpropan-l-yl ) carbonyl,
( 1-ethylpentyl ) carbonyl , ( 2-ethylhexyl ) carbonyl , and the like.
Examples of C1-C12 haloalkylcarbonyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylcarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylcarbonyl , chloromethylcarbonyl , bromomethylcarbonyl , iodomethylcarbonyl , dichloromethylcarbonyl , trichloromethylcarbonyl, difluoromethylcarbonyl , trifluoromethylcarbonyl, chiorodifluoromethylcarbonyl , bromodifluoromethylcarbonyl , dichlorofluoromethylcarbonyl , 2,2, 2-trichloroethylcarbonyl , 2,2, 2-trifluoroethylcarbonyl , pentafluoroethylcarbonyl , and the like.
Examples of C1-C12 alkoxycarbonyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxycarbonyl, such as methoxycarbonyl , ethoxycarbonyl , n-propoxycarbonyl , isopropoxycarbonyl , n-butoxycarbonyl , isobutoxycarbonyl , sec-butoxycarbonyl , tert-butoxycarbonyl , n-pentyloxycarbonyl , isopentyloxycarbonyl , neopentyloxycarbonyl , (1, 1-dimethylpropan-l-yloxy) carbonyl, n-hexyloxycarbonyl ,
( 1-ethylpentyloxy) carbonyl , ( 2-ethylhexyloxy) carbonyl , and the like . Examples of Ci-Ci2 haloalkoxycarbonyl include, but are not particularly limited to, Ci-Ci2 straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl , chloromethoxycarbonyl , bromomethoxycarbonyl , iodomethoxycarbonyl , dichioromethoxycarbonyl, trichloromethoxycarbonyl , difluoromethoxycarbonyl , trifluoromethoxycarbonyl ,
2,2, 2-trifluoroethoxymethyl , pentafluoroethoxycarbonyl ,
3.3.3-trifluoropropoxycarbonyl , 4,4, 4-trifluorobutoxycarbonyl , heptafluoroisopropoxycarbonyl , and the like.
Examples of C1-C12 cyanoalkyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkyl substituted with a cyano group, such as cyanomethyl, cyanoethyl, cyano-n-propyl , cyano-isopropyl , cyano-n-butyl , cyano-isobutyl , cyano-sec-butyl , cyano-tert-butyl , cyano-n-hexyl , and the like.
Examples of C1-C12 cyanoalkoxy include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkoxy substituted with a cyano group, such as cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano-hexyloxy, and the like.
Examples of C2-Ci2 alkenyl include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, and the like.
Examples of C2-Ci2 haloalkenyl include, but are not particularly limited to, 2 , 2-dichlorovinyl , 2 , 2-dibromovinyl , 2, 2-difluorovinyl, 3, 3-difluoro-2-allyl, 4, 4-difluoro-3-butenyl ,
4.4.4-trifluoro-2-butenyl, and the like.
Examples of C2-Ci2 alkynyl include, but are not particularly limited to, ethynyl, 2-propynyl (propargyl), l-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, and the like.
Examples of C2-Ci2 haloalkynyl include, but are not particularly limited to, fluoroethynyl , bromoethynyl , chloroethynyl , iodoethynyl, 3, 3, 3-trifluoro-l-propynyl, and the like .
Examples of C1-C12 alkylsulfinyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyl, such as methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, and the like .
Examples of C1-C12 haloalkylsulfinyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfinyl, chloromethylsulfinyl, bromomethylsulfinyl , iodomethylsulfinyl , dichloromethylsulfinyl , trichloromethylsulfinyl, difluoromethylsulfinyl , trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl , dichlorofluoromethylsulfinyl , 2,2, 2-trichloroethylsulfinyl , 2,2, 2-trifluoroethylsulfinyl, pentafluoroethylsulfinyl, and the like.
Examples of C1-C12 alkylsulfonyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, and the like .
Examples of C1-C12 haloalkylsulfonyl include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfonyl, chloromethylsulfonyl, bromomethylsulfonyl , iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl, difluoromethylsulfonyl , trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl , dichlorofluoromethylsulfonyl , 2,2, 2-trichloroethylsulfonyl , 2,2, 2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl, and the like. Examples of C1-C12 alkylthio include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylthio, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, and the like.
Examples of C1-C12 haloalkylthio include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylthio substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio, dichloromethylthio, trichloromethylthio, difluoromethylthio, trifluoromethylthio, chiorodifluoromethylthio, bromodifluoromethylthio, dichlorofluoromethylthio, 2,2, 2-trichloroethylthio,
2.2.2-trifluoroethylthio, pentafluoroethylthio, and the like.
Examples of C2-Ci2 alkenyloxy include, but are not particularly limited to, vinyloxy, 1-propenyloxy, isopropenyloxy, allyloxy,
2-butenyloxy, 3-butenyloxy, 1-methylallyloxy, and the like.
Examples of C2-Ci2 haloalkenyloxy include, but are not particularly limited to, 2 , 2-dichlorovinyloxy,
2.2-dibromovinyloxy, 2, 2-difluorovinyloxy,
3.3-difluoro-2-allyloxy, 4, 4-difluoro-3-butenyloxy,
4 , 4 , 4-trifluoro-2-butenyloxy, and the like.
Examples of C2-Ci2 alkynyloxy include, but are not particularly limited to, ethynyloxy, 2-propynyloxy, l-methyl-2-propynyloxy,
1 , l-dimethyl-2-propynyloxy, 1-butynyloxy, 2-butynyloxy,
3-butynyloxy, and the like.
Examples of C2-Ci2 haloalkynyloxy include, but are not particularly limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3, 3, 3-trifluoro-l-propynyloxy, and the like.
Examples of Ci-Ci2 alkylsulfonyloxy include, but are not particularly limited to, Ci-Ci2 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyloxy, ethylsulfonyloxy, n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and the like.
Examples of C1-C12 alkylsulfinyloxy include, but are not particularly limited to, C1-C12 straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy, ethylsulfinyloxy, n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and the like.
Examples of substituted or unsubstituted amino include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino, and the like. Examples of the alkyl include C1-C12 alkyl mentioned above, and the like. Examples of the acyl include C1-C12 alkoxycarbonyl , haloalkoxycarbonyl , arylcarbonyl mentioned above, and the like.
Examples of aryl include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
Examples of aryl C1-C12 alkyl include, but are not particularly limited to, benzyl, phenylethyl, phenyl-n-propyl and the like. These aryl C1-C12 alkyl can be further substituted at the alkyl part or the aryl part, or both.
Examples of aryloxy include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.
Examples of aryl C1-C12 alkoxy include, but are not particularly limited to, benzyloxy, phenylethoxy, phenyl-n-propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and the like .
Examples of heteroaryloxy include, but are not particularly limited to, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, and the like .
Examples of heteroaryl C1-C12 alkoxy include, but are not particularly limited to, pyridinylmethoxy, pyridinylethoxy, pyrimidinylethoxy, pyrazolylmethoxy, and the like.
Examples of arylsulfonyl include, but are not particularly limited to, phenylsulfonyl, 1 -naphthylsulfonyl, 2-naphthylsulfonyl, and the like.
Examples of arylsulfinyl include, but are not particularly limited to, phenylsulfinyl, 1 -naphthylsulfinyl, 2-naphthylsulfinyl, and the like.
Examples of heteroaryl include, but are not particularly limited to, thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl , pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl , triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, isoindolyl, indazolyl, quinazolinyl , carbazolyl, benzoxazolyl , benzisoxazolyl , benzothiazolyl , benzisothiazolyl , benzimidazolyl , quinolinyl, isoquinolinyl , pyridoindolyl , cinnolinyl, phthalazinyl , quinoxalinyl , purinyl, phenothiazinylfuranyl, benzofuranyl , chromanyl, benzothienyl, and the like.
All the Aryls and Heteroaryls mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
Examples of a heterocyclic group include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl, dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl , oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl , isoxazolinyl , thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl , isothiazolinyl , pyrazolyl, pyrazolidinyl , imidazolyl, imidazolinyl , imidazolidinyl , oxadiazolyl, oxadiazolinyl , thiadiazolinyl , triazolyl, triazolinyl, triazolidinyl , tetrazolyl, tetrazolinyl , pyridyl, dihydropyridyl, tetrahydropyridyl , piperidyl, oxazinyl, dihydroxazinyl , morpholino, thiazinyl, dihydrothiazinyl , thiamorpholino, pyridazinyl, dihydropyridazinyl , tetrahydropyridazinyl , hexahydropyridazinyl , oxadiazinyl, dihydrooxadiazinyl , tetrahydrooxadiazinyl , thiadiazolyl, thiadiazinyl , dihydrothiadiazinyl , tetrahydrothiadiazinyl , pyrimidinyl , dihydropyrimidinyl , tetrahydropyrimidinyl , hexahydropyrimidinyl , pyrazinyl, dihydropyrazinyl , tetrahydropyrazinyl , piperazinyl, triazinyl, dihydrotriazinyl , tetrahydrotriazinyl , hexahydrotriazinyl , tetrazinyl, dihydrotetrazinyl , indolyl, indolinyl, isoindolyl, indazolyl, quinazolinyl , dihydroquinazolyl , tetrahydroquinazolyl , carbazolyl, benzoxazolyl , benzoxazolinyl , benzisoxazolyl , benzisoxazolinyl , benzothiazolyl , benzisothiazolyl , benzisothiazolinyl , benzimidazolyl , indazolinyl, quinolinyl, dihydroquinolinyl , tetrahydroquinolinyl , isoquinolinyl , dihydroisoquinolinyl , tetrahydroisoquinolinyl, pyridoindolyl , dihydrobenzoxazinyl , cinnolinyl, dihydrocinnolinyl , tetrahydrocinnolinyl , phthalazinyl, dihydrophthalazinyl , tetrahydrophthalazinyl , quinoxalinyl , dihydroquinoxalinyl , tetrahydroquinoxalinyl , purinyl, dihydrobenzotriazinyl , dihydrobenzotetrazinyl , phenothiazinylfuranyl, benzofuranyl , chromanyl, benzothienyl , and the like.
These heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group.
All the heterocyclics mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
Examples of a substituent or substituents in "substituted" include: but are not particularly limited to, halogen, nitro, cyano, hydroxyl, formyl, C1-C12 alkyl, C1-C12 haloalkyl, C1-C12 alkoxy, C1-C12 haloalkoxy, C1-C12 alkoxy C1-C12 alkyl, C1-C12 haloalkoxy C1-C12 alkyl, C3-C12 cycloalkyl, C3-C12 cycloalkyl C1-C12 alkyl, C1-C12 alkylcarbonyl , C1-C12 haloalkylcarbonyl , arylcarbonyl , aryloxycarbonyl , C1-C12 alkoxycarbonyl , C1-C12 haloalkoxycarbonyl , C1-C12 cyanoalkyl, C1-C12 cyanoalkoxy, C2-C12 alkenyl, C2-C12 haloalkenyl, C2-C12 alkynyl, C2-C12 haloalkynyl, C1-C12 alkylsulfonyl, C1-C12 haloalkylsulfonyl, C1-C12 alkylsulfinyl, C1-C12 haloalkylsulfinyl, C1-C12 alkylthio, C1-C12 haloalkylthio, C3-C12 cycloalkylsulfonyl, C3-C12 cycloalkylsulfinyl, C3-C12 cycloalkylthio, C3-C122 cycloalkyl C1-C12 alkylsulfonyl, C3-C12 cycloalkyl C1-C12 alkylsulfinyl, C3-C12 cycloalkyl C1-C12 alkylthio, C1-C12 alkoxy C1-C12 alkylsulfonyl, C1-C12 alkoxy C1-C12 alkylsulfinyl, C1-C12 alkoxy C1-C12 alkylthio, C2-Ci2 alkenyloxy, C2-Ci2 haloalkenyloxy, C2-Ci2 alkynyloxy, C2-Ci2 haloalkynyloxy, Ci-Ci2 alkylsulfonyloxy, Ci-Ci2 haloalkylsulfonyloxy, Ci-Ci2 alkylsulfinyloxy, Ci-Ci2 haloalkylsulfinyloxy, OCN, SCN, SF5, substituted or unsubstituted amino, aryl, aryl Ci-Ci2 alkyl, aryloxy, aryl Ci-Ci2 alkoxy, arylsulfonyl, arylsulfinyl, arylthio, aryl Ci-Ci2 alkylsulfonyl, aryl Ci-Ci2 alkylsulfinyl, aryl Ci-Ci2 alkylthio, heterocyclic, heterocyclic Ci-Ci2 alkyl, heterocyclic oxy, and the like .
Of these, preferable substituents are halogen, nitro, cyano, Ci-Ci2 alkyl, 02-0i2 haloalkyl, 02-0i2 alkoxy, 02-0i2 haloalkoxy, 02-0i2 alkylsulfonyl, Ci-Ci2 alkoxycarbonyl , Ci-Ci2 haloalkylsulfonyl, Ci-Ci2 alkylsulfinyl, 02-0i2 haloalkylsulfinyl, 02-0i2 alkylthio, Ci-Ci2 haloalkylthio, substituted or unsubstituted amino, aryl, and heterocyclic, and more preferable substituents are fluorine, chlorine, bromine, iodine, cyano, nitro, methyl, ethyl, C(CH3)3 trifluoromethyl, methoxy, ethoxy, trifluoromethoxy, OCH2CF3 C02CH3, C02CH2CH3, or S02CH3.
Preferable substituted aryl groups are halogen-substituted aryl, dihalogen-substituted aryl, Ci-Ci2 alkyl-substituted aryl, Ci-Ci2 haloalkyl-substituted aryl, halogen and Ci-Ci2 haloalkyl-substituted aryl, Ci-Ci2 alkoxy-substituted aryl, Ci-Ci2 haloalkoxy-substituted aryl, and Ci-Ci2 alkylthio-substituted aryl . More preferable substituted aryl groups are chlorine-substituted aryl, dichlorine-substituted aryl, fluorine-substituted aryl, difluorine-substituted aryl, trifluoromethyl-substituted aryl, methyl-substituted aryl, chlorine- and trifluoromethyl-substituted aryl, trifluoromethoxy-substituted aryl, methoxy-substituted aryl, trifluoromethoxy-substituted aryl, and methylthio-substituted aryl.
Preferable substituted heteroaryl groups are halogen-substituted heteroaryl, Ci-Ci2 alkyl-substituted heteroaryl, Ci-Ci2 haloalkyl-substituted heteroaryl, halogen and Ci-Ci2 haloalkyl-substituted heteroaryl, Ci-Ci2 alkoxy-substituted heteroaryl, Ci-Ci2 haloalkoxy-substituted heteroaryl, and Ci-Ci2 alkylthio-substituted heteroaryl. More preferable substituted heteroaryl groups are chlorine-substituted heteroaryl, fluorine-substituted heteroaryl, trifluoromethyl-substituted heteroaryl, chlorine- and trifluoromethyl-substituted heteroaryl, trifluoromethoxy-substituted heteroaryl, and methoxy-substituted heteroaryl, and methylthio-substituted heteroaryl.
Preferable substituted heterocyclic groups are halogen-substituted heterocyclic, C1-C12 alkyl-substituted heterocyclic, C1-C12 haloalkyl-substituted heterocyclic, C1-C12 alkoxy-substituted heterocyclic, C1-C12 haloalkoxy-substituted heterocyclic, and C1-C12 alkylthio-substituted heterocyclic. More preferable substituted heterocyclic groups are chlorine-substituted heterocyclic, fluorine-substituted heterocyclic, trifluoromethyl-substituted heterocyclic, trifluoromethoxy-substituted heterocyclic, methoxy-substituted heterocyclic, and methylthio-substituted heterocyclic.
The salts of the compounds represented by Formula (1) may be any type of salts as long as they are agriculturally acceptable. Examples of the salts include inorganic acid salts, such as a hydrochloride salt, a sulfate salt, a nitrate salt, and the like; organic acid salts, such as an acetate salt, a methanesulfonic acid salt, and the like; alkali metal salts, such as a sodium salt, a potassium salt, and the like; alkaline earth metal salts, such as a magnesium salt, a calcium salt, and the like; quaternary ammonium salts, such as dimethylammonium, triethylammonium, and the like; and the like.
Xi represents C-Rs or N, X2 represents C-R9 or N, X3 represents C-R10 or N. However, when Xi represents a nitrogen atom, X2 and X3 represent C-R9 and C-R10, respectively; when X2 represents a nitrogen atom, Xi and X3 represent C-Rs and C-R10, respectively; and when X3 represents a nitrogen atom, X2 and X2 represent C-Rs and C-Rg, respectively .
Among compounds (1) of the present disclosure, a preferable compound is a compound in which Q represents an oxygen atom, or a sulfur atom, and a more preferable compound (1) is a compound in which Q represents an oxygen atom.
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R.6 and R7 each independently represent hydrogen, halogen, or C1-C12 alkyl, and a more preferable compound (1) is a compound in which R6 and R7 each independently represent hydrogen, chlorine, or methyl.
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R represents substituted or unsubstituted aryl or C1-C12 alkyl, and a more preferable compound (1) is a compound in which R represents halogen, alkyl, haloalkyl, alkoxy, or haloalkoxy-substituted aryl, unsubstituted aryl or methyl .
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R2 represents hydrogen, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl , and a more preferable compound (1) is a compound in which Ri represents hydrogen, unsubstituted C2-Ci2 alkenyl, unsubstituted C2-Ci2 alkynyl, unsubstituted Ci-Ci2 alkylcarbonyl, unsubstituted C3-Ci2 cycloalkylcarbonyl, substituted or unsubstituted Ci-Ci2 alkoxycarbonyl, unsubstituted aryloxycarbonyl, or substituted or unsubstituted arylcarbonyl.
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R2 represents hydrogen, substituted or unsubstituted Ci-Ci2 alkyl, and a more preferable compound (1) is a compound in which R2 represents hydrogen, methyl or ethyl.
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R3 represents substituted or unsubstituted Ci-Ci2 alkyl, and a more preferable compound (1) is a compound in which R3 represents methyl, ethyl or tri fluoromethyl . Among compounds (1) of the present disclosure, a preferable compound is a compound in which R4 and R5 each independently represent hydrogen, substituted or unsubstituted C1-C12 alkyl, and a more preferable compound (1) is a compound in which R4 and R5 each independently represent hydrogen or methyl .
Among compounds (1) of the present disclosure, a preferable compound is a compound in which Xlf X2 and X3 each independently represent C-R8 , C-Rg , C-R10 , or N, and a more preferable compound (1) is a compound in which X4, X2 and X3 each independently represent C-R8 , C-Rg , and C-R10 . However, when X4 represents a nitrogen atom, X2 and X3 represent C-Rg and C-R10 , respectively. When X2 represents a nitrogen atom, X4 and X3 represent C-Rs and C-R10, respectively. When X3 represents a nitrogen atom, X4 and X2 represent C-Rs and C-Rg , respectively .
Among compounds (1) of the present disclosure, a preferable compound is a compound in which R8 , Rg and Rio each independently represent hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, and a more preferable compound (1) is a compound in which Re , Rg and Rio represent independently of each other hydrogen, chloro, methyl or ethyl .
Of these, a more preferable compound of the present disclosure is a compound or a salt thereof in which
Q represents an oxygen atom;
R is halogen-, alkyl-, haloalkyl-, alkoxy-, or haloalkoxy-substituted aryl; unsubstituted aryl; or methyl;
Ri is hydrogen, unsubstituted C2-Ci2 alkenyl, unsubstituted C2-Ci2 alkynyl, unsubstituted Ci-Ci2 alkylcarbonyl , unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl ;
R2 is hydrogen, or substituted or unsubstituted Ci-Ci2 alkyl;
R3 is substituted or unsubstituted Ci-Ci2 alkyl;
R4 is hydrogen, or substituted or unsubstituted Ci-Ci2 alkyl;
R5 is hydrogen or methyl;
Xi represents C-R8 or N;
X2 represents C-Rg ; X3 represents C-Rio;
Rs is hydrogen, C1-C12 alkyl or halogen;
R9 is hydrogen, C1-C12 alkyl or halogen;
Rio is hydrogen, C1-C12 alkyl or halogen.
A particularly preferable compound of the present disclosure is a compound or a salt thereof in which
Q represents an oxygen atom;
Rg is hydrogen;
R7 is hydrogen;
R is substituted or unsubstituted aryl, or C1-C12 alkyl;
Ri is hydrogen, unsubstituted C2-Ci2 alkenyl, unsubstituted C2-Ci2 alkynyl, unsubstituted Ci-Ci2 alkylcarbonyl , unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , unsubstituted aryloxycarbonyl , or substituted or unsubstituted arylcarbonyl;
R2 is hydrogen, methyl or ethyl;
R3 is methyl, ethyl or trifluoromethyl ;
R4 is hydrogen or methyl;
R5 is hydrogen, or substituted or unsubstituted Ci-Ci2 alkyl;
X2 represents C-R3 or N;
X2 represents C-R9;
X3 represents C-Rio;
Rs is hydrogen, chloro, methyl or ethyl;
R9 is hydrogen, chloro, methyl or ethyl;
Rio is hydrogen, chloro, methyl or ethyl.
Another more preferable compound of the present disclosure is a compound or a salt thereof in which
Q represents an oxygen atom or a sulfur atom, preferably an oxygen atom;
R is Cg aryl substituted with halogen, Ci-Cg alkyl, Ci-Cg haloalkyl, Ci-Cg alkoxy, Ci-Cg haloalkoxy, and/or Ci-Cg haloalkylsulfonyl ;
Ri is hydrogen, unsubstituted Ci-Cg alkoxycarbonyl, unsubstituted Ci-Cg alkylcarbonyl, unsubstituted Ci-Cg haloalkylcarbonyl , unsubstituted C3-Cg cycloalkylcarbonyl, or unsubstituted Cg arylcarbonyl, or Ci-Cg haloalkyl-substituted Cg arylcarbonyl;
R2 is Ci-C3 alkyl;
R3 is hydrogen or Ci-C3 alkyl; R.4 is hydrogen or C1-C3 alkyl;
R5 is hydrogen or C1-C3 alkyl;
Xi represents C-Rs;
X2 represents C-Rg;
X3 represents C-Ri0;
R8 is hydrogen, C1-C3 alkyl, or fluorine;
Rg is hydrogen or C1-C3 alkyl;
Rio is hydrogen or C1-C3 alkyl.
A particularly preferable compound of the present disclosure is a compound or a salt thereof in which
Q represents an oxygen atom or a sulfur atom, preferably an oxygen atom;
R is Ce aryl substituted with fluorine, chlorine, bromine, C1-C3 alkyl, C1-C3 haloalkyl, and/or C1-C3 haloalkoxy;
Ri is hydrogen, unsubstituted Ci-C6 alkoxycarbonyl , unsubstituted Ci-C6 alkylcarbonyl , unsubstituted Ci-C6 haloalkylcarbonyl , or unsubstituted cyclopropylcarbonyl ;
R2 is methyl;
R3 is ethyl;
R4 is hydrogen, methyl, or ethyl;
R5 is hydrogen, methyl, or ethyl;
Xi represents C-Rs;
X2 represents C-Rg;
X3 represents C-R10;
Rs is hydrogen, methyl, or ethyl;
Rg is methyl;
Rio is hydrogen.
The present disclosure also incorporates preparation of the said novel substituted pyrazole compounds or a salt thereof as represented by formula (1) . There are various known synthesis procedures for the preparation of the compounds of the present disclosure. Hereinafter, the synthesis procedure for one type of compounds of the present disclosure will be described and shown in Scheme- 1 . However, the preparation of the novel substituted pyrazole compounds or a salt thereof is not limited to this method. Scheme- 1
Figure imgf000036_0001
wherein R, Ri, R2, R3, Xi, X2, X3 and Q are as defined above while LG and LGi are any of known leaving groups.
Step 1-1
This step provides a method of preparing compound (III) by the reaction of compound
Figure imgf000036_0002
with compound (II)
[Reaction Scheme 1-1]
Figure imgf000036_0003
Solvent , reflux
(I0> Step 1-1 (III)
Wherein, R is as defined above.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: fatty acid or alicyclic hydrocarbon-based solvents, such as n-hexane, cyclohexane, n-heptane, and the like; aromatic hydrocarbon-based solvents, such as benzene, chlorobenzene, toluene, xylene, and the like; halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ester solvents, such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; sulfoxide-based solvents, such as dimethyl sulfoxide, sulfolane and the like; tetrahydrofuran, A/,A/-dimethylformamide; and protic solvents like methanol, ethanol, isopropanol, tert-butanol or water, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound (I) .
The amount of compound (II) to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 1.5 mol, per 1 mol of the compound (I) .
The reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 60 minutes to 10 hours.
Step 1 -2
In this step the compound (III) is formylated to produce compound (IV) .
[Reaction Scheme 1-2]
Figure imgf000037_0001
(III) (IV)
Step 1-2
Wherein, R is as defined above.
Formylation can be done by any known procedures. Some examples of the formylation include, but are not limited to, using POCI3-DMF system or using hexamethylenetetramine. The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF), 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and trifluoroacetic acid, dimethyl sulfoxide, sulfolane, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (III) .
The amount of phosphorous oxychloride to be used is usually 1.0 to 20.0 mol , preferably 1.0 to 10.0 mol , per 1 mol of the compound
(III) . Similarly, the amount of hexamethylenetetramine to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (III) .
The reaction temperature varies depending on the starting compound, the reaction reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 50 to 120°C.
The reaction time varies depending on the compound, the reaction reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 1 to 10 hours.
Step 1 -3
This step consists of two phases. In the first phase, compound
( IV) is treated with a suitable peracid to produce one intermediate . In the second phase, this intermediate is hydrolyzed to produce the compound (V) .
[Reaction Scheme 1-3]
(i) Peracid, solvent
Figure imgf000038_0001
(V)
Wherein, R and Q is as defined above.
In the first phase any known peracid can be used, examples include but are not limited to, m-chloroperbenzoic acid, hydrogen peroxide, peracetic acid, etc. The amount of the peracid is usually 1.0 to 20.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (IV) .
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and dimethyl sulfoxide and sulfolane. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (IV) .
In the second phase, the hydrolysis of the intermediate can be done by any known procedure, examples include, but are not limited to, using an acid in protic solvents, or using a base in appropriate solvent. For acidic conditions, any well-known acid like hydrochloric acid, sulfuric acid, etc., can be used while in basic conditions, any known base, such as organic bases like triethylamine or inorganic bases like sodium hydroxide can be used.
The amount of the acid or base to be used is usually 1.0 to 20.0 mol, preferably 1.0 to 5.0 mol, per 1 mol of the compound (IV) .
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; dimethyl sulfoxide or sulfolane; and protic solvents like methanol, ethanol, water, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (IV) .
The reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 6 hours to 18 hours.
Step 1 -4
This step consists of reactions between compound (V) and compound (VI) in the presence of a base and solvent to produce the compound (VII) .
[Reaction Scheme 1-4]
Figure imgf000040_0001
Wherein, R, Xi, X2, X3 and Q are as defined above. LG represents any suitable leaving group, such as halogen, O-mesylates, O-sulfonates, O-tosylates, etc.
The base used for the above mentioned reaction is not particularly limited. As for the base, any conventionally known base can widely be used, and examples of the base include: alkali metal carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; alkali metal hydroxides, such as sodium hydroxide, potassium hydroxide, and the like; inorganic bases including alkali metal hydrides, such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases, such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine pyridine, piperidine, and the like. Any separate one of these bases or a combination of two or more types thereof can be used.
The amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 1.5 mol, per 1 mol of the compound (V) . The aforementioned reaction is performed in an appropriate solvent. No limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; amide-based solvents, such as tetrahydrofuran (THF) , 1,4-dioxane; acetonitrile; N, N-dimethylformamide (DMF) , N, N-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and dimethyl sulfoxide, sulfolane, and protic solvents, such as methanol, ethanol, water, etc. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (V) .
The reaction temperature varies depending on the starting compound, the reaction reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 100°C.
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 60 minutes to 12 hours.
Step 1 -5
This step involves the reduction of nitro group (N02) present in the compound (VII) to produce amino group (NH2) of the compound (VIII) .
[Reaction Scheme 1-5]
K-N'NΊ xfYN¾ Reduction
'b Qv'J>* *Y2'Xs Step 1-5
(VII)
Figure imgf000041_0001
Wherein, R, Xi, X2, X3 and Q are as defined above.
For the aforementioned reaction, various conventional methods are known and can widely be used. Some examples of the methods include but are not limited to: Palladium charcoal (Pd-C) under hydrogen atmosphere in protic solvents like methanol, ethanol; Raney Nickel (Raney Ni) under hydrogen atmosphere in protic solvents like methanol, ethanol; Iron powder in acetic acid; Zinc dust in acetic acid; sodium sulfide (Na2S) in ethanol; Zinc dust, ammonium chloride and a mixture of solvents like THF-MeOH, THF-EtOH; Stannous chloride in hydrochloric acid, etc.
The reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is usually from -40°C to the reflux temperature in the reaction system, preferably from 0 to 90°C.
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 5 minutes to 48 hours, preferably from 60 minutes to 6 hours.
Step 1 - 6
This step is a method of preparing the compound (X) from the reactions of compound (VIII) and compound (IX) in the presence of a catalyst and a suitable solvent.
[Reaction Scheme 1-6]
Figure imgf000042_0001
Wherein, R, R2, R3, Xi, X2, X3 and Q are as defined above.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: benzene, chlorobenzene, toluene, xylene, 1 , 2-dichloroethane, diphenyl ether, acetonitrile, A/,A/-dimethylformamide (DMF) , A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone, polyphosphoric acid Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound represented by formula (VIII) .
The aforementioned reaction can be performed under the presence of a catalyst. There are various conventional catalysts which can be used for this reaction and some examples of these catalysts include: trifluoroacetic acid; hydrochloric acid; sulfuric acid; p-toluene sulfonic acid; boron trifluoride etherate (BF3-Et20) ; aluminium chloride (AICI3) ; iron chloride (FeCls); titanium chloride (Tί014) ; tin chloride (SnCl4) .
The amount of the acid to be used is usually 1.0 to 5 mol, preferably 0.05 mol, per 1.5 mol of the compound (VIII) .
The amount of the acetoacetate (IX) to be used is usually 1.0 to 10.0 mol, preferably 1.0 to 5.0 mol of the compound (VIII) .
The reaction temperature varies depending on the type of the starting compound, the reagent, and the solvent and generally from 0°C to 2000 C .
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 2 hours to 16 hours.
Step 1 -7
This step produces the compound ( 1 ) by the treatment of compound (X) with compound (XI) .
[Reaction Scheme 1-7]
Figure imgf000043_0001
Wherein, R, Ri, R2, R3, Rg, Rio, Xi, X2, X3 and Q are as defined above. LGi represents any suitable leaving group, such as halogen, O-mesylates, O-sulfonates, O-tosylates, etc.
The aforementioned reaction is performed in an appropriate solvent or without any solvent. When the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction. Examples of such a solvent include: aromatic hydrocarbon-based solvents, such as benzene, chlorobenzene, toluene, xylene, and the like; halogenated hydrocarbon-based solvents, such as methylene chloride, 1 , 2-dichloroethane, chloroform, and carbon tetrachloride, and the like; ether-based solvents, such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and the like; ester solvents, such as methyl acetate, ethyl acetate, and the like s; amide-based solvents, such as acetonitrile; A/,A/-dimethylformamide (DMF) ,
A/,A/-dimethylacetamide, A/-methyl-2-pyrolidone and the like; and ketone-based solvents, such as acetone, methyl ethyl ketone, cyclohexanone, and the like; and dimethyl sulfoxide. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
The amount of the solvent to be used is usually 0.5 to 20 liters, preferably 0.5 to 10 liters, per 1 mol of the compound represented by formula (X) .
A base used for the above mentioned reaction is not particularly limited. As for the base, a conventionally known base can widely be used, and examples of the base include: alkali metal carbonates, such as sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like; metal hydroxides, such as sodium hydroxide, potassium hydroxide, and the like alkali; inorganic bases including alkali metal hydrides, such as sodium hydride and potassium hydride, and the like; alkali metal alkoxides, such as sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like; organic bases, such as pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylamine pyridine, piperidine, and the like; and preferably pyridine. Any separate one of these bases or a combination of two or more types thereof is used.
The amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 1.1 mol, per 1 mol of the compound (X) , sometimes, when an organic base is used it can serve as a solvent also.
The amount of compound (XI) to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (X) .
The reaction temperature varies depending on the starting compound, the reagent, the solvent and the like, but it is generally from — 10 ° C to boiling point of the solvent.
The reaction time varies depending on the compound, the reagent, the solvent and the reaction temperature and the like, but is usually from 10 minutes to 48 hours, preferably from 1 hour to 12 hours. Each compound represented in Scheme- 1 , after the completion of the reaction can be easily isolated from the reaction mixtures and purified by known isolations and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography.
Compound (1) of the present disclosure may be used as an active ingredient of a pest-controlling agent. Examples of pest-controlling agents include agents (agricultural and horticultural insecticide, miticides, nematicides, or soil insecticides) for controlling pests , mites, nematode, or soil pests that all cause problems in the agricultural and horticultural fields; animal-ectoparasite-controlling agents (e.g., pulicide, ixodicide, and pedivulicide) , and the like.
For use as an active ingredient of a pest-controlling agent, it is possible to use compound (1) of the present disclosure as is with no additional components. However, it is usually preferable to use the compound by it combining with a solid carrier, liquid carrier, or gaseous carrier (propellant) , and optionally with a surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms, 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 disclosure is usually contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt% .
Examples of the solid carrier include mineral carriers, such as pyrophyllite clay, kaolin clay, silicastone clay, talc, diatomaceous earth, zeolite, bentonite, acid clay, active clay, Attapulgus clay, vermiculite, perlite, pumice, white carbon (e.g. synthetic silicic acid or synthetic silicate) , titanium dioxide and the like; vegetable carriers, such as wood flour, corn culm, walnut shell, fruit stone, rice hull, sawdust, wheat bran, soybean flour, powder cellulose, starch, dextrin, saccharide and the like; inorganic salt carriers, such as calcium carbonate, ammonium sulfate, sodium sulfate, potassium chloride and the like; and polymer carriers, such as polyethylene, polypropylene, polyvinyl chloride, polyvinyl acetate, ethylene-vinyl acetate copolymer, urea-aldehyde resin and the like. Examples of the liquid carrier include monohydric alcohols, such as methanol, ethanol, propanol, isopropanol, butanol, cyclohexanol and the like; polyhydric alcohols, such as ethylene glycol, diethylene glycol, propylene glycol, hexylene glycol, polyethylene glycol, polypropylene glycol, glycerine and the like; polyhydric alcohol derivatives, such as propylene type glycol ether and the like; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone, diisobutyl ketone, cyclohexanone, isophorone and the like; ethers, such as ethyl ether, 1,4-dioxane, cellosolve, dipropyl ether, tetrahydrofuran and the like; aliphatic hydrocarbons, such as normal paraffin, naphthene, isoparaffin, kerosene, mineral oil and the like; aromatic hydrocarbons, such as toluene, Cg-Cio alkylbenzene, xylene, solvent naphtha, alkylnaphthalene, high-boiling aromatic hydrocarbon and the like; halogenated hydrocarbons , such as 1 , 2-dichloroethane, chloroform, carbon tetrachloride and the like; esters, such as ethyl acetate, diisopropyl phthalate, dibutyl phthalate, dioctyl phthalate, dimethyl adipate and the like; lactones, such as y-butyrolactone and the like; amides, such as dimethylformamide, diethylformamide, dimethylacetamide, N-alkylpyrrolidinone and the like; nitriles, such as acetonitrile and the like; sulfur compounds, such as dimethyl sulfoxide and the like; vegetable oils, such as soybean oil, rapeseed oil, cottonseed oil , coconut oil, castor oil and the like; and water.
As for the surfactant, there is no particular restriction. However, the surfactant preferably gels or swells in water. Examples include non-ionic surfactants, such as sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, sucrose fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene resin acid ester, polyoxyethylene fatty acid diester, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, polyoxyethylene dialkylphenyl ether, polyoxyethylene alkylphenyl ether-formalin condensate, polyoxyethylene polyoxypropylene block polymer, alkyl polyoxyethylene polypropylene block polymer ether, polyoxyethylene alkyl amine, polyoxyethylene fatty acid amide, polyoxyethylene fatty acid bisphenyl ether, polyalkylene benzyl phenyl ether, polyoxyalkylene styryl phenyl ether, acetylene diol, polyoxyalkylene-added acetylene diol, polyoxyethylene ether type silicone, ester type silicone, fluorine-containing surfactant, polyoxyethylene castor oil, polyoxyethylene hardened castor oil and the like; anionic surfactants, such as alkyl sulfate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl phenyl ether sulfate, polyoxyethylene styryl phenyl ether sulfate, alkylbenzenesulfonic acid salt, ligninsulfonic acid salt, alkylsulfosuccinic acid salt, naphthalenesulfonic acid salt, alkylnaphthalenesulfonic acid salt, naphthalenesulfonic acid-formalin condensate salt, alkylnaphthalenesulfonic acid-formalin condensate salt, fatty acid salt, polycarboxylic acid salt, N-methyl- fatty acid sarcosinate, resin acid salt, polyoxyethylene alkyl ether phosphate, polyoxyethylene alkylphenyl ether phosphate and the like; cationic surfactants including alkyl amine salts, such as laurylamine hydrochloride, stearylamine hydrochloride, oleylamine hydrochloride, stearylamine acetate, stearylaminopropylamine acetate, alkyl trimethyl ammonium chloride, alkyl dimethyl benzalkonium chloride and the like; and ampholytic surfactants, such as betaine type (e.g. dialkyldiaminoethylbetaine or alkyldimethylbenzylbetaine ) , amino acid type (e.g. dialkylaminoethylglycine or alkyldimethylbenzylglycine ) and the like .
As for the binder and the tackifier, examples include carboxymethyl cellulose or a salt thereof, dextrin, water-soluble starch, xanthane gum, guar gum, sucrose, polyvinylpyrrolidone, gum arabic, polyvinyl alcohol, polyvinyl acetate, sodium polyacrylate, polyethylene glycol having an average molecular weight of 6, 000 to 20,000, polyethylene oxide having an average molecular weight of 100,000 to 5,000,000, and natural phospholipid (e.g. cephalinic acid or lecithin) .
As for the thickening agent, examples include water-soluble polymers, such as xanthan gum, guar gum, carboxymethyl cellulose, polyvinylpyrrolidone, carboxyvinyl polymer, acrylic polymer, starch derivative, polysaccharide and the like; and inorganic fine powders, such as high-purity bentonite, white carbon and the like.
As for the coloring agent, examples include, inorganic pigments, such as iron oxide, titanium oxide, Prussian Blue and the like; and organic dyes, such as Alizarine dye, azo dye, metal phthalocyanine dye and the like.
As for the spreader, examples include silicone-based surfactant, cellulose powder, dextrin, processed starch, polyaminocarboxylic acid chelate compound, crosslinked polyvinylpyrrolidone, maleic acid and styrene, methacrylic acid copolymer, half ester between polyhydric alcohol polymer and dicarboxylic acid anhydride, and water-soluble salt of polystyrenesulfonic acid.
As for the sticker, examples include surfactant (e.g. sodium dialkylsulfosuccinate, polyoxyethylene alkyl ether, polyoxyethylene alkylphenyl ether, or polyoxyethylene fatty acid ester) , paraffin, terpene, polyamide resin, polyacrylic acid salt, polyoxyethylene, wax, polyvinyl alkyl ether, alkylphenol-formalin condensate, and synthetic resin emulsion.
As for the anti-freeze, examples include polyhydric alcohol (e.g. ethylene glycol, diethylene glycol, propylene glycol, or glycerine) .
As for the solidification inhibitor, examples include polysaccharide (e.g. starch, alginic acid, mannonse or galactose), polyvinylpyrrolidone, white carbon, ester gum and petroleum resin.
As for the disintegrator, examples include sodium tripolyphosphate, sodium hexametaphosphate, stearic acid metal salt, cellulose powder, dextrin, methacrylic acid ester copolymer, polyvinylpyrrolidone, polyaminocarboxylic acid chelate compound, sulfonated styrene-isobutylene-maleic anhydride copolymer, and starchpolyacrylonitrile graft copolymer.
As for the decomposition inhibitor, examples include, desiccants, such as zeolite, quick lime, magnesium oxide and the like; antioxidants, such as phenol type, amine type, sulfur type, phosphoric acid type and the like; and ultraviolet absorbents, such as salicylic acid type, benzophenone type and the like.
When the present pest control agent contains the above-mentioned additive components, their contents based on mass are selected in a range of ordinarily 5 to 95%, preferably 20 to 90% in the case of carrier (e.g. solid carrier or liquid carrier), ordinarily 0.1 to 30%, preferably 0.5 to 10% in the case of surfactant, and ordinarily 0.1 to 30%, preferably 0.5 to 10% in the case of other additives .
The present pest control agent is used in any formulation selected from dust formulation, dust-granule mixture, granule, wettable powder, water-soluble concentrate, water-dispersible granule, tablet, Jumbo, emulsifiable concentrate, oil formulation, solution, flowable concentrate, emulsion, microemulsion, suspoemulsion, ultra-low volume formulation, microcapsule, smoking agent, aerosol, baiting agent, paste, etc.
In actual use of the formulation, the formulation can be used per se or after dilution with a diluent (e.g. water) in a given concentration. The application of the formulation containing the present compound or its dilution product can be conducted by a method ordinarily used, such as dispersion (e.g. spraying, misting, atomizing, powder dispersion, granule dispersion, on-water-surface dispersion, or inbox dispersion) , in-soil application (e.g. mixing or drenching), on-surface application (e.g. coating, dust coating or covering), immersion, poison bait, smoking and the like. It is also possible to mix the above-mentioned active ingredients with a livestock feed in order to prevent the infestation and growth of injurious pests, particularly injurious insects in the excreta of livestock .
The proportion (mass %) of the active ingredient in the present pest control agent is appropriately selected so as to meet the necessity. The active ingredient is appropriately selected, for example, in the following ranges:
In dust formulation, dust-granule mixture, etc. : 0.01 to 20%, preferably 0.05 to 10%. In granule, etc.: 0.1 to 30%, preferably 0.5 to 20%. In wettable powder, water-dispersible granule, etc.:
1 to 70%, preferably 5 to 50% . In water-soluble concentrate, solution, etc.: 1-95%, preferably 10 to 80%. In emulsifiable concentrate, etc.: 5 to 90%, preferably 10 to 80%. In oil formulation, etc.: 1 to 50%, preferably 5 to 30%. In flowable concentrate, etc.: 5 to 60%, preferably 10 to 50%. In emulsion, microemulsion, suspoemulsion, etc. : 5 to 70%, preferably 10 to 60%. In tablet, bait, paste, etc.: 1 to 80%, preferably 5 to 50%. In smoking agent, etc.: 0.1 to 50%, preferably 1 to 30%. In aerosol, etc.: 0.05 to 20%, preferably 0.1 to 10%.
The formulation is sprayed after dilution in an appropriate concentration, or applied directly.
When the present pest control agent is used after dilution with a diluent, the concentration of active ingredient is generally 0.1 to 5, 000 ppm. When the formulation is used per se, the application amount thereof per unit area is 0.1 to 5,000 g per 1 ha in terms of active ingredient compound; however, the application amount is not restricted thereto. Incidentally, the present pest control agent is sufficiently effective when using the present compound alone as an active ingredient. However, the present pest control agent may be mixed or used in combination, as necessary, with fertilizers and agricultural chemicals, such as insecticide, miticide, nematocide, synergist, fungicide, antiviral agent, attractant, herbicide, plant growth-controlling agent and the like. In this case, a higher effect is exhibited.
Compound (1) of the present disclosure is effectively used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide. Specifically, compound (1) of the present disclosure is effective for controlling pests: for example, aphids, such as green peach aphids, cotton aphids, and the like; diamondback moths, Spodoptera litura, 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; gastropods, such as slugs, snails, and the like; hygiene-harming insects, such as rat mite, cockroaches, houseflies, house mosquitoes, and the like; stored-grain insects, such as angoumois grain moths , adzuki bean weevils , red flour beetles , mealworms, and the like; clothes-harming insects and house- and household-harming insects, such as casemaking clothes moths, black carpet beetles, subterranean termites, and the like; mites, including plant-parasitic 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 the like, and house dust mites, such as Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei, and the like; soil pests, including plant parasitic nematodes, such as root-knot nematodes, cyst nematodes, root-lesion nematodes, white-tip nematodes, strawberry bud nematodes, pine wood nematodes, and the like, and isopods, such as pill bugs, sow bugs, and the like; and the like.
Compound (1) of the present disclosure is characterized by having a particularly excellent fungicidal activity and a broad spectrum of activity. The compound may be used for controlling plant diseases ascribed to various fungal pathogens or resistant fungal pathogens. Examples of such fungal pathogens include those that cause cucumber gray mold, rice plant blast (Pyricularia grisea, millet) , 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.
Examples
The present disclosure describes in more detail with reference to the following preparation examples, formulation example and test examples. However, the present disclosure is not limited to these examples.
Preparation Example 1
Preparation of
2, 3-dimethyl- 6- ( (1- (p-tolyl) -liT-pyrazol-3-yl) oxy) quinolin-4-yl methyl carbonate (compound 1A-156)
(1) 1- (p-tolyl ) -IJJ-pyrazole
1 , 1 , 3 , 3-Tetramethoxypropane (24.90 g, 151.84 mmol, 1.2 equiv.) was added to p-tolylhydrazine hydrochloride (20.0 g, 126.53 mmol) in ethanol (300 mL) at room temperature and the reaction mixture was refluxed for 10 h ("h" means hour(s) .) . All volatiles were removed by distillation. The reaction mixture was diluted with distilled water (100 mL) and extracted with dichloromethane (3 x 100 mL) . The combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to afford 1- (p-tolyl ) -IJJ-pyrazole as a pale yellow oil (18.1 g, crude) . This crude product was used as such in the next step without any further purification.
½ NMR ( CDC13 ) : 7.89 (d, J = 2.0 Hz, 1H), 7.71 (s, 1H), 7.57 (d, J= 8.0 Hz, 2H) , 7.24 (bs, 2H) , 6.45 (bs, 1H) , 2.38 (s, 3H) ; MS (M+l) 159.17.
(2) 1- (p-tolyl) -lff-pyrazole-4-carbaldehyde
POCI3 (87.29 g, 569.33 mmol, 5.0 equiv.) was slowly added to DMF (41.61 g, 569.33 mmol, 5.0 equiv.) at 0 to 10°C under nitrogen atmosphere. This was then stirred for 15 minutes. To this mixture, a solution of 1- (p-tolyl ) -IJJ-pyrazole (18.0 g, 113.86 mmol, 1.0 equiv.) in DMF (25 ml) was slowly added and the reaction mixture was then stirred at 0 to 10°C for 30 minutes. Then the resulting mixture was brought to room temperature and heated to 110°C for 10 h . After cooling to room temperature , the reaction mixture was slowly poured into distilled water and pH of the reaction mixture was made basic by adding 10% NaOH solution to it. The product was then extracted with ethyl acetate (3 x 100 mL) . The combined organic layer was washed with distilled water , dried over sodium sulfate, filtered and concentrated under reduced pressure to give 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 afford 1- (p-tolyl ) -lff-pyrazole-4-carbaldehyde as a light yellow solid (16.5 g, Yield 78%) .
1H NMR (CDC13) : 9.96 (s, 1H) , 8.39 (s, 1H) , 8.15 (s, 1H) , 7.59 (d, J= 8.4 Hz, 2H) , 7.30-7.29 (m, 2H) , 2.41 (s, 3H) ; MS (M+l) 187.13.
(3) 1- (p-tolyl ) -lff-pyrazol-4-ol
m-Chloroperbenzoic acid (8.34 g, 48.36 mmol, 0.9 equiv.) was added to a solution of 1- (p-tolyl ) -lff-pyrazole-4-carbaldehyde (10.0 g, 53.74 mmol, 1.0 equiv.) in chloroform (500 mL) at room temperature under nitrogen atmosphere. The resulting mixture was refluxed for 4h. The reaction mixture was then cooled to room temperature, diluted with DCM (100 mL) , washed with sodium bicarbonate solution (3 x 100 mL) followed by distilled water (3 x 100 mL) , dried over sodium sulfate, filtered and concentrated under reduced pressure to give a crude product . Methanol (50 mL), distilled water (25 mL) , followed by concentrated HC1 (50 mL) was added to the crude product and then the reaction mixture was refluxed for lOh. After cooling to room temperature, all volatiles were distilled-off under reduced pressure . The pH of the reaction mixture was then made neutral by adding sodium bicarbonate solution and extracted with ethyl acetate (3 x 100 mL) . The combined organic layer was washed with distilled water , dried over sodium sulfate, filtered and concentrated under reduced pressure to give 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 afford 1- (p-tolyl ) -lJJ-pyrazol-4-ol as a light brown solid (7.0 g, Yield 75%) .
½ NMR (CDC13) : 7.56 (s, 1H) , 7.46 (d, J= 8.4 Hz, 2H) , 7.41 (s, 1H) , 7.22 (d, J = 8.4 Hz, 2H) , 4.86 (bs, 1H) , 2.36 (s, 3H) ; MS (M+l) 175.13.
(4) 4- ( 4-nitrophenoxy) -1- (p-tolyl) -1H-pyrazole
Cesium carbonate (4.21 g, 12.92 mmol, 1.5 equiv.) and 1-fluoro-4-nitrobenzene (1.21 g, 8.61 mmol, 1.0 equiv.) were sequentially added to a solution of 1- (p-tolyl ) -1H-pyrazol-4-ol (1.5 g, 8.61 mmol, 1.0 equiv.) in DMF (50 mL) at room temperature under nitrogen atmosphere. The resulting mixture was then heated to 70°C for 10 h. The reaction mixture was cooled to room temperature, poured into distilled water (100 mL) and extracted with ethyl acetate (3 x 80 mL) . The combined organic layer was washed with distilled water, dried over sodium sulfate and filtered. This was then concentrated under reduced pressure to afford
4- ( 4-nitrophenoxy) -1- (p-tolyl ) -IH-pyrazole as a yellow solid (1.65 g, crude) . This crude product was used as such in the next step without any further purification.
½ NMR ( CDCI3 ) : 8.23 (d. J = 9.2 Hz, 2H), 7.86 (s, 1H), 7.61 (s, 1H) , 7.55 (d, J= 8.4 Hz, 2H) , 7.28 (d, J= 8.4 Hz, 2H) , 7.15 (d, J= 9.2 Hz, 2H) , 2.40 (s, 3H) ; MS (M+l) 296.16.
(5) 4- ( (1- (p-tolyl) -lff-pyrazol-4-yl ) oxy) aniline
To a solution of 4- (4-nitrophenoxy) -1- (p-tolyl) -lH-pyrazole (1.50 g, 5.08 mmol) in THF:methanol (1:1, 50 mL) and distilled water (5 mL) was added ammonium chloride (2.72 g, 50.83 mmol, 10.0 equiv. ) , followed by portion wise addition of zinc dust (3.32 g, 50.83 mmol, 10 equiv.) at room temperature. The resulting mixture was stirred at room temperature for 2h. The reaction mixture was then diluted with ethyl acetate (100 ml) and filtered through Celite bed. The filtrate was washed distilled water, dried over sodium sulfate, filtered. This was then concentrated under reduced pressure to afford 4- ( ( 1- (p-tolyl ) -lff-pyrazol-4-yl ) oxy) aniline as an off-white solid (1.34 g, crude) . This crude product was used as such in the next step without any further purification.
¾ NMR (CDCI3) : 7.64 (s, 1H) , 7.51-7.49 (m, 3H) , 7.27 (d, J = 8.4 Hz, 2H) , 6.94 (d, J= 8.8 Hz, 2H) , 6.66 (d, J= 8.8 Hz, 2H) , 4.63 (bs, 2H) , 2.37 (s, 3H) ; MS (M+l) 266.22.
(6)
2.3-dimethyl- 6- ( (1- (p-tolyl) -lJJ-pyrazol-4-yl ) oxy) -quinolin-4 (1H ) -one
Ethyl 2-methyl-3-oxobutanoate (0.74 g, 5.14 mmol, l.l equiv.) and p-toluene sulphonic acid (catalytic amount) were sequentially added to a solution of 4- ( (1- (p-tolyl) -lff-pyrazol-4-yl ) oxy) aniline (1.24 g, 4.67 mmol, 1.0 equiv.) in xylene (30 mL) under nitrogen atmosphere. The resulting mixture was refluxed using a Dean-Stark apparatus for 16h. All the volatiles were distilled-off under reduced pressure to give a crude product. The crude product thus obtained was purified by column chromatography on silica gel with a mixture of methanol and dichloromethane as an eluent to afford
2.3-dimethyl- 6- ( (1- (p-tolyl) -1H-pyrazol-4-yl ) oxy) quinolin-4 ( 1H) -one as a brown solid (0.7 g, Yield 43%) .
½ NMR (DMSO-cW : d 11.52 (bs, 1H) , 8.59 (s, 1H) , 7.73-7.71 (m, 3H) , 7.54-7.52 (m, 1H) , 7.47-7.43 (m, 1H) , 7.31 (d, J= 8.0 Hz, 2H) , 7.11 (d, J = 7.6 Hz, 1H) , 2.37 (s, 3H) , 2.34 (s, 3H) , 1.94 (s, 3H) ; MS (M+l) 346.20.
(7) 2, 3-Dimethyl- 6- ( (1- (p-tolyl) -1H-pyrazol-4-yl ) oxy)
quinolin-4-yl methyl carbonate (1A-156)
Potassium tert-butoxide (16 mg, 0.14 mmol, 1.0 equiv.) was added to a mixture of
2.3-dimethyl- 6- ( (1- (p-tolyl) -lH-pyrazol-4-yl) oxy) quinolin-4 ( 1H) -one (50 mg, 0.14 mmol) in THF (10 mL) at room temperature under nitrogen atmosphere and stirred for 15 minutes. Methyl chloroformate (13 mg, 0.14 mmol, 1.0 equiv.) was added to this solution and the reaction mixture was then stirred at room temperature for 10 h. The reaction mixture was then diluted with ethyl acetate (20 mL) and the organic layer was washed with sodium bicarbonate solution followed by distilled water. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to give 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 afford
2.3-dimethyl- 6- ( (1- (p-tolyl) -lff-pyrazol-4-yl ) oxy) quinolin-4-yl methyl carbonate as an off-white solid (40 mg, Yield 68.5%) .
½ NMR ( CDC13 ) : 5 7.99 (d, J = 9.2 Hz, 1H), 7.81 (s, 1H), 7.62 (s, 1H) , 7.55 (d, J= 8.4 Hz, 2H) , 7.49-7.46 (dd, J = 9.2, 2.8 Hz, 1H) , 7.32 (d, J = 2.4 Hz, 1H) , 7.27 (s, 1H) , 7.25 (s, 1H) , 3.91 (s, 3H) , 2.71 (s, 3H) , 2.39 (s, 3H) , 2.30 (s, 3H) ; MS (M+l) 404.51.
Preparation Example 2
Preparation of
2.3-dimethyl- 6- ( (1- (p-tolyl) -lff-pyrazol-4-yl ) oxy) quinolin-4-yl ethyl carbonate (compound 1A-157)
Potassium tert-butoxide (16 mg, 0.14 mmol, 1.0 equiv.) was added to a mixture of
2.3-dimethyl- 6- ( (1- (p-tolyl) -1H-pyrazol-4-yl ) oxy) quinolin-4 ( 1H)
-one (50 mg, 0.14 mmol) in THF (10 ml) at room temperature under nitrogen atmosphere and stirred for 15 minutes. Ethyl chloroformate (15 mg, 0.14 mmol, 1.0 equiv.) was added to this solution and the reaction mixture was then stirred at room temperature for 10 h. The reaction mixture was diluted with ethyl acetate (20 mL) and the organic layer was washed with sodium bicarbonate solution followed by distilled water. The organic layer was dried over sodium sulfate, filtered and concentrated under reduced pressure to give 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 afford
2.3-dimethyl- 6- ( (1- (p-tolyl) -lff-pyrazol-4-yl ) oxy) quinolin-4-yl ethyl carbonate as an off-white solid (40 mg, Yield 66.2%) .
½ NMR ( CDCI3 ) : 5 7.99 (d, J = 9.2 Hz, 1H), 7.82 (s, 1H), 7.62 (s,
1H) , 7.55 (d, J= 8.4 Hz, 2H) , 7.49-7.46 (dd, J= 9.2, 2.8 Hz, 1H) ,
7.30 (d, J = 2.8 Hz, 1H) , 7.27 (s, 1H) , 7.25 (s, 1H) , 4.33-4.28 (q,
J = 7.2 Hz, 2H) , 2.71 (s, 3H) , 2.39 (s, 3H) , 2.30 (s, 3H) , 1.32 (t,
J= 7.2 Hz, 3H) ; MS (M+l)418.86.
Representative compounds of the present disclosure are exemplified in the following Tables 1 to 4, but the present disclosure is not limited to these compounds.
The compounds shown in Tables 1 to 4, other than the compounds obtained in preparation examples 1 to 2, were produced by methods similar to the methods described in preparation examples 1 to 2 or methods described in the description. The abbreviations in Tables 1 to 4 are indicated as below: F: fluoro, Cl: chloro, Br: bromo, Me: methyl, Et: ethyl, n-Pr: n-propyl, n-Bu: n-butyl, tBu: tert-butyl, Ph: phenyl, CeHn: cyclohexyl, CF3: trifluoromethyl, C3F7: heptafluoroisopropyl , OCF3: trifluoromethoxy, OMe : methoxy, COMe : methylcarbonyl , OPh: phenoxy,
CCbMe : methoxycarbonyl , C02Et: ethoxycarbonyl , CC^Ph: phenoxycarbonyl , Cy-pr: cyclopropyl, Cy-pent : cyclopentyl, F2-Ph: difluorophenyl, Cl2-Ph: dichlorophenyl , Cl3-Ph: trichlorophenyl , S02Me: methylsulfonyl, SC^Et: ethylsulfonyl, SO2CF3: trifluoromethylsulfonyl, CN : cyano, N02 : nitro.
Table 1:
Figure imgf000056_0001
Figure imgf000056_0002
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
*Both the isomers were inseparable by column chromatography
Table 2 :
Me
Figure imgf000066_0001
Figure imgf000067_0002
Table 3:
Figure imgf000067_0001
Figure imgf000067_0003
Figure imgf000068_0002
*Both the isomers were inseparable by column chromatography.
Table 4: Detail of 1H NMR and LC-MS of the compounds synthesized belonging to the Structures (1A, IB & 1C) of the present disclosure:
Figure imgf000068_0001
LC-MS
Figure imgf000069_0001
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
Figure imgf000074_0001
Figure imgf000075_0001
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Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
Figure imgf000093_0001
Figure imgf000094_0001
Figure imgf000095_0001
Figure imgf000096_0001
Figure imgf000097_0001
Figure imgf000098_0001
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Figure imgf000100_0001
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Figure imgf000102_0001
Figure imgf000103_0001
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Figure imgf000107_0001
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Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Formulation Example 1 : Emul sions
10 parts of each compound of the present disclosure was dissolved in 45 parts of Solvesso 150 and 35 parts of N-methylpyrrolidone . 10 parts of an emulsifier (tradename: Sorpol
3005X, produced by Toho Chemical Industry Co., Ltd.) was added thereto . The mixtures were mixed by stirring to give 10% emulsions . Formulation Example 2 : Wettable powders
20 parts of each compound of the present disclosure 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 blending in a juice mixer to give 20% wettable powders.
Formulation Example 3 : Granules
2 parts of sodium dodecylbenzenesulfonate, 10 parts of bentonite, and 83 parts of clay were added to 5 parts of each compound of the present disclosure, and each mixture was sufficiently mixed by stirring. An appropriate amount of water was added thereto. The resulting mixtures were further stirred and granulated with a granulator. The granules were air-dried to give 5% granules.
Formulation Example 4 : Dusts
1 part of each compound of the present disclosure was dissolved in an appropriate amount of acetone. 5 parts of fine powder of synthetic hydrated silicon dioxide, 0.3 parts of acidic isopropyl phosphate (PAP), and 93.7 parts of clay were added thereto. The mixtures were mixed by blending in a juice mixer, and acetone was removed by evaporation to give l%dust.
Formulation Example 5 : Flowable preparations
20 parts of each compound of the present disclosure 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.
Some Test Examples are given below to demonstrate that the compounds of the present disclosure are useful as an active ingredient for insecticides, miticides and fungicides.
Compound A, Compound B and Flometoquin are the representative compounds mentioned in the specification of W02006/013896A1, W02007/088978A1.
Figure imgf000121_0001
Compound A Compound B Flometoquin
Test Example 1 (Aphicidal test on Cotton aphid)
Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A cucumber leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Another cucumber leaf with cotton aphid (about 30 aphid samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25±2°C and a humidity of 40% for overnight. Next morning the top leaf was removed as aphid population has already moved to lower leaf.
Insecticidal formulations containing the compound of the present disclosure (100 ppm) were prepared by adding an aqueous solution (100 ppm) of Sorpol 355 (manufactured by TOHO Chemical Industry Co., Ltd.) to a methanol solution of the compound of the present disclosure.
These Insecticidal formulations were sprayed onto the leaves, and the leaves were air-dried and placed in a thermostatic chamber (25±2°C and a humidity of 50%) . The mortality rate of the cotton aphid was calculated after 3 days. Compounds 1A-10, 1A-11, 1A-12, 1A-18, 1A-19, 1A-21 , 1A-100, 1A-115, 1A-117, 1A-156, 1A-159, 1A-172, 1A-180 , 1A-181, 1A-183, 1A-252, 1A-254 , 1A-264, 1A-266, 1A-314 , IB-3 , IB-35 , IB-36 , IB-38, IB-46, IB-47, IB-59, IB-62, IB-64, IB-66 and IB-69 showed 80% or more mortality whereas the reference compounds (Compound A, Compound B and Flometoquin) each showed 100% mortality .
Test Example 2 (Insecticidal test on Spodoptera litura)
Insecticidal formulations containing the compound of the present disclosure (100 ppm and 20 ppm) prepared in the same manner as in test example 1. These Insecticidal formulations were sprayed onto the castor leaves (4 x 4 cm) , leaves were air-dried and placed in a plastic cup over moist paper . 4 days old Spodoptera larvae (12-15 Nos.) were released, and cup is closed and placed in a thermostatic chamber (25±2°C and a humidity of 50%) . The mortality rate of the spodoptera was calculated after 3 days. Compounds 1A-5, 1A-6, 1A-7, 1A-8 , 1A-9 , 1A-10, 1A-32 , 1A-33, 1A-81, 1A-84 , 1A-85, 1A-86, 1A-87, 1A-88 , 1A-91, 1A-92 , 1A-93, 1A-94, 1A-96, 1A-97, 1A-134, 1A-160, 1A-161 , 1A-175, 1A-185, 1A-186, 1A-188, 1A-190, 1A-193, 1A-194, 1A-195 , 1A-202 , 1A-240, 1A-241, 1A-255, 1A-258, 1A-267, 1A-269, 1A-292 , 1A-293 , 1A-294, 1A-295, 1A-296, 1A-297, 1A-298, 1A-299, 1A-300 , 1A-301 , 1A-306, 1A-315, 1A-321, 1A-324 , 1A-348, 1A-349, 1A-352 , 1A-353 , 1A-360, 1A-361, 1A-362, 1A-363, 1A-364 , 1A-367, 1A-369 , 1A-370 , 1A-371, 1A-373, 1A-374 , 1A-375, 1A-376, 1A-377, 1A-378 , 1A-379, 1A-383, 1A-384 , 1A-385, 1A-386, 1A-387, 1A-388, 1A-389 , 1A-390 , 1A-391, 1A-392, 1A-393, 1A-394 , 1A-395, 1A-396, 1A-397 , 1A-398 , 1A-406, 1A-407, 1A-408, 1A-409, 1A-410, 1A-411, 1A-412, 1A-413, 1A-414, 1A-415, 1A-416, 1A-417, 1A-418, 1A-419, 1A-420 , 1A-428 , 1A-429, 1A-430, 1A-432, 1A-434, 1A-435, 1A-436, 1A-437 , 1A-449, 1A-452, 1A-453, 1A-454, 1A-455, 1A-456, 1A-457, 1A-458 , 1A-459 , 1A-460, 1A-463, 1A-464, 1A-465, 1A-466, 1A-467, 1A-468, 1A-469, 1A-470, 1A-471, 1A-472, 1A-473, 1A-477, 1A-478, 1A-480 , 1A-481 , 1A-484, 1A-485, 1A-486, 1A-487, 1A-489, 1A-490, 1A-491, 1A-492, IB-11, IB-48, IB-49, IB-55, IB-57 , IB-77, IB-78, IB-80 , IB-81, IB-82 , IB-83, IB-84 , IB-85, IB-86, IB-87, IB-88, 1C-4 , 1C-6 , 1C-13 , 1C-34 , 1C-37 , 1C-40, 1C-41, 1C-43, 1C-49, and 1C-50 showed 80% or more mortality at 100 ppm whereas the reference Compound A showed 0% mortality at 100 ppm, and the reference Compound B and Flometoquin each showed less than 30% mortality at 500 ppm against Spodoptera litura. Compounds 1A-84 , 1A-85, 1A-87, 1A-88, 1A-91 , 1A-92 , 1A-93 , 1A-94, 1A-96, 1A-97, 1A-175, 1A-185, 1A-186, 1A-188 , 1A-190 , 1A-193, 1A-194, 1A-195, 1A-240, 1A-241, 1A-255, 1A-292 , 1A-293 , 1A-295, 1A-296, 1A-297, 1A-299, 1A-300, 1A-301, 1A-348 , 1A-353 , 1A-361, 1A-362, 1A-363, 1A-364 , 1A-373, 1A-374 , 1A-376, 1A-377 , 1A-378, 1A-379, 1A-387, 1A-388, 1A-389, 1A-394 , 1A-395 , 1A-396 , 1A-397, 1A-398, 1A-406, 1A-407, 1A-408, 1A-409, 1A-411 , 1A-412, 1A-414, 1A-415, 1A-416, 1A-417, 1A-418, 1A-419, 1A-420 , 1A-428 , 1A-429, 1A-430, 1A-434, 1A-435, 1A-436, 1A-437, 1A-452 , 1A-453 , 1A-454, 1A-455, 1A-456, 1A-457, 1A-458, 1A-459, 1A-463, 1A-465, 1A-466, 1A-467, 1A-468, 1A-469, 1A-470, 1A-471, 1A-472 , 1A-484 , 1A-487, 1A-490, IB-48, IB-55, IB-80, IB-81, IB-83, 1C-4 , and 1C-13 showed 80% or more mortality at 20 ppm. Test Example 3 (Miticidal test on two-spotted spider mite)
Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Another kidney bean leaf with two-spotted spider mites (about 30 mite samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25±2°C and a humidity of 40% overnight. Next morning the top leaf was removed as the mite population had already moved to the lower leaf.
Miticidal formulations containing the compound of the present disclosure (100 ppm) prepared in the same manner as in test example 1. These miticidal formulations were sprayed onto the leaves, and the leaves were air-dried and placed in a thermostatic chamber (25±2°C and a humidity of 50%) . The mortality rate of the two-spotted spider mites was calculated after 2 days. Compounds IB-25, IB-38, IB-39 , IB-41, IB-46, IB-47, IB-61, IB-62, IB-63, IB-64, IB-66, IB-69, IB-73 , IB-75 , IB-76, IB-78, IB-82, IB-83 and IB-89 showed 80% or more mortality whereas the reference Compound A showed 0% mortality at 100 ppm, and the reference Compound B and Flometoquin each showed less than 30% mortality at 500 ppm against two-spotted spider mite.
Test Example 4 (Ovicidal test on Two-Spotted Spider Mites)
Apiece of non-woven fabric (4.5 x 5.5 cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5 x 4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Twenty female adults of two-spotted spider mite were placed on the top of the leaf, and the fabric and leaf were placed in a thermostatic chamber having a temperature of 25±2°C and a humidity of 40% and 16L8D.
The next day, after the number of the female adults was adjusted once more to 20, Miticidal formulations containing the compound of the present disclosure (500 ppm and 100 ppm) prepared in the same manner as in test example 1 was sprayed onto the leaf, and the leaf was air-dried and placed in a thermostatic chamber (25±2°C and a humidity of 50%) . The ovicidal rate of the two-spotted spider mites was calculated 6 days after the spraying of the miticidal formulation. Compounds IB-38, IB-39, IB-41, IB-46, IB-47, IB-59, IB-61, IB-62, IB-63 , IB-64 , IB-66, IB-69, IB-70, IB-73, IB-75, IB-78 and IB-83 showed 80% or more mortality at 100 ppm whereas the reference compounds Compound A showed 40% mortality at 500 ppm and 0% mortality at 100 ppm, and the reference Compound B and Flometoquin each showed less than 30% mortality at 500 ppm. Compounds IB-3, IB-6, IB-7, IB-8, IB-10 , IB-38 , IB-39 , IB-41, IB-42, IB-46, IB-47, IB-59, IB-60, IB-61, IB-62 , IB-63 , IB-64, IB-65, IB-66, IB-69, IB-70, IB-71, IB-73, IB-74 , IB-75 , IB-76 , IB-78, IB-82, IB-83, IB-85, IB-87, IB-88, IB-89, and IB-91 showed 80% or more mortality at 500 ppm.
Test example 5 (Fungicidal test on Pyricularia grisea, millet)
The small bit of mycelium of Pyricularia grisea was taken from culture tube and transferred on mathur media plate aseptically . The inoculated plate was kept for 7 days at 25°C. Then plates were incubated at 25°C for 5 days under the exposure to black light blue, 16L8D. After five days the plates were fully covered with spores of fungus. The spores were washed from plate with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain 2 x 105 cfu spore per ml .
The solution of the compound of the present disclosure (500 ppm) prepared in the same manner as in test example 1 was sprayed on fresh healthy two weeks old millet plants. The plants were air-dried and inoculated with freshly prepared spore suspension. The inoculated plants were then placed in a dew chamber (25°C and a humidity of 100%) . One day after inoculation the plants were shifted to thermostatic chamber (25°C, a humidity of 80% , andl6L8D) . The percent disease control was assessed after 5-7 days from leaf disease area compared to control. Compounds 1A-276, 1A-325, IB-7 and IB-33 showed 80% or more control whereas the reference compounds (Compound A, Compound B and Flometoquin) showed less than 50%, less than 30%, and less than 30% control at 500 ppm, respectively.
Test example 6 (Fungicidal test on Sphaerotheca fullglnea , cucumber)
Sphaerotheca fuliginea was cultured on intact cucumber plants . Infected leaves with spores were washed with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain 2 x 105 cfu spore per ml .
The solution of the compound of the present disclosure (500 ppm) prepared in the same manner as in test example 1 was sprayed on fresh healthy two weeks old cucumber plants. The plants were air-dried and inoculated with freshly prepared spore suspension. The inoculated plants were then placed in green house (25°C, a humidity of 60% and 16L8D) . The percent disease control was assessed after 12 days from leaf disease area compared to control. Compounds 1A-172 , 1A-181, 1A-254 , 1A-262, 1A-264, 1A-266, 1A-325, 1A-431, IB-33, IB-57, IB-60, IB-66 and lC-10 showed 80% or more control whereas the reference Compound A showed such a strong phytotoxicity on cucumber at 500 ppm that evaluation was impossible, and the reference Compound B and Flometoquin showed 100% and less than 70% control at 500 ppm, respectively.
Industrial applicability
The substituted pyrazole compounds or a salt thereof of the present disclosure shows an excellent controlling effect against a wide range of pests, such as aphids, spodoptera, mites, etc. and are useful as a pesticide agent for agricultural and horticultural use .
(Note )
As described above, the present disclosure is illustrated by preferable embodiments of the present disclosure. However, it will be understood that the scope of the present disclosure should be interpreted only by the claims . It is understood that patents, patent applications and literatures cited herein are incorporated herein by reference, as if the contents thereof are specifically described herein. The present application claims priority to Indian Patent Application No. 201811024217 filed on June 29, 2018 with the Indian Patent Office (Intellectual Property India), the entire content of which is incorporated herein by reference.

Claims

[Claim 1]
A substituted pyrazole compound represented by formula (1) :
Figure imgf000126_0001
or a salt thereof,
wherein,
Q represents an oxygen atom, a sulfur atom, CR.6R7 or direct bond; R6 and R7 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C2-Ci2 alkenyl , substituted or unsubstituted C2-Ci2 alkenyloxy, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C2-Ci2 alkynyloxy, substituted or unsubstituted Ci-Ci2 alkylsulfinyl, substituted or unsubstituted Ci-Ci2 alkylsulfonyl, substituted or unsubstituted C3-Ci2 cycloalkyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted Ci-Ci2 alkoxycarbonyl , substituted or unsubstituted Ci-Ci2 alkylcarbonylamino, substituted or unsubstituted Ci-Ci2 alkylsulfonyloxy, substituted or unsubstituted Ci-Ci2 alkylsulfinyloxy, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl or substituted or unsubstituted saturated heterocyclic;
R represents hydrogen, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, substituted or unsubstituted Ci-Ci2 alkyl, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted Ci-Ci2 alkylsulfinyl, substituted or unsubstituted Ci-Ci2 alkylsulfonyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl, substituted or unsubstituted Ci-Ci2 alkoxycarbonyl, substituted or unsubstituted C3-C22 cycloalkyl, or substituted or unsubstituted saturated heterocyclic;
Ri represents hydrogen, substituted or unsubstituted Ci-Ci2 alkyl, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C3-Ci2 cycloalkyl, substituted or unsubstituted C1-C12 alkylcarbonyl , substituted or unsubstituted C2-C12 alkenylcarbonyl , substituted or unsubstituted C2-C12 alkynylcarbonyl , substituted or unsubstituted C3-C12 cycloalkylcarbonyl , substituted or unsubstituted C1-C12 alkoxycarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted heteroaryloxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted heteroarylcarbonyl , substituted or unsubstituted heterocyclecarbonyl , substituted or unsubstituted C1-C12 alkylsulfinyl, substituted or unsubstituted C1-C12 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, substituted or unsubstituted heteroarylsulfinyl, substituted or unsubstituted arylsulfonyl, substituted or unsubstituted heteroarylsulfonyl ;
R2 and R3 each independently represents hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1- C12 alkoxy, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-Ci2 alkynyl, substituted or unsubstituted C3-C12 cycloalkyl, substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted heterocyclic;
R4 and R5 each independently represent hydrogen, halogen, cyano, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio or substituted or unsubstituted aryl;
Xi represents C-Rs or N,
X2 represents C-R9 or N, and
X3 represents C-R10 or N,
with the proviso that, when Xi represents a nitrogen atom, X2 and X3 represent C-R9 and C-R10 , respectively, when X2 represents a nitrogen atom, Xi and X3 represent C-Rs and C-R10 , respectively, and when X3 represents a nitrogen atom, Xi and X2 represent C-Rs and C-Rg, respectively; and
Re, R9 and Rio each independently represent hydrogen, halogen, substituted or unsubstituted C1-C12 alkyl, substituted or unsubstituted C1-C12 alkoxy, substituted or unsubstituted C1-C12 alkylthio, substituted or unsubstituted C1-C12 alkoxycarbonyl, cyano, nitro, or substituted or unsubstituted amino.
[Claim 2] The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein Q represents an oxygen atom, or a sulfur atom.
[Claim 3]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R represents substituted or unsubstituted aryl, substituted or unsubstituted heteroaryl, or substituted or unsubstituted C1-C12 alkyl.
[Claim 4]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R represents substituted or unsubstituted C6-Ci0 aryl, or unsubstituted C1-C12 alkyl.
[Claim 5]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein Ri represents hydrogen, substituted or unsubstituted C2-Ci2 alkenyl, substituted or unsubstituted C2-C22 alkynyl, substituted or unsubstituted Ci-Ci2 alkylcarbonyl , substituted or unsubstituted C3-Ci2 cycloalkylcarbonyl , substituted or unsubstituted C2-Ci2 alkoxycarbonyl , substituted or unsubstituted arylcarbonyl , substituted or unsubstituted aryloxycarbonyl , substituted or unsubstituted C2-Ci2 alkylsulfinyl, substituted or unsubstituted Ci-Ci2 alkylsulfonyl, substituted or unsubstituted arylsulfinyl, or substituted or unsubstituted arylsulfonyl .
[Claim 6]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R2 represents hydrogen, substituted or unsubstituted C2-C22 alkenyl, unsubstituted C2-C22 alkynyl, unsubstituted C2-Ci2 alkylcarbonyl, unsubstituted C3-C22 cycloalkylcarbonyl, unsubstituted C2-Ci2 alkoxycarbonyl, substituted or unsubstituted C6-C10 arylcarbonyl, unsubstituted C6-C10 aryloxycarbonyl, or unsubstituted C6-C10 arylsulfonyl.
[Claim 7]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R2 represents hydrogen, halogen, or substituted or unsubstituted C1-C12 alkyl.
[Claim 8]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R2 represents hydrogen, or unsubstituted Ci-Ci2 alkyl.
[Claim 9]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R3 represents substituted or unsubstituted Ci-Ci2 alkyl.
[Claim 10]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R4 and R5 each independently represent hydrogen, halogen, or substituted or unsubstituted Ci-Ci2 alkyl.
[Claim 11]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R4 and R5 each independently represent hydrogen, or unsubstituted Ci-Ci2 alkyl.
[Claim 12]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein X4 represents C-Rs, X2 represents C-Rg, X3 represents C-R10, and Rs, R9 and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, or substituted or unsubstituted Ci-Ci2 alkoxy .
[Claim 13]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein X4 represents C-Rs, X2 represents C-Rg, X3 represents C-R10, and Rs, R9 and Rio are independently of each other hydrogen, halogen, substituted or unsubstituted Ci-Ci2 alkyl, or unsubstituted Ci-Ci2 alkoxy.
[Claim 14]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein Q represents an oxygen atom.
[Claim 15]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R represents substituted or unsubstituted C6 aryl.
[Claim 16]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein Ri represents hydrogen, unsubstituted C1-C12 alkylcarbonyl , unsubstituted C3-C12 cycloalkylcarbonyl , unsubstituted C1-C12 alkoxycarbonyl , or substituted or unsubstituted C6 arylcarbonyl .
[Claim 17]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R2 represents unsubstituted Ci-C6 alkyl.
[Claim 18]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R3 represents unsubstituted C2-C6 alkyl.
[Claim 19]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein R4 and R5 each independently represent hydrogen, or unsubstituted C1-C6 alkyl.
[Claim 20]
The substituted pyrazole compound or a salt thereof according to any one of the preceding claims, wherein X2 represents C-Rs, X2 represents C-Rg, X3 represents C-R10, and R3, R9 and Rio are, independently of each other, hydrogen, halogen, unsubstituted C1-C6 alkyl, or unsubstituted C1-C6 alkoxy.
[Claim 21]
A pest controlling agent comprising the substituted pyrazole compound or a salt thereof according to any one of claims 1 to 20 as an active ingredient.
[Claim 22]
A method for using the substituted pyrazole compound or a salt thereof according to any one of claims 1 to 20 for controlling pests .
[Claim 23]
A method for controlling pests, which comprises applying the substituted pyrazole compound or a salt thereof according to any one of claims 1 to 20 to a plant or its vicinity, or soil where a plant is cultivated.
[Claim 24]
A method for controlling pests, which comprises applying an effective amount of substituted pyrazole compound or a salt thereof according to any one of claims 1 to 20 to pests, a habitat of a pests, or a place where inhabitation is predicted.
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