WO2018138692A1 - Nouveaux composés fongicides de carbamate - Google Patents

Nouveaux composés fongicides de carbamate Download PDF

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Publication number
WO2018138692A1
WO2018138692A1 PCT/IB2018/050512 IB2018050512W WO2018138692A1 WO 2018138692 A1 WO2018138692 A1 WO 2018138692A1 IB 2018050512 W IB2018050512 W IB 2018050512W WO 2018138692 A1 WO2018138692 A1 WO 2018138692A1
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WO
WIPO (PCT)
Prior art keywords
alkyl
compound
methyl
optionally substituted
salt
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Application number
PCT/IB2018/050512
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English (en)
Inventor
Surendra Kumar KUMAWAT
Ashish BHATT
Pramod Kumar CHAUHAN
Md. Jawed Ashraf
Amit CHOUHAN
Rajesh Kumar Singh
Manish Kumar SINGH
Bhupender Kumar SATOLIYA
Tetsuya Imai
Original Assignee
Insecticides (India) Limited
Oat Agrio Co., Ltd.
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Application filed by Insecticides (India) Limited, Oat Agrio Co., Ltd. filed Critical Insecticides (India) Limited
Publication of WO2018138692A1 publication Critical patent/WO2018138692A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/22—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/20—N-Aryl derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen

Definitions

  • the present invention relates to novel carbamate
  • the invention further provides an agricultural and horticultural fungicide composition comprising the said compounds.
  • Patent Literature (PTL) 1 Patent Literature (PTL) 1 and WO
  • Patent Literature (PTL) 2 disclose the compounds represented by the formula (A) which has a pyrazole moiety in the molecule. These publications also mentioned that the compound represented by the formula (A) is useful as fungicide to control plant diseases.
  • Ri is halogen, C1-C4 alkyl group
  • R2 is hydrogen, halogen, C1-C4 alkyl group
  • R3 is hydrogen, halogen, C 1 -C3 alkyl group, C1-C3 alkoxy group, C 3 -C 4 cycloalkyl group
  • Z is halogen C1-C3 alkyl group, C1-C3 alkoxy group
  • Q is represented by Qi, Q 2 and Q 3 as shown below:
  • R 4 is C 1 -C3 alkyl group
  • R 5 is hydrogen, hydroxy, methyl
  • R 6 is hydrogen, hydroxy, methyl, methoxy
  • X x is oxygen, sulfur
  • X2 is oxygen, sulfur, NR 7 or a direct bond
  • R 7 is hydrogen, C 1 -C3 alkyl group.
  • the present invention provides novel carbamate compounds which exhibit excellent fungicidal activity against drug resistant fungi as well as drug sensitive fungi.
  • the present invention also provides a process for
  • 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 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 carbamate compound is represented by the formula (1) :
  • R x , R3 and R 6 are identical or different and each represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, carboxy, optionally substituted amino, Ci-6 alkyl, Ci_ 6
  • Ci_ 5 haloalkyl, Ci_ 6 alkoxy, Ci_ 6 haloalkoxy, Ci_ 6 alkoxy Ci_ 6 alkyl, Ci_6 haloalkoxy Ci-6 alkyl, Ci_ 6 alkoxycarbonyl , Ci_ 5
  • 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 _ 6 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
  • haloalkynyloxy Ci- 6 alkylsulfonyloxy, Ci_ 6 alkylsulfinyloxy, Ci-6 alkylcarbonyl, Ci_ 6 haloalkylcarbonyl , OCN, SCN, SF 5 , optionally substituted aryloxy, optionally substituted aryl Ci-6 alkyloxy, 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, or optionally substituted
  • R 2 represents hydrogen, halogen, or Ci_ 6 alkyl
  • R 4 and R 5 are identical or different and each represents hydrogen, halogen, or Ci-e alkyl
  • R 7 represents hydrogen, hydroxyl, formyl, cyano, Ci_ 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxy, Ci_ 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 , C 2 - 6 haloalkoxycarbonyl, C 2 - 6 alkenyl, C 2 - 6 haloalkenyl, C 2 -e cyanoalkenyl, C 2 -6 alkynyl, C 2 -6 haloalkynyl, C 2 _6 cyanoalkynyl, Ci_ 6 alkylsulfonyl , Ci_ 6 alkylsulf
  • cycloalkylsulfonyl C 3 - 8 cycloalkylsulfinyl , C 3 _ 8 cycloalkyl Ci_ 6 alkylsulfonyl, C 3 _ 8 cycloalkyl Ci- 6 alkylsulfinyl , optionally substituted arylsulfonyl, optionally substituted arylsulfinyl , or optionally substituted aryl;
  • R 8 represents hydrogen, or Ci-6 alkyl
  • X and Xi independently represent oxygen, or sulfur
  • Y represents oxygen, or sulfur
  • Z represents oxygen, or sulfur
  • 1 is an integer of 0 to 2;
  • n is an integer of 0 to 3;
  • n is an integer of 0 to 4.
  • 1, m or n when 1, m or n is more than one, the 1, m or n may be the same or different.
  • Item 2 The carbamate compound or a salt thereof according to Item 1, wherein each Ri is independently hydrogen, halogen, nitro, Ci_ 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkoxycarbonyl, cyano Ci-6 alkyl, optionally substituted aryl.
  • Item 3 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 2 is hydrogen or Ci-6 alkyl .
  • Item 4 The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R 3 is
  • Ci_ 6 alkyl independently hydrogen, halogen or Ci_ 6 alkyl.
  • Item 5 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 4 and R 5 each
  • Item 6 The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R 6 is
  • Ci- 6 alkyl or Ci-6 alkoxy independently hydrogen, halogen, Ci- 6 alkyl or Ci-6 alkoxy.
  • Item 7 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 7 is hydrogen, Ci-6 alkyl or Ci_ 6 alkylcarbonyl .
  • Item 8 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 8 is Ci-6 alkyl.
  • Item 9 The carbamate compound or a salt thereof according to any one of the preceding items, wherein X and Xi are oxygen.
  • Item 10 The carbamate compound or a salt thereof according to any one of the preceding items, wherein Y is oxygen.
  • Item 11 The carbamate compound or a salt thereof according to any one of the preceding items, wherein Z is sulfur and the 1,3-thiazole ring containing Z is selected from the group consisting of: and the * is the point of attachment to the parent compound.
  • Item 12 The carbamate compound or a salt thereof according to any one of the preceding items, wherein each Ri is
  • Ci_ 6 alkyl or Ci_ 6 haloalkyl independently hydrogen, halogen, Ci_ 6 alkyl or Ci_ 6 haloalkyl.
  • Item 13 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 2 is Ci_ 6 alkyl.
  • Item 14 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 2 is methyl.
  • Item 15 The carbamate compound or a salt thereof according to any one of the preceding items, wherein each R 3 is hydrogen.
  • Item 16 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R and R5 each
  • Item 17 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 6 is hydrogen, halogen or Ci-6 alkyl.
  • Item 18 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 7 is hydrogen or 0 ⁇ _ 6 alkylcarbonyl .
  • Item 19 The carbamate compound or a salt thereof according to any one of the preceding items, wherein R 8 is methyl or ethyl.
  • Item 20 The carbamate compound or a salt thereof according to any one of the preceding items, wherein Rg is methyl.
  • Item 21 The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1,3-thiazole ring is : and the * is the point of attachment to the parent compound.
  • Item 22 The carbamate compound or a salt thereof according to any one of the preceding items, wherein the carbamate compound is represented by the formula (1A) :
  • Item 23 The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1 , 3-thiazole ring is : and the * is the point of attachment to the parent compound.
  • Item 24 The carbamate compound or a salt thereof according to any one of the preceding items, wherein the 1, 3-thiazole ring is : and the * is the point of attachment to the parent compound.
  • Item 25 A carbamate compound selected from the group
  • Item 26 A carbamate compound selected from the group consisting of:
  • Item 28 A carbamate compound selected from the group consisting of:
  • Item 29 A carbamate compound selected from the group consisting of:
  • Item 30 A plant disease-controlling agent containing the carbamate compound or a salt thereof according to any one of Items 1 to 29.
  • Item 31 A fungicide containing the carbamate compound or a salt thereof according to any one of Items 1 to 29.
  • a carbamate compound or a salt thereof according to the present invention achieves an excellent fungicidal effect on fungal plant pathogens. Additionally, the heterocyclic
  • compound or a salt thereof according to the present invention is useful as a new type of fungicide that exhibits excellent fungicidal activity not only against chemical-sensitive fungi, but also against chemical-resistant fungi.
  • the invention provides a carbamate compound or a salt thereof represented by the formula (1) for use in agriculture and horticulture.
  • each group is also applied when the group is one part of or a substituent on other groups.
  • Ci-6 alkyl means a linear or branched, saturated
  • hydrocarbon group having one to six carbon atoms 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
  • C2-6 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 alkyl having a partially bridged structure.
  • Ci-6 alkoxy refers to a "Ci-6 alkyloxy group", and the "Ci-6 alkyl” moiety is defined the same as the above-described "Ci-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
  • 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, isobutoxy, sec-butoxy, tert-butoxy, and the like.
  • Ci-e 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-e 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
  • alkoxy 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.
  • 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
  • chloromethoxymethyl bromomethoxymethyl , iodomethoxymethyl , difluoromethoxymethyl , trifluoromethoxymethyl, 2,2,2- tri fluoroethoxymethyl , and the like.
  • C 3 ⁇ 8 cycloalkyl examples include, but are not
  • cyclopropyl particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C3-8 cycloalkyl C ⁇ - 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
  • Ci_ 6 straight-chain or branched-chain alkylcarbonyl groups such as methylcarbonyl (acetyl)
  • Ci_ 6 haloalkylcarbonyl 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 ,
  • Ci_ 6 alkoxycarbonyl examples include, but are not particularly limited to Ci_ 6 straight-chain or branched-chain alkoxycarbonyl groups, such as methoxycarbonyl , ethoxycarbonyl , n-propoxycarbonyl , isopropoxycarbonyl, n-butoxycarbonyl , isobutoxycarbonyl , sec-butoxycarbonyl, tert-butoxycarbonyl , and the like.
  • 0 ⁇ _ ⁇ 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 ,
  • 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.
  • 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 Ci-6 alkoxy examples include Cx- 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 Ci-6 alkoxy examples include Cx- 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.
  • C 2 -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
  • C 2 -e 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 -6 haloalkynyl examples include, but are not
  • chloroethynyl iodoethynyl, 3, 3, 3-trifluoro-l-propynyl, and the like.
  • cyano C2-6 alkenyl examples include, but are not
  • 2-cyanovinyl 2, 2-dicyanovinyl, 3- cyano-2-allyl , 3 , 3-dicyano-2-allyl , 4 -cyano-3-butenyl , 4,4- dicyano-3-butenyl, 4 , 4 , 4-tricyano-2-butenyl, and the like.
  • cyano C2-6 alkynyl examples include, but are not
  • Ci-6 alkylsulfonyl examples include, but are not
  • 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, fluoromethylsulfonyl ,
  • chloromethylsulfonyl bromomethylsulfonyl, iodomethylsulfonyl , dichloromethylsulfonyl , trichloromethylsulfonyl ,
  • chlorodifluoromethylsulfonyl bromodifluoromethylsulfonyl , dichlorofluoromethylsulfonyl, 2,2, 2-trichloroethylsulfonyl, 2, 2, 2-trifluoroethylsulfonyl, pentafluoroethylsulfonyl , and like Ci-6 straight-chain or branched-chain alkylsulfonyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms.
  • Ci-6 alkylsulfinyl examples include, but are not particularly limited to Ci-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.
  • 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,
  • C 3 - 8 cycloalkylsulfonyl examples include, but are not particularly limited to, cyclopropylsulfonyl ,
  • C 3 _ 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.
  • Ci-6 alkylsulfonyl examples include, but are not particularly limited to, cyclopropylmethylsulfonyl, 2- cyclopropylethylsulfonyl , 3-cyclopropylpropylsulfonyl ,
  • Ci-6 alkylsulfinyl examples include, but are not particularly limited to, cyclopropylmethylsulfinyl , 2- cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl ,
  • Ci- 6 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 Ci_ 6 straight- chain or branched-chain alkylthio is substituted with Ci ⁇ e straight-chain or branched-chain alkoxy, such as
  • C 2 -e alkenyloxy examples include, but are not
  • C2-6 haloalkenyloxy examples include, but are not particularly limited to, 2 , 2-dichlorovinyloxy, 2,2- dibromovinyloxy, 2 , 2-difluorovinyloxy, 3 , 3-difluoro-2-allyloxy 4 , 4-difluoro-3-butenyloxy, 4 , 4 , 4-trifluoro-2-butenyloxy, and the like.
  • C 2 ⁇ 6 alkynyloxy examples include, but are not
  • C 2 -e haloalkynyloxy examples include, but are not particularly limited to, fluoroethynyloxy, bromoethynyloxy, chloroethynyloxy, iodoethynyloxy, 3 , 3 , 3-trifluoro-1- propynyloxy, and the like.
  • Ci_ 6 alkylsulfonyloxy examples include, but are not particularly limited to Ci_ 6 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 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 alkoxycarbonyl ,
  • aryl examples include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
  • aryl Ci_ 6 alkyl examples include, but are not
  • aryl Ci-6 alkyl 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
  • heteroaryl Ci- 6 alkoxy examples include, but are not particularly limited to, pyridinylmethoxy, pyridinylethoxy, pyrimidinylethoxy , pyrazolylmethoxy , and 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
  • phenylsulfinyloxy 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.
  • 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,
  • 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 ,
  • 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,
  • 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.
  • heterocyclic groups include those substituted at any subst itutable 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, Ci_ 6 haloalkoxy, Ci_6 alkoxy Ci- 6 alkyl, Ci- 6 haloalkoxy Ci-6 alkyl, C 3 _ 8 cycloalkyl, C 3 -s cycloalkyl Ci-6 alkyl, Ci_ 6 alkylcarbonyl , Ci_6 haloal kylcarbonyl , arylcarbonyl , aryloxycarbonyl , C 1 - 6
  • alkylsulfonyl aryl Ci- 6 alkylsulfinyl, aryl Ci-6 alkylthio, heterocyclic, heterocyclic Ci-g alkyl, heterocyclic oxy, and the like.
  • preferable substituents are 1 halogen, nitro, cyano, Ci_ 6 alkyl, Ci-6 haloalkyl, Ci_ 6 alkoxy, Ci- 6 haloalkoxy, Ci_6 alkylsulfonyl , Ci-6 haloalkylsulfonyl, Ci_ 6 alkylsulfinyl , Ci_ 6 haloalkylsulfinyl, Ci- 6 alkylthio, Ci- 6 haloalkylthio, substituted or unsubst ituted amino, aryl, and heterocyclic, and more preferable substituents are fluorine, chlorine, nitro, methyl, ethyl, trifluoromethyl , methoxy, and tri
  • substituted aryl groups are halogen- substituted aryl, Ci_ 6 alkyl-substituted aryl, Ci_ 6 haloalkyl- substituted aryl, halogen and Ci_6 haloalkyl-substituted aryl, Ci-6 alkoxy-subst ituted aryl, Ci_6 haloalkoxy-substituted aryl, and Ci-6 al kylthio-substituted aryl. More preferable
  • substituted aryl groups are chlorine-substituted aryl
  • substituted heteroaryl groups are halogen- substituted heteroaryl, Ci-e alkyl-substituted heteroaryl, C 6 haloalkyl-substituted heteroaryl, halogen and Ci-6 haloalkyl- substituted heteroaryl, Ci-6 alkoxy-substituted heteroaryl, Ci- 6 haloalkoxy-substituted heteroaryl, and Ci_6 alkylthio- substituted heteroaryl. More preferable substituted heteroaryl groups are chlorine-substituted heteroaryl, fluorine- substituted heteroaryl, trifluoromethyl-substituted heteroaryl, chlorine- and trifluoromethyl-subst ituted heteroaryl,
  • substituted heterocyclic groups are halogen- substituted heterocyclic, Ci-6 alkyl-substituted heterocyclic, Ci-6 haloalkyl-substituted heterocyclic, Ci_ 6 alkoxy-substituted heterocyclic, Ci-6 haloalkoxy-substituted heterocyclic, and Ci-6 alkylthio-subst ituted heterocyclic. More preferable
  • substituted heterocyclic groups are chlorine-substituted heterocyclic, fluorine-substituted heterocyclic,
  • the salts of the compoun'ds represented by Formula (1) may be any type of salts as long as they are agriculturally
  • 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
  • X and Xi represents oxygen or sulfur
  • Y represents oxygen, or sulfur
  • Z represents oxygen, or sulfur
  • 1 is an integer 0 to 2;
  • n is an integer 0 to 3;
  • n is an integer 0 to 4.
  • preferable compound is a compound in which R x is hydrogen, halogen, nitro, Ci- 6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkylcarbonyl , cyano Ci-6 alkyl, optionally substituted aryl and a more preferable compound (1) is a compound in which Ri is hydrogen, chlorine, bromine, methyl, chloromethyl , trifluoromethyl , methoxycarbonyl , ethoxycarbonyl , or cyanomethyl .
  • preferable compound is a compound in which R2 is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R 2 is methyl.
  • preferable compound is a compound in which R3 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 R 4 is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R 4 is hydrogen.
  • preferable compound is a compound in which R5 is hydrogen, or Ci-6 alkyl and a more preferable compound (1) is a compound in which R 5 is hydrogen.
  • preferable compound is a compound in which Rg is hydrogen, halogen, Ci-e alkyl or Ci_ 6 alkoxy and a more preferable
  • compound (1) is a compound in which R is hydrogen, chlorine, methyl, or methoxy.
  • preferable compound is a compound in which R 7 is hydrogen, Ci_ 6 alkyl or Ci_6 alkylcarbonyl and a more preferable compound (1) is a compound in which R 7 is hydrogen, methyl, ethyl,
  • preferable compound is a compound in which R 8 is Ci_ 6 alkyl and a more preferable compound (1) is a compound in which R 8 is methyl .
  • preferable compound is a compound in which X is oxygen, or sulfur and a more preferable compound (1) is a compound in which X is oxygen.
  • preferable compound is a compound in which Xi is oxygen, or sulfur and a more preferable compound (1) is a compound in which Xi is oxygen.
  • preferable compound is a compound in which Y is oxygen, or sulfur and a more preferable compound (1) is a compound in which Y is oxygen.
  • preferable compound is a compound in which Z is oxygen, or sulfur and a more preferable compound (1) is a compound in which Z is sulfur.
  • a more preferable compound of the present invention is a compound or a salt thereof in which
  • Ri is hydrogen, halogen, nitro, Ci-6 alkyl, Ci_ 6 haloalkyl, Ci_ 6 alkylcarbonyl, or cyano Ci_ 6 alkyl;
  • R 2 is hydrogen or Ci-6 alkyl
  • R 3 is hydrogen, halogen, or Ci_ 6 alkyl
  • R is hydrogen or Ci-6 alkyl
  • R5 is hydrogen or Ci-6 alkyl
  • R 6 is hydrogen, halogen, Ci_ 6 alkyl or Ci_ 6 alkoxy
  • R 7 is hydrogen, Ci-6 alkyl or Ci_ 6 alkylcarbonyl
  • R 8 is Ci-6 alkyl
  • X and Xi independently represent oxygen, or sulfur
  • Y represents oxygen or sulfur
  • Z represents oxygen or sulfur
  • n is an integer of 0 to 4.
  • a more particularly preferable compound of the present invention is a compound or a salt thereof in which
  • Ri is hydrogen, halogen, Ci-e alkyl, or Ci-g haloalkyl
  • R2 is hydrogen or methyl
  • R3 is hydrogen
  • R 4 is hydrogen
  • R 5 is hydrogen
  • R 6 is hydrogen, chlorine, methyl or methoxy
  • R 7 is hydrogen, methyl, ethyl, isopropyl, acetyl, propionyl or isobutyryl ;
  • R 8 is methyl
  • X and Xi independently represent oxygen
  • Y represents oxygen
  • 1 is an integer of 0 to 2;
  • n is an integer of 0 to 3;
  • n is an integer of 0 to 4.
  • the invention also provides a process for preparing a carbamate or a salt thereof represented by the formula (1)
  • Ri, R 2 , R3, R , RS A R7, X, Xi, Y, Z, 1, m and n are as defined above.
  • the carbamate compound represented by Formula (1) can be readily prepared according to following reaction scheme 1 to scheme 4, but is not limited to these methods.
  • the carbamate compound represented by Formula (ID) can be prepared by the reaction of a 2-substituted five-membered heterocycle compound (2a) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 1:
  • Ri, R 2 , R3, R4, R5, Re, Rs/ X, Xi, Y, Z, 1, m and n are as defined above.
  • A represents halogen, methanesulfonyloxy, p- toluenesulfonyloxy or trifluoromethanesulfonyloxy .
  • R 9 represents hydrogen, Ci-6 alkyl (the substituent may form -CH 2 CH2-, -C (CH 3 ) 2-C (CH 3 ) 2- or -CH 2 -CH 2 -CH 2 - with two adjacent Rg) .
  • the aforementioned reaction can be performed in the presence of a transition metal catalyst.
  • a transition metal catalyst a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II), tet akis ( triphenylphosphine ) palladium ( 0 ) , bis ( triphenylphosphine ) palladium ( I I ) dichloride,
  • the amount of the palladium catalyst to be used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, per 1 mol of the compound (3) .
  • the amount of the compound (2a) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .
  • the aforementioned reaction can be performed in the absence or presence of a base.
  • the reaction is performed preferably in the presence of the base.
  • a conventionally known base can widely be used, and examples of the bases 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 such as 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
  • sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium hydride any 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 2.0 mol, per 1 mol of the compound (3) .
  • Examples of such a solvent include: fatty acid or
  • alicyclic hydrocarbon-based solvents such as n-hexane
  • 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, N-dimethylformamide (DMF), N,N- dimethylacetamide, N-methyl-2-pyrolidone and the like; and sulfoxide-based solvents such as dimethyl sulfoxide,
  • aromatic hydrocarbon- based solvents such as benzene, chloro
  • 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 (3) .
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -10°C and a boiling point of the solvent used and preferably 0 to 120°C.
  • Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.
  • the carbamate compound represented by Formula (IE) can be prepared by the reaction of a 5-substituted five-membered heterocycle compound (2b) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 2:
  • Ri, R 2 , R 3 , ⁇ , Rs, R-6 A X, Xi, Y, Z, 1, m and n are as defined above.
  • A represents halogen, methanesulfonyloxy, p- toluenesulfonyloxy or trifluoromethanesulfonyloxy .
  • R g represents hydrogen, Ci_ 6 alkyl (the substituent may form -CH 2 CH 2 -, -C (CH 3 ) 2 -C (CH 3 ) 2 - or -CH 2 -CH 2 -CH 2 - with two adj acent R 9 ) .
  • the aforementioned reaction can be performed in the presence of a transition metal catalyst.
  • a transition metal catalyst a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II), tetrakis ( triphenylphosphine )palladium(0) , bis ( triphenylphosphine ) palladium ( I I ) dichloride,
  • the amount of the palladium catalyst to be used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, per 1 mol of the compound (3) .
  • the amount of the compound (2b) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .
  • the aforementioned reaction can be performed in the absence or presence of a base.
  • the reaction is performed preferably in the presence of the base.
  • a conventionally known base can widely be used, and examples of the bases 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 such as 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
  • sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and sodium Hydride any 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 2.0 mol, per 1 mol of the compound (3) .
  • 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 , N-dimethylformamide (DMF), N,N- dimethylacetamide ,
  • 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 (3) .
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -10°C and a boiling point of the solvent used and preferably 0 to 120°C.
  • Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.
  • the carbamate compound represented by Formula (IF) can be prepared by the reaction of a 4 -substituted five-membered heterocycle compound (2c) with a boron compound (3) in the presence of a catalyst, a base and a solvent as mentioned in reaction scheme 3: Reaction scheme 3
  • R l7 R 2 , R 3 , R 4 , Rs, Re, Re, X, i, Y, Z, 1, m and n are as defined above.
  • A represents halogen, methanesulfonyloxy , p- toluenesulfonyloxy or trifluoromethanesulfonyloxy .
  • Rg represents hydrogen, Ci_6 alkyl (the substituent may form -CH 2 CH 2 -, -C (CH 3 ) 2 -C (CH 3 ) 2 - or -CH 2 -CH 2 -CH 2 - with two adj acent Rg) .
  • the aforementioned reaction can be performed in the presence of a transition metal catalyst.
  • a transition metal catalyst a conventionally known transition metal catalyst can widely be used, and examples of the transition metal catalyst include palladium compounds such as palladium acetate (II) , tetrakis (triphenylphosphine) palladium ( 0 ) , bis (triphenylphosphine) palladium ( II ) dichloride,
  • the amount of the palladium catalyst to be used is usually 0.01 to 1.0 mol, preferably 0.05 to 0.1 mol, per 1 mol of the compound (3) .
  • the amount of the compound (2c) to be used is usually 0.5 to 5 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .
  • the aforementioned reaction can be performed in the absence or presence of a base.
  • the reaction is performed preferably in the presence of the base.
  • a conventionally known base can widely be used, and examples of the bases 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 such as 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, t riethylamine , diethylamine , dimethylamine , methylamine, imidazole, benzimidazole, diisopropylethylamine , 4-dimethylamine pyridine, piperidine, and
  • the amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (3) .
  • Examples of such a solvent include: fatty acid or
  • alicyclic hydrocarbon-based solvents such as n-hexane
  • 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- dimethylacetamide , N-methyl-2-pyrolidone and the like; and sulfoxide-based solvents such as 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 1.0 to 20 liters, preferably 1.0 to 10 liters, per 1 mol of the compound (3) .
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between -10°C and a boiling point of the solvent used and preferably 0 to 120°C.
  • Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.
  • the compound (3) used in this step can be produced according to a known method (for example, the method described in WO2016/114165, WO2016/11 164 , O2016/114162 and
  • the carbamate compound represented by Formula (1) can be prepared by the reaction of a reagent (4) with a compound (1G) in the presence of a catalyst, a base and a solvent as
  • R lf R 2 , R 3 , R 4 , R 5 , Re, R 7 , R ' e, , Xi, Y, Z, 1, m and n are as defined above, and G represents a leaving group.
  • the ratio between the compound (1G) and a reagent (4) used in the reaction is not particularly limited and can appropriately be selected from a wide range.
  • the amount of a reagent (4) to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 2.0 mol, per 1 mol of the compound (1G) .
  • the aforementioned reaction can be performed in the absence or presence of a base. Among the above, the reaction is performed preferably in the presence of 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;
  • alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and the like
  • inorganic bases such as 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
  • alkali metal carbonates and alkali metal hydrides more preferably sodium carbonate, potassium
  • the amount of the base to be used is usually 1.0 to 5.0 mol, preferably 1.0 to 3.0 mol, per 1 mol of the compound (1G).
  • the aforementioned reaction can be performed by further adding a radical initiator.
  • the radical initiator include, but are not particularly limited to sulfurous acid adducts, such as sulfurous acid, a sulfurous acid salt,
  • Rongalite compound name, sodium formaldehydesulfoxylate
  • the base and' the radical initiator can be used in combination .
  • the amount of the radical initiator to be used is usually 0.1 to 10.0 mol, preferably 0.1 to 5.0 mol, per 1 mol of the compound (1G) .
  • solvents 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, carbon tetrachloride, and the like; ether-based solvents such as diethyl ether, THF, 1,4-dioxane, and the like; ester-based solvents such as methyl acetate, ethyl acetate, and the like; amide-based solvents such as acetonit rile ; DMF, N,N- dimethylacetamide , N-methyl-2-pyrrolidone , and the like;
  • polar solvents such as alcohol-based solvents such as
  • sulfolane methanol, ethanol, isopropyl alcohol, and the like; water; and the like. 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 (1G) .
  • 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 5 minutes to 48 hours, preferably from 10 minutes to 24 hours.
  • isolation means and purification means for example,
  • 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, In these formulations, the present compound is contained in a range of usually 0.1 to 99%, preferably 0.2 to 90% by weight.
  • the solid carrier examples include clays (for example, 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, and examples of 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), aliphatic hydrocarbons (for example, n-hexane, cyclohexane and kerosene), esters (for example, ethyl acetate and butyl acetate) , nitriles (for example, acetonitrile and iso
  • diisopropyl ether diisopropyl ether
  • acid amides for example, N,N-dimethyl formamide (DMF) and dimethylacetamide
  • halogenated for example, N,N-dimethyl formamide (DMF) and dimethylacetamide
  • hydrocarbons for example, dichloroethane trichloroethylene and carbon tetrachloride
  • 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.
  • stickers include stickers, dispersers and stabilizers, specifically casein, gelatin, polysaccharides (for example, starch, gum arabic, cellulose derivatives and alginic acid) , lignin
  • polymers for example, polyvinyl alcohol, polyvinyl
  • 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. In the
  • 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, atransplantation, an administration via injection
  • 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 agricultural lands or the others for cultivating the following ' 'plant' ' .
  • 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,
  • parsley, celery and parsnip parsley, celery and parsnip
  • chenopodiaceous vegetables for example, spinach and Swiss chard
  • lamiaceous vegetable's for example, Perilla frutescens, mint and basil
  • strawberry sweet potato
  • Dioscorea japonica colocasia and the others;
  • 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, walnuts, hazelnuts, almond, pistachio, cashew nuts and macadamia nuts), berry fruits (for example, blueberry, cranberry, blackberry and raspberry) , grape, kaki persimmon, olive, Japanese plum, banana, coffee, date palm, coconuts, 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 formosana, plane tree, zelkova, Japanese
  • arborvitae fir wood, hemlock, juniper, Pinus, Picea, and Taxus cuspidata
  • 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
  • Pear diseases scab (Venturia nashicola, V. pirina) , black spot (Alternaria alternata Japanese pear pathotype) and rust (Gymnosporangium haraeanum) ;
  • Grapes disease's anthracnose (Elsinoe ampelina) , ripe rot
  • 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 (Colletotrichum glycines, C. truncatum) , Rhizoctonia aerial blight (Rhizoctonia solani), septoria brown spot (Septoria glycines) and 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
  • reticulatum reticulatum
  • white scab Elsinoe leucospila
  • gray blight Pestalotiopsis sp.
  • anthracnose Coldletotrichum theae- sinensis
  • 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 homoeocarpa) , brown patch and large patch (Rhizoctonia solani); and
  • Delphacidae for example, Laodelphax
  • Deltocephalinae for example, Nephotettix cincticeps, or
  • Nephotettix virescens Nephotettix virescens
  • Aphididae for example, Aphis gossypii, Myzus persicae, Brevicoryne brassicae, Macrosiphum euphorbiae, Aulacorthum solani, Rhopalosiphum padi, Toxoptera citricidus
  • Pentatomidae for example, Nezara antennata, Riptortus
  • Halyomorpha mista, or Lygus lineolaris Halyomorpha mista, or Lygus lineolaris ) ; Aleyrodidae (for example, Trialeurodes vaporariorum, or Bemisia argentifolii ) ; Coccoidea (for example, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, or Icerya purchasi); Tingidae, Psyllidae; Bed bugs (Cimex lectularius) and the others .
  • Aleyrodidae for example, Trialeurodes vaporariorum, or Bemisia argentifolii
  • Coccoidea for example, Aonidiella aurantii, Comstockaspis perniciosa, Unaspis citri, Ceroplastes rubens, or Icerya purchasi
  • Lepidoptera Pyralidae (for example, Chilo suppressalis ,
  • Trichoplusia spp. Trichoplusia spp., Heliothis spp., or Helicoverpa spp.;
  • Pieridae for example, Pieris rapae
  • Tortricidae for example, Adoxophyes spp.
  • Grapholita molesta Cydia pomonella
  • Adoxophyes orana fasciata Adoxophyes sp . , Homona magnanima, Archips fuscocupreanus , Cydia pomonella); Gracillariidae (for example, Caloptilia theivora, Phyllonorycter ringoniella) ;
  • Carposinidae for example, Carposina niponensis
  • Lyonetiidae for example, Lyonetia spp.
  • Lymantriidae for example,
  • Lymantria spp., or Euproctis spp. Lymantria spp., or Euproctis spp.
  • Yponomeutidae for example, Plutella xylostella
  • Gelechiidae for example, Pectinophora gossypiella or Phthorimaea operculella
  • Arctiidae for example,
  • Tineidae for example, Tinea translucens, or Tineola bisselliella
  • 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,
  • 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,
  • Pyroglyphidae for example, Dermatophagoides farinae, or
  • Cheyletidae for example, Cheyletus eruditus, Cheyletus malaccensis, or Cheyletus
  • 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.
  • pests examples include Ixodes spp. (for example, Ixodes scapularis), Boophilus spp. (for example, Boophilus microplus), Amblyomma spp., Hyalomma spp., Rhipicephalus spp. (for example, Rhipicephalus sanguineus), Haemaphysalis spp.
  • Ixodes spp. for example, Ixodes scapularis
  • Boophilus spp. for example, Boophilus microplus
  • Amblyomma spp. for example, Hyalomma spp.
  • Rhipicephalus spp. for example, Rhipicephalus sanguineus
  • Sarcoptes spp. for example, Sarcoptes scabiei
  • Psoroptes spp. Chorioptes spp.
  • Demodex spp. Eutrombicula spp.
  • Trichostrongylus axei Trichostrongylus colubriformis
  • Trichinella spp. for example, Trichinella spiralis
  • Haemonchus contortus Haemonchus contortus
  • Nematodirus spp. for example,
  • the carbamate (1) of the invention is used, for example, as active ingredient for a fungicide.
  • the carbamate (1) of the invention can be used by being made into the desirable form such as an oil, emulsion, wettable powder, flowable preparation, granules, powder, aerosol, fumigant or the like.
  • the content of the carbamate (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 carbamate (1) of the invention as the active ingredient can be produced
  • the carbamate (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 8cerite, 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 8cerite 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 ,
  • ethers such as diisopropyl ether, dioxane, etc.
  • acid amides such as N, N-dimethylformamide, N, -dimethylacetamide, etc.
  • halogenated hydrocarbon such as dichloromethane , trichloroethane , carbon tetrachloride, etc.
  • dimethylsulfoxide soybean oil, cotton seed oil, vegetable oils and so on.
  • 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 ) , BRA (mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl- -methoxyphenol ) , vegetable oils, mineral oils, fatty acids, esters thereof and the like.
  • PAP acidic isopropyl phosphate
  • BBH 2, 6-di-tert-butyl-4- methylphenol
  • BRA mixture of 2-tert-butyl-4-methoxyphenol and 3-tert-butyl- -methoxyphenol
  • 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.
  • 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
  • pathogenic fungi examples 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.
  • Cuprous chloride (0.74 g, 7.5 mmol) was added to a cooled solution of 1- ( 2-nitrobenzyloxy ) -4-bromo-2-methylbenzene (1.2 g, 3.7 mmol) in methanol (10 ml) .
  • sodium borohydride (0.69 g, 18.7 mmol) was then portion-wise added. The resulting mixture was then stirred at room temperature for 2h. The reaction mixture was then quenched by saturated
  • reaction mixture was then diluted with ethyl acetate.
  • organic layer was then washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced
  • reaction mixture was filtered and diluted with ethyl acetate (100 mL) and washed with water (3 x 60 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure to afford the title compound as a light yellow solid (0.60 g, crude) . It was used as such in the next step without any further purification.
  • phenylcarbamate (0.65 g, 1.6 mmol) was added to the reaction mixture and then it was stirred at 100°C for 12h.
  • the reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 40 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure.
  • the crude compound was
  • dichloromethane complex (19 mg, 0.02 mmol) and methyl (3- methy1-2- ( ( 2 -methyl- 4 - (4,4,5, 5-tetramethyl-l , 3 , 2-dioxaborolan- 2-yl ) phenoxy ) methyl ) phenyl ) carbamate (0.10 g, 0.20 mmol) under nitrogen atmosphere.
  • the reaction was stirred at 100°C for 12h.
  • the reaction mixture was diluted with ethyl acetate (50 mL) and washed with water (3 x 20 mL) , dried over sodium sulfate and evaporated to dryness under reduced pressure.
  • F fluoro
  • CI chloro
  • Br bromo
  • Me methyl
  • Et ethyl
  • iPr isopropyl
  • t-Bu tert-butyl
  • CF 3 trifluoromethyl
  • Ph :
  • CDCI 3 /TMS 8.01 (bs, IH) , 7.82-
  • CDCI 3 /TMS 8.00 (bs, IH), 7.80-
  • CDCI 3 /TMS 8.12 (bs, IH) , 7.86-
  • CDCI 3 /TMS 7.78-7.75 (m, 3H) ,A- 7.35-7.26 (m, 2H) , 7.04-6.99 (m,
  • CDCI 3 /TMS 8.10 (s, IH) , 7.86-
  • CDCI 3 /TMS 9.07 (bs, IH) , 8.42
  • CDCI 3 /TMS 8.37 (s, IH) , 7.84 (d,
  • CDCI 3 /TMS 7.88 (s, IH) , 7.81 (d,
  • CDCI 3 /TMS 8.38 (s, IH), 7.85-
  • CDCI 3 /TMS 8.01-7.94 (m, 3H) , 7.86-7.82 (m, 2H) , 7.59 (bs,A- 4- (4- IH) , 7.41-7.37 (m, IH) , 7.34-
  • CDCI 3 /TMS 8.01-8.00 (m, IH) , 7.72 (bs, IH) , 7.39-7.35 (m, IH) , 7.31-7.27 (m, IH) , 7.09-A-
  • CDCI 3 /TMS 7.85 (bs, IH) , 7.73
  • Formulation example 1 Emulsifiable concentrate 10 parts of each compound of the invention was dissolved in 45 parts of Solvesso ® 150 and 35 parts of N- methylpyrrolidone . 10 parts of emulsifier (trade name: Sorpol ® 3005X, manufactured by Toho Kagaku Co., Ltd.) was added
  • 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,
  • Rhodorsil ® 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.
  • Test example is given below to demonstrate that the compound of the invention is useful as active ingredients of a
  • Test Examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for fungicides.
  • Test example 1 Fungicidal test on Sphaerotheca fuliginea, cucumber )
  • the solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old cucumber plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension (l> ⁇ 10 6 cfu spore per ml) .
  • the disease area rate after 12 days of inoculation was measured and the activity of the compound was shown as
  • Preventive value ⁇ 1- (disease area rate on treated) / (disease area rate on control) ⁇ x 100.
  • the solution of the compound of the invention (500 ppm and 200 ppm) was sprayed on fresh healthy cucumber plant at least three leaf stage.
  • the cotyledon of the treated plant was cut, and its leaf was put on moist tissue paper on plastic tray.
  • 50 ⁇ 1 of spore suspension (lxl0 6 cfu spore per ml) was dropped on the middle of the leaf using micropipette .
  • a small disc of absorbent cotton was put on the spore drop, and again the 50 ⁇ 1 of spore suspension was dropped on the disc. Leaves were kept at room temperature (20°C) .
  • the compounds that exhibited the preventive value of 50% or more at a treatment concentration of 500 ppm are as
  • the compounds that exhibited the preventive value of 50% or more at a treatment concentration of 200 ppm are as
  • Test example 3 Fungicidal test on Phytophthora infestans
  • the solution of the compound of the invention (500 ppm) was sprayed on fr'esh healthy tomato plant at least at the three leaf stage.
  • the plants were air-dried and inoculated with freshly prepared sporangia suspension (l> ⁇ 10 6 cfu zoospore per ml) .
  • the inoculated plants were then placed in a dew
  • thermostatic chamber (20°C, a humidity of 80%, and 16L8D) .
  • the disease area rate after 5 days of inoculation was measured and the activity of the compound was shown as preventive value calculated according to the following
  • Preventive value ⁇ 1- (disease area rate on treated) / (disease area rate on control) ⁇ x 100.
  • Test example 4 Fungicidal test on Pyricularia grisea
  • the solution of the compound of the invention (500 ppm) was sprayed on fresh healthy two week old millet plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension (lxl0 6 cfu spore per ml) .
  • 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%, and 16L8D) .
  • Preventive value ⁇ 1- (disease area rate on treated) / (disease area rate on control) ⁇ x 100.
  • the carbamate compound of the present invention has a controlling effect against plant diseases and is useful as an active ingredient of a plant control agent.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
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Abstract

Un des objets de la présente invention est de fournir un composé de carbamate ou un sel de celui-ci capable de lutter contre des maladies. La présente invention concerne un composé de carbamate représenté par la formule (1), ou un sel de celui-ci. Dans la formule, R1, R3 et R6 sont identiques ou différents et représentent chacun l'hydrogène, ou similaire ; R2 représente l'hydrogène, l'halogène ou un groupe alkyle en C1-C6 ; R4 et R5 sont identiques ou différents et représentent chacun l'hydrogène ou similaire ; R7 représente l'hydrogène ou similaire ; R8 représente l'hydrogène, ou un alkyle en C1-e ; X et Χ1 représentent indépendamment l'oxygène, ou le soufre ; Y représente l'oxygène, ou le soufre ; Z représente l'oxygène et/ou le soufre ; l est un nombre entier de 0 à 2 ; m est un nombre entier de 0 à 3 ; n est un nombre entier de 0 à 4 ; et lorsque l, m ou n est supérieur à un, les l, m ou n peuvent être identiques ou différents.
PCT/IB2018/050512 2017-01-30 2018-01-29 Nouveaux composés fongicides de carbamate WO2018138692A1 (fr)

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Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015147336A1 (fr) 2014-03-28 2015-10-01 住友化学株式会社 Composé aromatique et ses utilisations
WO2015147314A1 (fr) 2014-03-28 2015-10-01 住友化学株式会社 Composés aromatiques et leurs utilisations
EP3040332A1 (fr) * 2013-08-29 2016-07-06 Sumitomo Chemical Company, Limited Composé tétrazolinone et son utilisation
WO2016114161A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et son utilisation
WO2016114165A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et utilisation associée
WO2016114162A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et utilisation associée
WO2016114164A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé de carbamate et son utilisation

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3040332A1 (fr) * 2013-08-29 2016-07-06 Sumitomo Chemical Company, Limited Composé tétrazolinone et son utilisation
WO2015147336A1 (fr) 2014-03-28 2015-10-01 住友化学株式会社 Composé aromatique et ses utilisations
WO2015147314A1 (fr) 2014-03-28 2015-10-01 住友化学株式会社 Composés aromatiques et leurs utilisations
WO2016114161A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et son utilisation
WO2016114165A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et utilisation associée
WO2016114162A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé carbamate et utilisation associée
WO2016114164A1 (fr) 2015-01-13 2016-07-21 住友化学株式会社 Composé de carbamate et son utilisation

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