WO2018167677A1 - Nouveau composé dithiolane, un sel ou un n-oxyde et utilisation associée - Google Patents

Nouveau composé dithiolane, un sel ou un n-oxyde et utilisation associée Download PDF

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WO2018167677A1
WO2018167677A1 PCT/IB2018/051686 IB2018051686W WO2018167677A1 WO 2018167677 A1 WO2018167677 A1 WO 2018167677A1 IB 2018051686 W IB2018051686 W IB 2018051686W WO 2018167677 A1 WO2018167677 A1 WO 2018167677A1
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optionally substituted
compound
salt
oxide
alkyl
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PCT/IB2018/051686
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Surendra Kumar KUMAWAT
Manish Kumar SINGH
Pramod Kumar CHAUHAN
Amit CHOUHAN
Md. Jawed Ashraf
Bhupender Kumar SATOLIYA
Ananya TIWARI
Tetsuya Imai
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Oat & Iil India Laboratories Private Limited
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D339/00—Heterocyclic compounds containing rings having two sulfur atoms as the only ring hetero atoms
    • C07D339/02—Five-membered rings
    • C07D339/06—Five-membered rings having the hetero atoms in positions 1 and 3, e.g. cyclic dithiocarbonates

Definitions

  • the present invention relates to a novel dithiolane compound or a salt or an N-oxide and a process for preparing the same.
  • the invention further provides an agricultural and horticultural fungicide composition comprising the said compounds .
  • Patent Literature (PTL) 1 discloses the compounds represented by the formula (A) : (A) wherein, X is 0, S or NR 4 ; Y and Z are independently O, S, NR 5 or C(R 6 R 7 ); A is hydrogen, alkyl, haloalkyl, cycloalkyl, halocycloalkyl , aryl, heteroaryl, various electron-withdrawing groups like, nitro, cyano, acetyl, carboxy, or the like; Q is alkyl, haloalkyl, cycloalkyl, aryl, heteroaryl, heterocyclic group, or the like; R 1 , R 2 and R 3 are independently hydrogen, halogen, Ci_ 6 alkyl, Ci_ 6 haloalkyl, C 3 _ 7 cycloalkyl, Ci_ 6 alkoxy, Ci-6 haloalkoxy, or optionally substituted phenyl.
  • X is 0, S or NR 4 ; Y and
  • Patent literature WO 2015/162271 (Patent Literature (PTL) 2) and WO 2015/162269 (Patent Literature (PTL) 3) also disclose imidazole substituted compounds represented by the Formula (B) :
  • X and Y are independently 0, S or NR 5 ;
  • R 1 , R 2 and R 4 are independently hydrogen, halogen, Ci-6 alkyl, Ci_ 6 haloalkyl, Ci-6 cycloalkyl, Ci-6 alkoxy, Ci- 6 haloalkoxy;
  • R 3 is phenyl, which is substituted by at least one substituent R 6 or an aromatic five-membered heterocycles; and
  • R 5 is hydrogen, Ci_ 6 alkyl, alkoxy, or Ci_ 6 cycloalkyl .
  • Patent literature WO 2015/162268 Patent literature WO 2015/162268
  • Literature (PTL) 4 also disclosed imidazole substituted compounds represented by the Formula (C) :
  • X and Y are independently 0, S or NR 4 ;
  • R 1 , R 2 and R 3 are independently hydrogen, halogen, C X - 6 alkyl, Ci-6 haloalkyl, C -6 alkoxy, Ci- 6 haloalkoxy Z 1 , Z 2 , Z 3 , Z 4 and Z 5 are
  • the present invention provides novel dithiolane compound or a salt or an N-oxide which exhibit excellent fungicidal activity against drug resistant fungi as well as drug
  • the present invention also provides a process for preparing the said dithiolane compound or a salt or an N- oxide.
  • the present invention further provides a new type of fungicide for agriculture and horticulture which exhibits a remarkable fungicidal effect against chemical-resistant fungi as well as chemical-sensitive fungi.
  • the present inventors conducted extensive research, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt or an N-oxide thereof that has fungicidal activity.
  • the present inventors have conducted further research based on the above findings.
  • the present invention has ;thereby been accomplished.
  • the present invention includes the following embodiments:
  • a dithiolane compound represented by Formula (1) A dithiolane compound represented by Formula (1)
  • R 1 , R 2 and R 3 are identical or different and each represents hydrogen, halogen, Ci- 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxy, Ci-e haloalkoxy, Ci-6 alkoxy Ci_ 6 alkyl, Ci-6 haloalkoxy Ci_ 6 alkyl, C 2 -6 alkenyl, C 2 _ 6 haloalkenyl, C 2 _ 6 alkynyl, C 2 _ 6 haloalkynyl, C 3 - 8 cycloalkyl, C3-8 cycloalkyl Ci-6 alkyl, optionally substituted aryl, optionally substituted
  • heteroaryl or optionally substituted heterocyclic group
  • two of R 1 , R 2 and R 3 groups, taken together, may form a ring, via or not via at least one heteroatom, the groups represented as R 1 , R 2 , and R 3 may optionally be further substituted;
  • Y 1 represents optionally substituted aryl, optionally substituted pyridyl, optionally substituted pyrazinyl, optionally substituted pyrimidinyl or optionally substituted pyridazinyl ;
  • Y 2 represents optionally substituted aryl or optionally substituted heteroaryl
  • Q represents hydrogen, nitro, cyano, Ci_ 6 alkyl, Ci_ 6 haloalkyl, C 3 - 8 cycloalkyl, C 3 - 8 cycloalkyl Ci_ 6 alkyl, Ci_ 6 alkylcarbonyl , Ci_6 haloalkylcarbonyl , C 3 - 8 cycloal kylcarbonyl , Ci-6 alkoxycarbonyl , Ci_ 6 haloalkoxycarbonyl , C 3 _ 8
  • Ci_ 6 alkylthio Ci_ 6 haloalkylthio, C 3 - 8 cycloalkylthio, C 3 _ 8 cycloalkyl
  • Ci- 6 alkylthio Ci- 6 alkoxy Ci-6 alkylthio, Ci- 6 alkylsulfonyl , Ci_ 6 alkylsulfinyl, Ci_ 6
  • cycloalkylsulfonyl C 3 - 8 cycloalkylsulfinyl, C 3 _ 8 cycloalkyl Ci_ 6 alkylsulfonyl , C 3 - 8 cycloalkyl Ci- 6 alkylsulfinyl, optionally substituted arylthio, optionally substituted aryl Ci_ 6
  • alkylthio optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted aryl,
  • Y 1 is a phenyl ring represented by Y la :
  • R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally substituted amino, Ci-6 alkyl, Ci_6
  • Ci_styrene resin Ci_ 6 alkoxy, Ci-6 haloalkoxy, Ci- 6 alkoxy Ci-6 alkyl, Ci_ 6 haloalkoxy Ci_ 6 alkyl, Ci-6 alkoxycarbonyl , Ci_s
  • haloalkoxycarbonyl cyano Ci-6 alkyl, cyano C]- 6 alkoxy, C 2 -e alkenyl, C 2 _ 6 haloalkenyl, cyano C 2 - 6 alkenyl, C 2 - 6 alkynyl, C 2 - 6 haloalkynyl, cyano C 2 - 6 alkynyl, C 3 - 8 cycloalkyl, C3-8 cycloalkyl C -6 alkyl, Ci- 6 alkylthio, Ci-6 haloalkylthio, C 3 - 8
  • Ci-6 alkylthio C 3 _ 8 cycloalkyl Ci-6 alkylthio, Ci_ 5 alkoxy Ci- 6 alkylthio, Ci- 6 alkylsulfonyl , Ci_ 6 alkylsulfinyl , Ci_ 6
  • haloalkynyloxy Ci ⁇ e alkylsulfonyloxy, Ci_6 alkylsulfinyloxy, Cj 6 alkylcarbonyl , Ci-6 haloalkylcarbonyl , carboxyl, OCN, SCN, SF 5 , optionally substituted aryloxy, optionally substituted aryl Ci-6 alkoxy, optionally substituted arylthio, optionally substituted aryl Ci_6 alkylthio, optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted
  • arylsulfonyloxy optionally substituted arylsulfinyloxy, optionally substituted aryl, optionally substituted
  • heteroaryl or optionally substituted heterocyclic group
  • * is the point of attachment to the parent compound.
  • R 4 , R 5 , R 6 , R ; and R 8 are identical or different and each represents hydrogen, halogen, Ci_ 6 alkyl, Ci-6 haloalkyl, Ci- 6 alkoxy or Ci_ 6
  • R 9 , R 10 , R 11 , R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 , and R are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, optionally
  • alkylsulfinyl C 2 _ 6 alkenyloxy, C 2 _ 6 alkynyloxy, C 2 _ 6
  • arylsulfonyl optionally substituted arylsulfonyl , optionally substituted arylsulfinyl, optionally substituted heteroaryloxy, optionally substituted arylsulfonyloxy, optionally substituted
  • arylsulfinyloxy optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted heterocyclic group
  • dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y 2 is optionally substituted aryl.
  • Y 2 is a phenyl ring represented by Y 2a :
  • R , R , R , and R are identical or
  • Ci-6 alkyl Ci_ haloalkyl, Ci-6 alkoxy, Ci_ 6 haloalkoxy, Ci_ 6 alkoxy Ci_ 6 alkyl, Ci-6 haloalkoxy Ci-6 alkyl, Ci-6 alkoxycarbonyl, Ci_ 6
  • haloalkoxycarbonyl cyano Ci- 6 alkyl, cyano Ci_ 6 alkoxy, C 2 - 6 alkenyl, C 2 _ 6 haloalkenyl , cyano C 2 _ 6 alkenyl, C 2 - 6 alkynyl, C 2 - 6 haloalkynyl, cyano C 2 ⁇ e alkynyl, C 3 - 8 cycloalkyl, C 3 _ 8 cycloalkyl Ci-6 alkyl, Ci_ 6 alkylthio, Ci_ 6 haloalkylthio, C 3 - 8
  • Ci- 6 alkylthio C 3 - 8 cycloalkyl
  • Ci_ 6 alkoxy Ci- 6 alkylthio
  • cycloalkylsulfonyl C 3 _ 8 cycloalkylsulfinyl, C 3 - 8 cycloalkyl, Ci 6 alkylsulfonyl, C 3 - 8 cycloalkyl Ci- 6 alkylsulfinyl, C 2 -6
  • haloal kynyloxy Ci-6 alkylsulfonyloxy, Ci- 6 alkylsulfinyloxy, Ci 6 alkylcarbonyl, C 6 haloalkylcarbonyl , carboxyl, OCN, SCN, SF 5 , optionally substituted aryloxy, optionally substituted aryl Ci- 6 alkoxy, optionally substituted arylthio, optionally substituted aryl Ci-6 alkylthio, optionally substituted
  • arylsulfonyl optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted
  • arylsulfonyloxy optionally substituted arylsulfinyloxy, optionally substituted aryl, optionally substituted
  • heteroaryl or optionally substituted heterocyclic group
  • * is the point of attachment to the parent compound.
  • R 21 , R 22 , R 23 , R 24 , and R 25 are identical or different and each represents hydrogen, halogen, nitro, cyano, optionally substituted amino, Ci-g alkyl, Ci- 6 haloalkyl, Ci-6 alkoxy, C 6 haloalkoxy, or optionally substituted aryl.
  • dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y 2 is optionally substituted heteroaryl.
  • Y 2 is optionally substituted pyridyl, optionally substituted pyrazinyl, optionally substituted pyrimidinyl, optionally substituted pyridazinyl or optionally substituted thiazolyl.
  • Y 2 is optionally substituted pyridyl, optionally substituted pyrazinyl, or optionally substituted thiazolyl.
  • dithiolane compound or a salt or an N-oxide thereof according to any one of the preceding items, wherein Y 2 is optionally substituted pyridyl.
  • Y 2 is optionally substituted 4-pyridyl, optionally substituted 3- pyridyl, or optionally substituted 2-pyridyl.
  • Y 2 is a pyridine ring represented by any one of Y 2b , Y 2c and Y 2d :
  • Ci-6 alkylsulfonyl C 3 _ 8 cycloalkyl
  • alkylsulfinyl C 2 ⁇ e alkenyloxy, C 2 -e alkynyloxy, C 2 -6
  • haloalkenyloxy C 2 _ 6 haloalkynyloxy, Ci_ 6 alkylsulfonyloxy, Ci-6 alkylsulfinyloxy, Ci- 6 alkylcarbonyl , Ci ⁇ 6 haloalkylcarbonyl , carboxyl, OCN, SCN, SF 5 , optionally substituted aryloxy, optionally substituted aryl Ci_ 6 alkoxy, optionally substituted arylthio, optionally substituted aryl Ci_ 6 alkylthio,
  • arylsulfonyl optionally substituted arylsulfonyl , optionally substituted arylsulfinyl , optionally substituted heteroaryloxy, optionally substituted arylsulfonyloxy, optionally substituted
  • arylsulfinyloxy optionally substituted aryl, optionally substituted heteroaryl, or optionally substituted heterocyclic group
  • Y 2 is selected from the group consisting of:
  • the * is the point of attachment to the parent compound.
  • a dithiolane compound selected from the group consisting of compounds lc-1, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-SL, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-llL, lc-13H, lc-13L, lc-14H, lc- 15H, lc-16, 1C-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc- 24, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc- 28L
  • a dithiolane compound selected from the group consisting of compounds lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5L, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-13H, lc-13L, lc-14H, lc-15H, lc-16, lc-16H, lc-19, lc-20, lc-23, lc-23H, lc-23L, lc-24H, lc-25H, lc-25L, lc-26, lc-26H, lc-26L, lc-27H, lc-29H, lc-29L, lc-32H, l
  • a dithiolane compound selected from the group consisting of compounds lc-1, lc- ⁇ , lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-7H, lc-7L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc-lOH, lc-lOL, lc-HH, lc-llL, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc-16, lc-16H, lc-16L, lc-17H, lc-18L, lc-19H, lc-19L, lc-20, lc
  • a dithiolane compound selected from the group consisting of compounds lc-1, lC-16, lc-16H, lc-16L, and lc-19H, or a salt or an N-oxide thereof.
  • a dithiolane compound selected from the group consisting of compounds lc-1, lc-lL, lc-2H, lc-2L, lc-3, lc-3H, lc-3L, lc-4H, lc-4L, lc-5H, lc-5L, lc-6, lc-6H, lc-6L, lc-8, lc-8H, lc-8L, lc-9, lc-9H, lc-9L, lc- ⁇ , lc-lOL, lc-HH, lc-llL, lc- 12, lc-12H, lc-13, lc-13H, lc-13L, lc-14H, lc-15H, lc-15L, lc- 16, lc-16H, lc-16L, lc-17H, lc-18L, lc-19, lc-19L, lc-20, lc- 21H,
  • a dithiolane compound or a salt or an N-oxide thereof according to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the dithiolane compound or a salt or an N-oxide thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi .
  • a dithiolane compound or a salt or an N-oxide thereof The invention provides a dithiolane compound or a salt or an N-oxide thereof represented by the Formula (1) for use in agriculture and horticulture.
  • R 1 , R 2 , R 3 , Y 1 , Y 2 and Q are as defined above.
  • the presence of one more possible asymmetric carbon atoms in a compound of Formula (1) means that the compounds may occur in optionally isomeric form, i.e. enantiomeric or diastereomeric forms.
  • the presence of one or more possible double bonds in a compound of Formula (1) means that the compounds may occur in various diastereomeric forms.
  • Formula (1) is intended to include all those possible isomeric forms and mixtures thereof.
  • the present invention includes all those possible isomeric forms and mixtures thereof for a compound of Formula (1).
  • Formula (1) is intended to include all possible tautomers.
  • the present invention includes all possible tautomeric forms for compound of Formula (1) .
  • substituted is not particularly limited if it is
  • Ci-6 alkyl means a linear or branched, saturated hydrocarbon group having one to six carbon atoms.
  • C 2 -6 alkenyl means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and
  • C 2 -6 alkynyl means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and
  • C3-8 cycloalkyl means a cyclic alkyl having three to eight carbon atoms, and includes those cyclic alkyls having a partially bridged structure.
  • Ci-6 alkoxy refers to a “Ci_ 6 alkoxy group", and the "Ci_6 alkyl” moiety is defined the same as the above-described "C 6 alkyl” .
  • Aryl means a monocyclic or polycyclic aromatic
  • 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.
  • 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 include besides carbon atoms 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.
  • Ci-6 alkyl examples include, but are not particularly limited to Ci_6 straight-chain or branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec- butyl, tert-butyl, n-pentyl, n-hexyl, and the like.
  • Ci-6 haloalkyl examples include, but are not
  • Ci-6 alkoxy examples include, but are not particularly limited to Ci- 6 straight-chain or branched-chain alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy,
  • 0 ⁇ _ ⁇ haloalkoxy examples include, but are not
  • halogen atoms such as fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy , pentafluoroethoxy, 3, 3, 3-trifluoropropoxy, 4 , 4 , 4-trifluorobutoxy, heptafluoroisobutoxy, and the like.
  • Ci-6 alkoxy Ci_ 6 alkyl examples include, but are not particularly limited to alkoxyalkyl in which Ci ⁇ 6 straight- chain or branched-chain alkyl is substituted with Ci_ 6
  • Ci_ 6 haloalkoxy Ci-6 alkyl examples include, but are not particularly limited to straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxymethyl ,
  • C 8 cycloalkyl examples include, but are not
  • cyclopropyl particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C 3 - 8 cycloalkyl Ci-6 alkyl examples include, but are not particularly limited to, cyclopropylmethyl , cyclobutylethyl , cyclopentylmethyl , cyclohexylmethyl , and the like.
  • Ci-6 alkylcarbonyl examples include, but are not particularly limited to, Ci-6 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 sec-butylcarbonyl
  • tert- butylcarbonyl sec-butylcarbonyl
  • Ci_6 haloal kylcarbonyl examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylcarbonyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylcarbonyl ,
  • chloromethylcarbonyl bromomethylcarbonyl , iodomethylcarbonyl , dichloromethylcarbonyl , trichloromethylcarbonyl ,
  • chlorodifluoromethylcarbonyl bromodifluoromethylcarbonyl , dichlorofluoromethylcarbonyl , 2,2, 2-trichloroethylcarbonyl, 2, 2, 2-trifluoroethylcarbonyl, pentafluoroethylcarbonyl, and the like.
  • C X -6 alkoxycarbonyl examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkoxycarbonyl groups, such as methoxycarbonyl ,
  • C 6 haloalkoxycarbonyl examples include, but are not particularly limited to, Ci_ 6 straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethoxycarbonyl ,
  • C3-8 cycloal kylcarbonyl examples include, but are not particularly limited to, cyclopropylcarbonyl ,
  • C 3 - a cycloal koxycarbonyl examples include, but are not particularly limited to, cyclopropyloxycarbonyl ,
  • cyano Ci-6 alkyl examples include, but are not particularly limited to, Ci-6 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.
  • cyano C s alkoxy examples include C 1 - 6 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.
  • cyano C s alkoxy examples include C 1 - 6 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
  • C2-6 alkenyl examples include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl , and the like.
  • C2-6 haloalkenyl examples include, but are not
  • C2-6 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 -e haloalkynyl examples include, but are not
  • cyano C 2 -e alkenyl examples include, but are not particularly limited to, 2-cyanovinyl , 2, 2-dicyanovinyl, 3- cyano-2-allyl, 3, 3-dicyano-2-allyl, 4 -cyano-3-butenyl , 4,4- dicyano-3-butenyl , , , -tricyano-2-butenyl, and the like.
  • cyano C 2 ⁇ 6 alkynyl examples include, but are not particularly limited to, cyanoethynyl , 3-cyano-l-propynyl , and the like.
  • Ci- 6 alkylsulfonyl examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyl, ethylsulfonyl, n-propylsulfonyl , isopropylsulfonyl , n-butylsulfonyl ,
  • Ci-6 haloalkylsulfonyl examples include, but are not particularly limited to, Ci_ 6 straight-chain or branched-chain alkylsulfinyl groups substituted with 1 to 9, preferably 1 to 5, halogen atoms, such as fluoromethylsulfonyl ,
  • chloromethylsulfonyl bromomethylsulfonyl, iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl ,
  • Examples of ⁇ c 6 alkylsulfinyl include, but are not particularly limited to, C x _6 straight-chain or branched-chain alkylsulfinyl groups, such as methylsulfinyl , ethylsulfinyl , n-propylsulfinyl , isopropylsulfinyl , n-butylsulfinyl ,
  • Ci_ 6 haloalkylsulfinyl examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfinyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylsulfinyl,
  • chloromethylsulfinyl bromomethylsulfinyl, iodomethylsulfinyl , dichloromethylsulfinyl , trichloromethylsulfinyl ,
  • chlorodifluoromethylsulfinyl bromodifluoromethylsulfinyl, dichlorofluoromethylsulfinyl , 2,2,2-trichloroethylsulfinyl, 2,2,2-trifluoroethylsulfinyl, pentafluoroethylsulfinyl , and the like.
  • Ci-6 alkylthio examples include, but are not
  • Ci-6 straight-chain or branched-chain alkylthio such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio , sec-butylthio , tert- butylthio, and the like.
  • Ci-6 haloalkylthio examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylthio substituted with 1 to 9, and preferably 1 to 5, halogen atoms, such as fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio , dichloromethylthio, tri chloromethylthio, difluoromethylthio, trifluoromethylthio , chlorodifluoromethylthio , bromodifluoromethylthio,
  • dichlorofluoromethylthio 2 , 2 , 2-trichloroethylthio, 2,2,2- trifluoroethylthio, pentafluoroethylthio , and the like.
  • C3-8 cycloalkylsulfonyl examples include, but are not particularly limited to, cyclopropylsulfonyl ,
  • C3-8 cycloalkylsulfinyl examples include, but are not particularly limited to, cyclopropylsulfinyl ,
  • C 3 _ 8 cycloalkylthio examples include, but are not particularly limited to, cyclopropylthio, cyclobutylthio, cyclopentylthio , cyclohexylthio, and the like.
  • C 3 8 cycloalkyl Ci-6 alkylsulfonyl examples include, but are not particularly limited to, cyclopropylmethylsulfonyl , 2- cyclopropylethylsulfonyl, 3-cyclopropylpropylsulfonyl , cyclohexylmethylsulfonyl , and the like.
  • C 8 cycloalkyl Ci-6 alkylsulfinyl examples include, but are not particularly limited to, cyclopropylmethylsulfinyl , 2- cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl, cyclohexylmethylsulfinyl , and the like.
  • Ci-s alkylthio examples include, but are not particularly limited to, cyclopropylmethylthio, 2- cyclopropylethylthio, 3-cyclopropylpropylthio,
  • Ci-6 alkoxy Ci_ 6 alkylthio examples include, but are not particularly limited to, alkoxyalkylthio in which C e
  • C 2 -6 alkenyloxy examples include, but are not
  • C 2 -6 haloalkenyloxy examples include, but are not particularly limited to, 2 , 2-dichlorovinyloxy , 2,2- dibromovinyloxy, 2 , 2-difluorovinyloxy, 3, 3-difluoro-2- allyloxy, 4 , -difluoro-3-butenyloxy, 4 , 4 , 4-trifluoro-2- butenyloxy, and the like.
  • C 2 -6 alkynyloxy examples include, but are not ; particularly limited to, ethynyloxy, 2-propynyloxy, 1-methyl- 2-propynyloxy, 1 , l-dimethyl-2-propynyloxy , 1-butynyloxy , 2- butynyloxy, 3-butynyloxy , and the like.
  • C 2 -6 haloalkynyloxy examples include, but are not particularly limited to, fluoroethynyloxy , bromoethynyloxy , chloroethynyloxy, iodoethynyloxy, 3, 3, 3-trifluoro-1- propynyloxy, and the like.
  • Ci_6 al kylsulfonyloxy examples include, but are not particularly limited to, Ci-e straight-chain or branched-chain alkylsulfonyl groups, such as methylsulfonyloxy,
  • ethylsulfonyloxy n-propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and the like.
  • Ci-6 alkylsulfinyloxy examples include, but are not particularly limited to, Ci-6 straight-chain or branched-chain alkylsulfinyloxy groups, such as methylsulfinyloxy,
  • ethylsulfinyloxy n-propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, sec-butylsulfinyloxy, tert-butylsulfinyloxy, and the like.
  • substituted or unsubstituted amino examples include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino , and the like.
  • alkyl examples include Ci_ 6 alkyl mentioned above, and the like.
  • acyl examples include Ci-6 alkylcarbonyl , C 6
  • haloalkylcarbonyl Ci- 6 al koxycarbonyl , C ⁇ 6 haloalkoxycarbonyl , arylcarbonyl , aryloxycarbonyl mentioned above, and the like.
  • aryl examples include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
  • aryl Ci-e alkyl examples include, but are not
  • aryl Ci- 6 alkyls can be further substituted at both the parts alkyl as well as aryl.
  • aryloxy examples include, but are not particularly limited to, phenoxy, 1-naphthyloxy, 2-naphthyloxy, and the like.
  • aryl Ci_6 alkoxy examples include, but are not
  • benzyloxy particularly limited to, benzyloxy, phenylethoxy, phenyl-n- propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2- naphthylmethoxy, and like.
  • heteroaryloxy examples include, but are not
  • pyridinyloxy particularly limited to, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, and the like.
  • arylsulfonyl examples include, but are not
  • phenylsulfonyl particularly limited to, phenylsulfonyl , 1-naphthylsulfonyl , 2-naphthylsulfonyl , and the like.
  • arylsulfinyl examples include, but are not
  • phenylsulfinyl particularly limited to, phenylsulfinyl , 1-naphthylsulfinyl , 2-naphthylsulfinyl , and the like.
  • arylthio examples include, but are not particularly limited to, phenylthio, ; 1-naphthylthio, 2-naphthylthio , and the like.
  • arylsulfonyloxy examples include, but are not
  • phenylsulfonyloxy particularly limited to, phenylsulfonyloxy, 1- naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.
  • arylsulfinyloxy examples include, but are not particularly limited to, phenylsulfinyloxy, 1- naphthylsulfinyloxy , 2-naphthylsulfinyloxy , and the like.
  • aryl Ci_6 alkylthio examples include, but are not particularly limited to, benzylthio, phenylethylthio, phenyl- n-propylthio, phenyl-n-butylthio, 1-naphthylmethylthio, 2- naphthylmethylthio, and the like.
  • arylcarbonyl examples include, but are not
  • phenylcarbonyl particularly limited to, phenylcarbonyl , 1-naphthylcarbonyl , 2-naphthylcarbonyl , and the like.
  • aryloxycarbonyl examples include, but are not
  • phenyloxycarbonyl particularly limited to, phenyloxycarbonyl , 1- naphthyloxycarbonyl , 2-naphthyloxycarbonyl , 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 ,
  • 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 ,
  • 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 ,
  • tetrahydropyrazinyl piperazinyl, triazinyl, dihydrotriazinyl , tetrahydrotriazinyl , hexahydrotriazinyl , tetrazinyl,
  • tetrahydrocinnolinyl phthalazinyl , dihydrophthalazinyl , tetrahydrophthalazinyl, quinoxalinyl , dihydroquinoxalinyl, tetrahydroquinoxalinyl , purinyl, dihydrobenzotriazinyl , dihydrobenzotetrazinyl , phenothiazinylfuranyl , benzofuranyl , chromanyl, benzothienyl , and the like.
  • heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group.
  • heterocyclics mentioned above may optionally be further substituted.
  • Examples of the number of substituents include, but are not particularly limited to, 1 to 20
  • substituted or substituted include: but are not particularly limited to, the halogen, nitro, cyano, hydroxyl, formyl, Ci_ 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxy, C x _ 6 haloalkoxy, Ci- 6 alkoxy Ci_6 alkyl, Ci_ 6 haloalkoxy Ci- 6 alkyl, C 3 _ 8 cycloalkyl, C 3 - 8 cycloalkyl Ci_ 6 alkyl, Ci- 6 alkylcarbonyl , Ci_ 6 haloalkylcarbonyl, Ci_6 alkoxycarbonyl , Ci-6 haloalkoxycarbonyl , arylcarbonyl , aryloxycarbonyl , Ci- 6 cyanoalkyl, Ci-6
  • alkylsulfonyl aryl Ci_ 6 alkylsulfinyl , aryl Ci_ 6 alkylthio, heterocyclic, heterocyclic Ci ⁇ 6 alkyl, heterocyclic oxy, and the like.
  • 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.
  • the N-oxide is a compound having atom constituting the ring in the heterocyclic group oxidized.
  • a heterocyclic group which may constitute an N-oxide may, for example, be a condensed ring containing a pyridine ring, a condensed ring containing a pyrazine ring, a condensed ring containing a pyridazine ring or a condensed ring
  • preferable compound is a compound in which R 1 is hydrogen, halogen or C x _ 6 alkyl, and a more preferable compound (1) is a compound in which R 1 is hydrogen or methyl.
  • preferable compound is a compound in which R 2 is hydrogen, halogen or Ci_6 alkyl, and a more preferable compound (1) is a compound in which R 2 is hydrogen.
  • preferable compound is a compound in which R 3 is hydrogen, halogen or Ci-6 alkyl, and a more preferable compound (1) is a compound in which R 3 is hydrogen.
  • preferable compound is a compound in which Y 1 is optionally substituted aryl or optionally substituted pyridyl, and a more preferable compound (1) is a compound in which Y 1 is
  • an especially preferable compound (1) is a compound in which Y 1 is optionally substituted 3-pyridyl.
  • preferable compound is a compound in which Y 2 is optionally substituted aryl or optionally substituted pyridyl and a more preferable compound (1) is a compound in which Y 2 is
  • preferable compound is a compound in which Q is cyano .
  • preferable compound is a compound in which R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and each is hydrogen, halogen, Ci-6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxy or Ci_6 haloalkoxy, and a more preferable compound (1) is a compound in which R 4 , R 5 , R 6 , R 7 and R 8 are identical or different and each is hydrogen, fluorine, chlorine, bromine, tert-butyl, trifluoromethyl, methoxy or trifluoromethoxy .
  • preferable compound is a compound m which R% R , R 1 , R x % R 13 , R 14 , R 15 , R 16 , R 17 ;.
  • R 18 , R 19 and R 20 are identical or
  • preferable compound (1) is a compound in which R 9 , R 10 , R 11 ,
  • R 12 , R 13 , R 14 , R 15 , R 16 , R 17 , R 18 , R 19 and R 20 are hydrogen or chlorine .
  • a preferable compound is a compound in which R 21 , R 22 , R 23 , R 24 and R 25 are identical or different and each is hydrogen, halogen, nitro, cyano, optionally substituted amino, Ci-6 alkyl, Ci_ 6 haloalkyl, Ci- 6 alkoxy, Ci- 6 haloalkoxy or optionally
  • a more preferable compound (1) is a compound in which R are identical or different and each is hydrogen, fluorine, chlorine, bromine, nitro, cyano, amino, methyl, trifluoromethyl , methoxy,
  • preferable compound is a compound in which R 26 , R 27 , R 28 , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 are identical or
  • preferable compound (1) is a compound in which R , R , R , R 29 , R 30 , R 31 , R 32 , R 33 , R 34 , R 35 , R 36 and R 37 is hydrogen.
  • a more preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which
  • R 1 is hydrogen, halogen, or C 6 alkyl
  • R 2 is hydrogen, halogen, or Ci_ 6 alkyl
  • R 3 is hydrogen, halogen, or Ci- 6 alkyl
  • Y 1 is optionally substituted aryl or optionally substituted pyridyl ;
  • Y 2 is optionally substituted aryl or optionally substituted pyridyl ; Q is cyano.
  • a more particularly preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen
  • R 3 is hydrogen
  • Y 1 is optionally substituted phenyl, optionally substituted 3- pyridyl or optionally substituted 4-pyridyl;
  • Y 2 is optionally substituted phenyl
  • a especially particularly preferable compound of the present invention is a compound or a salt or an N-oxide thereof in which
  • R 1 is hydrogen or methyl
  • R 2 is hydrogen
  • R 3 is hydrogen
  • Y 1 is optionally substituted 3-pyridyl
  • Y 2 is optionally substituted phenyl
  • the invention also provides a process for preparing a dithiolane or a salt or an N-oxide thereof represented by the Formula ( 1 ) :
  • R 1 , R 2 , R 3 , Y 1 , Y 2 and Q are as defined above.
  • the dithiolane compound represented by Formula (1) of the present invention can be readily prepared according to
  • the dithiolane compound represented by Formula (1) can be prepared by the reaction of a compound (2) with a compound (3) and carbon disulfide in the presence of a base and a solvent as mentioned in reaction scheme 1.
  • R 1 , R 2 , R 3 , Y 1 , Y 2 and Q are as defined above. While, ⁇ and B are identical or different and each represents a
  • suitable leaving group such as chlorine, bromine, and iodine; substituted or unsubst ituted Ci- 6 alkyl sulfonate; and
  • the amount of the compound (3) to be used is usually 0.5 to 5 mol, preferably 1 to 2 mol, per 1 mol of the compound (2) .
  • the amount of the carbon disulfide to be used is usually 2 to 10 mol, preferably 1 to 2 mol, per 1 mol of the compound (2) .
  • the reaction is carried out in the presence of a suitable base.
  • a suitable base a conventionally known base can widely be used, and examples of the bases include: alkali metal
  • alkali metal hydroxides such as sodium
  • alkali metal hydrides such as sodium hydride and potassium hydride, and the like
  • alkali metal hydrides such as sodium hydride and sodium hydride
  • 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 -dimethylaminopyridine , piperidine, and the like, preferably sodium hydroxide,
  • potassium hydroxide sodium hydride, potassium hydride sodium methoxide, sodium ethoxide and potassium tert-butoxide. Any separate one of these bases or a combination of two cor more types thereof is used.
  • organic base when used, it can be used in large excess to serve as a solvent.
  • the amount of the base to be used is usually 2 to 5 mol, preferably 2 to 3 mol, per 1 mol of the compound (2) .
  • the aforementioned reaction is performed in an
  • Such a solvent examples 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; ether-based solvents such as diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, dimethoxyethane , and the like; esters solvents such as methyl acetate, ethyl acetate, and the like; acetonitrile ; amide- based solvents such as , N-dimethylformamide (DMF), N,N- dimethylacetoamide , N-
  • sulfoxide-based solvents such as dimethyl sulfoxide (DMSO) , sulforane and the like; H 2 0; acetic acid, preferably, DMSO, DMF, toluene and THF. 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 to 20 liter, preferably 1 to 10 liters, per 1 mol of the compound (2) .
  • the reaction is usually done at a temperature from -10°C to boiling point of the solvent.
  • the reaction time is usually in the range of 0.25 hour to 24 hours or more depending on the completion of the reaction.
  • the compound (2) used in this step can be produced according to a known method (for example, the method described in WO2007/045989, Synlett (15), 2223-2227 (2011) and Molecular Diversity 18(2), 307-322 (2014)).
  • the compound (3) used in this step can be produced according to a known method (for example, the method described in WO2006/110804, WO2015/003991 , WO2015/11194 and
  • the compound represented by Formula (1) obtained by the method shown in Scheme 1 is easily isolated from a reaction mixture and can be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column
  • the present compound is usually prepared by mixing the present compound with solid carriers, liquid carriers, gas carriers, surfactants and the others, and if necessary, adding stickers, dispersers and stabilizers, to formulate into wettable powders, water dispersible granules, flowables, granules, dry flowables, emulsifiable concentrates, aqueous solutions, oil solutions, smoking agents, aerosols, microcapsules and the others.
  • the present compound is contained in a range of usually 0.1 to 99%, preferably 0.2 to 90% by weight.
  • solid carriers examples include clays (for example
  • kaolin kaolin, diatomaceous earth, synthetic hydrated silicon dioxide, Fubasami clay, bentonite and acid clay) , talcs or the other inorganic minerals (for example, sericite, quartz powder, sulfur powder, activated charcoal, calcium carbonate and hydrated silica) in the form of fine powders or particulates
  • the liquid carries include water, alcohols (for example, methanol and ethanol), ketones (for example, acetone and methyl ethyl ketone), aromatic hydrocarbons (for example, benzene, toluene, xylene,
  • ethylbenzene and methyl naphthalene examples include aliphatic hydrocarbons (for example, n-hexane, cyclohexane and kerosene), esters (for example, ethyl acetate and butyl acetate), nitriles (for example, acetonitrile and isobutyronitrile), ethers (for
  • dioxane and diisopropyl ether examples include dioxane and diisopropyl ether), acid amides (for example, DMF and dimethylacetamide ) , halogenated hydrocarbons (for example, dichloroethane trichloroethylene and carbon tetrachloride) and the others.
  • acid amides for example, DMF and dimethylacetamide
  • halogenated hydrocarbons for example, dichloroethane trichloroethylene and carbon tetrachloride
  • surfactants examples include alkyl sulfates, alkyl sulfonates, alkyl aryl sulfonates, alkyl aryl ethers and polyoxyethylenated compounds thereof, polyethylene glycol ethers, polyol esters and sugar alcohol derivatives.
  • auxiliary agents for formulation examples include stickers, dispersers and stabilizers, specifically casein, gelatin, polysaccharides (for example, starch, gum arabic, cellulose derivatives and alginic acid) , lignin derivatives, bentonite, sugars, water-soluble synthetic polymers (for example, polyvinyl alcohol, polyvinyl
  • PAP acidic isopropyl phosphate
  • BHT 2, 6-di-tert -butyl-4 -methylphenol
  • BHA a mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4- methoxyphenol
  • vegetable oils mineral oils, fatty acids or fatty acid esters thereof and the others.
  • the method for applying the present compound is not particularly limited, as far as the applying form is a form by which the present compound may be applied substantially, and includes, for example, an application to plants such as a foliage application; an application to area for cultivating plants such as a submerged treatment; and an application to soil such as seed disinfection.
  • the application dose varies depending on weather
  • the emulsifiable concentrate, the wettable powder or the suspension concentrate, etc. is usually applied by diluting it with water.
  • the concentration of the present compound after dilution is in the range of usually 0.0005 to 2% by weight, and preferably 0.005 to 1% by weight.
  • the dust formulation or the granular formulation etc. is usually applied, as itself without diluting it.
  • the amount of the present compound is in the range of usually from 0.001 to 100 g, and preferably from 0.01 to 50 g per 1 kg of the seeds.
  • examples of the place where the pests live include paddy fields, fields, tea gardens, orchards, non- agricultural lands, houses, nursery trays, nursery boxes, nursery soils and nursery bed.
  • the present compound can be administered to the inside (inside of the body) or the outside (body surface) of the below-mentioned vertebrate to exterminate systemically or unsystemically living things or parasites which are parasitic on the
  • Examples of a method of the internal medication include an oral administration, an anal administration, a transplantation, an administration via injection
  • Examples of a method of outside medication include a transdermal
  • the present compound can be ingested to a livestock animal so as to exterminate sanitary insects which occur in the excrement of the animal.
  • the dose varies depending on the administration method etc., but it is desirable in general to administer the present compound so that a dose of the active ingredient (the present compound or salts thereof) is in the range of generally from 0.1 mg to 2,000 mg and preferably 0.5 mg to 1,000 mg per 1 kg of body weight of the animal.
  • the present compound can be used as an agent for
  • the compound of the present invention can control diseases occurred in the
  • Crops corn, rice, wheat, barley, rye, oat, sorghum, cotton, soybean, peanut, buckwheat, beet, rapeseed, sunflower, sugar cane, tobacco, and the others;
  • Vegetables solanaceous vegetables (for example, eggplant, tomato, pimento, pepper and potato), cucurbitaceous vegetables (for example, cucumber, pumpkin, zucchini, water melon and melon) , cruciferous
  • vegetables for example, Japanese radish, white turnip, horseradish, kohlrabi, Chinese cabbage, cabbage, leaf mustard, broccoli, cauliflower), asteraceous vegetables (for example, burdock, crown daisy, artichoke and lettuce) , liliaceous vegetables (for example, green onion, onion, garlic and asparagus), ammiaceous vegetables (for example, carrot, parsley, celery and parsnip), chenopodiaceous vegetables (for example, spinach and Swiss chard), lamiaceous vegetables (for example, Perilla frutescens, mint and basil), strawberry, sweet potato, Dioscorea japonica, colocasia and the others; Flowers: Ornamental foliage plants: Fruits: pomaceous fruits (for example, apple, pear, Japanese pear, Chinese quince and quince), stone fruits (for example, peach, plum, nectarine, Prunus mume, cherry fruit, apricot and prune), citrus fruits (for example, Citrus unshiu, orange, lemon, lime and
  • Grapefruit nuts (for example, chestnut, walnut, hazelnut, almond, pistachio, cashew nut and macadamia nut), berry fruits (for example, blueberry, cranberry, blackberry and raspberry), grape, kaki persimmon, olive, Japanese plum, banana, coffee, date palm, coconut, and the others; Trees other than fruit trees: tea, mulberry, flowering plant, roadside trees (for example, ash, birch, dogwood, Eucalyptus, Ginkgo biloba, lilac, maple, Quercus, poplar, Judas tree, Liquidambar
  • the above-mentioned "plant” includes genetically modified crops .
  • the pests on which the present compound has a control efficacy include plant pathogens such as filamentous fungus, as well as harmful arthropods such as harmful insects and harmful mites, and nemathelminth such as nematodes, and specifically include the following examples, but are not limited thereto.
  • Rice diseases blast (Magnaporthe grisea) , brown spot (Cochliobolus miyabeanus), sheath blight (Rhizoctonia solani) , bakanae disease (Gibberella fujikuroi), and downy mildew
  • Barley diseases powdery mildew (Erysiphe graminis), fusarium blight (Fusarium graminearum, F. avenaceum, F.
  • Cotton diseases anthracnose (Colletotrichum gossypii), grey mildew (Ramularia areola) , alternaria leaf spot
  • Coffee diseases rust (Hemileia vastatrix) ;
  • Citrus diseases melanose (Diaporthe citri), scab
  • Apple diseases blossom blight (Monilinia mali), canker (Valsa ceratosperma) , powdery mildew (Podosphaera
  • Grapes diseases anthracnose (Elsinoe ampelina) , ripe rot (Glomerella cingulata) , powdery mildew (Uncinula necator) , rust (Phakopsora ampelopsidis ) , black rot (Guignardia
  • anthracnose (Gloeosporium kaki) and leaf spot (Cercospora kaki, Mycosphaerella nawae) ;
  • anthracnose Cold-totrichum lagenarium
  • powdery mildew Sphaerotheca fuliginea
  • gummy stem blight Didymella bryoniae
  • target spot Corynespora cassiicola
  • fusarium wilt Fusarium oxysporum
  • downy mildew Pseudoperonospora cubensis
  • phytophthora rot Phytophthora sp.
  • damping-off Pythium sp.
  • Tomato diseases early blight (Alternaria solani), leaf mold (Cladosporium fulvum) , leaf mold ( Pseudocercospora fuligena) , and late blight (Phytophthora infestans) ;
  • Eggplant disease brown spot (Phomopsis vexans) and powdery mildew (Erysiphe cichoracearum) ;
  • Soybean diseases purple stain (Cercospora kikuchii) , sphaceloma scad (Elsinoe glycines), pod and stem blight
  • target spot (Corynespora cassiicola)
  • anthracnose Cold spot
  • Rhizoctonia aerial blight Rhizoctonia solani
  • septoria brown spot Septoria glycines
  • frog eye leaf spot Cercospora sojina
  • Kidney bean diseases anthracnose (Colletotrichum
  • Peanut diseases early leaf spot (Cercospora personata) , late leaf spot (Cercospora arachidicola ) and southern blight (Sclerotium rolfsii);
  • Potato diseases early blight (Alternaria solani), late blight ( Phytophthora infestans), and verticillium wilt
  • brown spot Alternaria longipes
  • powdery mildew Erysiphe cichoracearum
  • Rose diseases black spot (Diplocarpon rosae) and powdery mildew ( Sphaerotheca pannosa) ;
  • Botrytis leaf blight Botrytis cinerea, B. byssoidea, B. squamosa
  • gray-mold neck rot Botrytis allii
  • small sclerotial rot Botrytis squamosa
  • gray mold Botrytis cinerea
  • sclerotinia rot Sclerotinia sclerotiorum
  • Turfgrass diseases dollar spot (Sclerotinia
  • Delphacidae for example, Laodelphax
  • Deltocephalinae for example, Nephotettix cincticeps, or
  • Nephotettix virescens Nephotettix virescens
  • Aphididae for example, Aphis
  • Pentatomidae for example, Nezara antennata
  • Aleyrodidae for example, Trialeurodes vaporariorum, or Bemisia argentifolii
  • Coccoidea for example, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens,
  • Lepidoptera Pyralidae (for example, Chilo suppressalis , Tryporyza incertulas, Cnaphalocrocis medinalis, Notarcha derogata, Plodia interpunctella , Ostrinia furnacalis, Hellula undalis, Pediasia teterrellus) , Noctuidae (for example,
  • Trichoplusia spp. Trichoplusia spp., Heliothis spp., or Helicoverpa spp.
  • Pieridae for example, Pieri;s rapae
  • Tortricidae for example, Pieri;s rapae
  • Adoxophyes spp. Grapholita molesta, Cydia pomonella, Leguminivora glycinivorella , Matsumuraeses azukivora,
  • Arctiidae for example, Hyphantria cunea
  • Tineidae for example, Tinea translucens, or Tineola bisselliella
  • the others ;
  • Thysanoptera Thysanoptera (for example, Frankliniella occidentalis , Thrips palmi, Scirtothrips dorsalis, Thrips tabaci, Frankliniella intonsa, Frankliniella fusca) ;
  • Diptera Musca domestica, Culex pipiens pallens, Tabanus trigonus, Hylemya antiqua, Hylemya platura, Anopheles sinensis, Agromyza oryzae, Hydrellia griseola, Chlorops oryzae, Dacus cucurbitae, Ceratitis capitata, Liriomyza trifolii, and the others;
  • Coleoptera Epilachna vigintioctopunctata , Aulacophora femoralis, Phyllotreta striolata, Oulema oryzae, Echinocnemus squameus, Lissorhoptrus oryzophilus, Anthonomus grandis, Callosobruchus chinensis, Sphenophorus venatus, Popillia japonica, Anomala cuprea, Diabrotica spp., Leptinotarsa decemlineata , Agriotes spp., Lasioderma serricorne, Anthrenus verbasci, Tribolium castaneum, Lyctus brunneus, Anoplophora malasiaca, Tomicus piniperda, and the others;
  • Orthoptera Locusta migratoria, Gryllotalpa africana, Oxya yezoensis, Oxya japonica, and the others;
  • Hymenoptera Athalia rosae, Acromyrmex spp., Solenopsis spp., and the others;
  • Nematodes Aphelenchoides besseyi, Nothotylenchus acris, Heterodera glycines, Meloidogyne incognita, Pratylenchus , Nacobbus aberrans, and the others;
  • Blattariae Blattella germanica, Periplaneta fuliginosa, Periplaneta americana, Periplaneta brunnea, Blatta orientalis, and the others;
  • Acarina Tetranychidae (for example, Tetranychus urticae,
  • Panonychus citri, or Oligonychus spp. Panonychus citri, or Oligonychus spp.
  • Eriophyidae for example, Aculops pelekassi
  • Tarsonemidae for example,
  • Pyroglyphidae for example, Dermatophagoides farinae, or
  • Cheyletidae for example, Cheyletus eruditus, Cheyletus malaccensis, or Cheyletus moorei
  • Dermanyssidae and the others.
  • the formulation comprising the present compound or salts thereof can also be used in the field relating to a treatment of livestock diseases or livestock industry, and for example, can exterminate the living things or parasites which are parasitic on the inside and/or the outside of a vertebrate such as human being, cow, sheep, pig, poultry, dog, cat and fish, so as to maintain public health.
  • the pests include Ixodes spp . (for example, Ixodes scapularis), Boophilus spp. (for example, Boophilus microplus), Amblyomma spp., Hyalomma spp., Rhipicephalus spp.
  • Haematobia spp. Tabanus spp., Simulium spp., Triatoma spp., Phthiraptera (for example, Damalinia spp.), Linognathus spp., Haematopinus spp., Ctenocephalides spp. (for example,
  • Ctenocephalides felis Xenopsylla spp., monomorium pharaonis and nematodes, hairworm (for example, Nippostrongylus
  • Trichostrongylus axei Trichostrongylus
  • Trichinella spp. for example, Trichinella spiralis
  • Haemonchus contortus for example, Nematodirus spp.
  • Nematodirus battus for example, Nematodirus battus
  • Ostertagia circumcincta for example,
  • the dithiolane (1) of the invention is used, for example as active ingredient for a fungicide.
  • the dithiolane (1) of the invention can be used by being made into the desirable form such as oil, emulsion, wettable powder, flowable preparation, granules, powder, aerosol, fumigant or the like.
  • the content of the dithiolane (1) of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the form of preparation, kind of disease to be treated, kind of plant, severity of disease, place of application, time of application, method of application, chemicals to be used in combination (insecticide, nematicide, acaricide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), amount and kind of fertilizer and so on.
  • the content is usually about 0.01 to about 95% by weight, based on the total amount of the
  • a fungicidal preparation containing the dithiolane (1) of the invention as the active ingredient can be produced
  • the dithiolane (1) of the invention may be mixed with a carrier such as a solid carrier, a liquid carrier, a gaseous carrier or the like.
  • Useful carriers can be any of known ones which are usually used in this field.
  • useful solid carriers are fine or granules of clays (kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, fubasami clay, acid clay, and the like), talcs, ceramics, other inorganic minerals, cerite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.), and so on.
  • clays kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, fubasami clay, acid clay, and the like
  • talcs ceramics, other inorganic minerals, cerite, quartz, sulfur, activated carbon, calcium carbonate, hydrated silica, etc.
  • Useful liquid carriers are, for example, water, alcohols (such as methanol, ethanol, etc.), ketones (such as acetone, methyl ethyl ketone, etc.), aromatic hydrocarbons (such as benzene, toluene, xylene, ethylbenzene , methylnaphthalene , etc.), aliphatic hydrocarbons (such as hexane, cyclohexane, kerosene, light oil, etc.), esters (such as ethyl acetate, butyl acetate, etc.), nitriles (such as acetonitrile, isobutyronitrile, etc.), ethers (such as diisopropyl ether, dioxane, etc.), acid amides (such as N, -dimethylformamide, N , N-dimethylacetamide , etc.), haloqenated hydrocarbons (such as dichloromethane
  • useful gaseous carriers are butane gas, LPG (liquefied petroleum gas), dimethyl ether, carbon dioxide, etc.
  • useful surfactants are alkyl ester sulfates, alkyl sulfonates, alkylarylsulfonates, alkyl aryl ethers, polyoxyethylenated products thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol compounds, etc .
  • useful adjuvants for preparation are fixing agents such as casein, gelatin, polysaccharides (starch powder, gum arabic, cellulose compound, alginic acid, etc.) ?
  • lignin compounds bentonite, saccharides, synthetic water- soluble polymers (polyvinyl alcohol, polyvinyl pyrrolidone, polyacrylic acid, etc.), and the like; stabilizers such as PAP (acidic isopropyl phosphate), BBH (2, 6-di-tert-butyl-4- methylphenol ) , BHA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol ) , vegetable oils, mineral oils, fatty acids, esters thereof, and the like.
  • PAP acidic isopropyl phosphate
  • BBH 2, 6-di-tert-butyl-4- methylphenol
  • BHA mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl-4-methoxyphenol
  • vegetable oils mineral oils, fatty acids, esters thereof, and the like.
  • the fungicidal preparation of the invention thus obtained can be used as it is or as diluted with water.
  • the preparation may be prepared by being mixed with any of insecticides, nematicides, acaricides, fungicides, herbicides, plant growth control agents, synergists, soil conditioners, etc.
  • the preparation of the invention may be applied simultaneously with other preparations.
  • the amount of the preparation of the invention is not limited and can be suitably selected from a wide range according to various conditions such as the concentration of active ingredient, the form of preparation, kind of disease to be treated, kind of plant, severity of disease or mite, time for application, method of application, chemicals to be used in combination (insecticide, nematicide, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), amount and kind of a fertilizer and so on.
  • the amount is usually about 0.001 to about 100 g per 100 m 2 of the area.
  • the concentration of the fungicidal or miticidal preparation is about 0.1 to about 1000 ppm, preferably about 1 to 500 ppm.
  • the granules, particles or the like are applied as such without dilution.
  • the compound of the invention is characterized by having an excellent fungicidal activity and a broad spectrum of activity.
  • the compound can be used for control of plant diseases ascribed to pathogenic fungi and resistant pathogenic fungi.
  • pathogenic fungi include those that cause or are resistant to fungicides to treat rice plant blast, rice plant sheath blight, grey mould on tomato, and the like, 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, potato blight, and the like.
  • the two regio-isomers of the title compound could be separated on TLC and the one at higher Rf value was assigned as lc-3H while the another one at lower Rf values on the TLC was assigned as lc-3L, using the solvent system of n-hexane and ethyl acetate.
  • F fluoro
  • CI chloro
  • Br bromo
  • Me methyl
  • t-Bu tert- butyl
  • CF 3 trifluoromethyl
  • Ph phenyl
  • N0 2 nitro
  • C cyano
  • OMe methoxy
  • CF 3 0 trifluoromethoxy
  • NH 2 amino.
  • H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of /i-hexane and ethyl acetate.
  • H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of n-hexane and ethyl acetate.
  • H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of n-hexane and ethyl acetate.
  • H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of /i-hexane and ethyl acetate.
  • H and L here refer to two regio-isomers of the compound at higher and lower Rf values on the TLC, respectively, using the solvent system of n-hexane and ethyl acetate.
  • each compound of the invention was added to the mixture of 2 parts of sodium lauryl sulfate, 4 parts of sodium lignin sulfonate, 20 parts of fine powders of water- containing synthetic silicon oxide and 54 parts of clay. These ingredients were mixed while stirring by a juice mixer, thereby producing 20% wettable powders.
  • Rhodorsxl ® 426R manufactured by RhodiaChimie .
  • the mixture was pulverized by a mill (trade name: DYNO-Mill, and manufactured by Willy A. Bachofen AG) using a ;wet method, and further mixed with 60 parts of water- containing 8 parts of propylene glycol and 0.32 parts of xanthan gum, thereby producing a 20% suspension in water.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

Un des objets de la présente invention est de fournir un composé dithiolane ou un sel ou un N-oxyde de celui-ci capable de lutter contre des maladies. La présente invention concerne un composé dithiolane représenté par la formule (1) ou un sel ou un N-oxyde de celui-ci. Dans la formule (1), R1 représente l'hydrogène, halogène, alkyle en C1-6 ou un substituant tel que défini dans la description ; R2 représente l'hydrogène, halogène, un groupe alkyle en C1-6 ou un substituant tel que défini dans la description ; R3 représente l'hydrogène, halogène, un groupe alkyle en C1-6 ou un substituant tel que défini dans la description ; Y1 représente un groupe aryle éventuellement substitué, pyridyle éventuellement substitué ou un substituant tel que défini dans la description ; Y2 représente un aryle éventuellement substitué, pyridyle éventuellement substitué ou un substituant tel que défini dans la description ; Q représente un cyano ou un substituant tel que défini dans la description.
PCT/IB2018/051686 2017-03-15 2018-03-14 Nouveau composé dithiolane, un sel ou un n-oxyde et utilisation associée WO2018167677A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5061716A (en) * 1990-09-13 1991-10-29 Uniroyal Chemical Company, Inc. Fungicidal 3,3-bisthioalkyl-2-pyridylacrylic acid compounds
WO2006110804A2 (fr) 2005-04-12 2006-10-19 Philadelphia Health & Education Corporation D/B/A Drexel University College Of Medicine Synthese de chromophore au nitrodibenzylfurane pour la photodeprotection de molecules organiques
WO2007045989A1 (fr) 2005-10-20 2007-04-26 Pfizer Limited Dérivés de pyridyle pouvant être employés en tant que ligands h3
WO2015003991A1 (fr) 2013-07-12 2015-01-15 Syngenta Participations Ag Nouveaux microbiocides
WO2015011194A1 (fr) 2013-07-26 2015-01-29 Syngenta Participations Ag Nouveaux microbiocides
WO2015162269A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés imidazoliques microbicides
WO2015162271A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés imidazoliques microbicides
WO2015162268A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés microbiocides d'imidazole

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5061716A (en) * 1990-09-13 1991-10-29 Uniroyal Chemical Company, Inc. Fungicidal 3,3-bisthioalkyl-2-pyridylacrylic acid compounds
WO2006110804A2 (fr) 2005-04-12 2006-10-19 Philadelphia Health & Education Corporation D/B/A Drexel University College Of Medicine Synthese de chromophore au nitrodibenzylfurane pour la photodeprotection de molecules organiques
WO2007045989A1 (fr) 2005-10-20 2007-04-26 Pfizer Limited Dérivés de pyridyle pouvant être employés en tant que ligands h3
WO2015003991A1 (fr) 2013-07-12 2015-01-15 Syngenta Participations Ag Nouveaux microbiocides
WO2015011194A1 (fr) 2013-07-26 2015-01-29 Syngenta Participations Ag Nouveaux microbiocides
WO2015162269A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés imidazoliques microbicides
WO2015162271A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés imidazoliques microbicides
WO2015162268A1 (fr) 2014-04-25 2015-10-29 Syngenta Participations Ag Dérivés microbiocides d'imidazole

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
MOLECULAR DIVERSITY, vol. 18, no. 2, 2014, pages 307 - 322
SYNLETT, vol. 15, 2011, pages 2223 - 2227

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AR111179A1 (es) 2019-06-12

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