WO2018051252A2 - Nouveau composé amide, son procédé de production et miticide - Google Patents

Nouveau composé amide, son procédé de production et miticide Download PDF

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WO2018051252A2
WO2018051252A2 PCT/IB2017/055542 IB2017055542W WO2018051252A2 WO 2018051252 A2 WO2018051252 A2 WO 2018051252A2 IB 2017055542 W IB2017055542 W IB 2017055542W WO 2018051252 A2 WO2018051252 A2 WO 2018051252A2
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Prior art keywords
substituted
compound
alkyl
unsubstituted
salt
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PCT/IB2017/055542
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WO2018051252A3 (fr
Inventor
Tetsuya Imai
Surendra Kumar KUMAWAT
Manish Kumar SINGH
Pramod Kumar CHAUHAN
Ashish BHATT
Nikhil Vilas SURAMWAR
Amol Vasant SHELKE
Rajesh Kumar Singh
Ram Kishore
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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 WO2018051252A2 publication Critical patent/WO2018051252A2/fr
Publication of WO2018051252A3 publication Critical patent/WO2018051252A3/fr

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    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
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    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
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    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
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    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
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    • C07D235/24—Benzimidazoles; Hydrogenated benzimidazoles 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 in position 2
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    • C07D237/10—Heterocyclic compounds containing 1,2-diazine or hydrogenated 1,2-diazine rings not condensed with other rings having 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
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    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
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    • 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
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Definitions

  • the present invention relates to a novel amide compound, method for producing the same, and miticide containing the compound.
  • Patent Literature PTL-1 JP 2011/042611 discloses a compound represented by following Formula (A) :
  • R 5 represents substituted or unsubstituted C 1 -20 alkyl, substituted or unsubstituted amino, N-containing heterocycles, or the like, and reports that this compound exhibits miticidal activity.
  • PTL-1 mainly, urea compounds are produced, and in case of the amide compounds only those where R 5 is alkyl, haloalkyl, aryl, or cycloalkyl are disclosed, but the compounds of the present invention are not included.
  • PTL 1 nowhere discloses that the above compound (A) exhibits ovicidal activity.
  • Patent Literature PTL-2 discloses some bicyclic compounds as pest control agents and one type of general structure of this publication is represented by the formula (B) :
  • An object of the present invention is to provide a novel amide compound or a salt thereof that exhibits miticidal activity.
  • Another object of the present invention is to provide a method for producing the amide compound or the salt thereof.
  • a further object of the present invention is to provide a new type of miticide containing the amide compound or the salt thereof.
  • the present inventors conducted extensive research to achieve the above objects, and succeeded in synthesizing a compound represented by the following Formula (1) or a salt thereof that has miticidal 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:
  • Item 1 An amide compound represented by Formula (1)
  • R 1 represents C 1 _ 6 alkyl or C 1 _ 6 haloalkyl
  • R 2 and R 3 are identical or different and each represents hydrogen, halogen, cyano, nitro, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 1 _ 6 haloalkoxy C 1 _ 6 alkyl;
  • Q represents Q-1 or Q-2:
  • R 4 represents hydrogen, hydroxyl, formyl, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, C 1 _ 6 alkylcarbonyl, C 1 _ 6 haloalkylcarbonyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, cyano C 1 _ 6 alkyl, 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 2
  • R 5 and R 6 are identical or different and each represents hydrogen, halogen, C 1 _ 6 alkyl, or C 1 _ 5 haloalkyl; R 5 and R 6 , taken together with the carbon atom, may bond to each other to form a 3- to 7-membered ring, via or not via at least one heteroatom;
  • R 7 represents hydrogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 1 _ 6 haloalkoxy C 1 _ 6 alkyl, C 1 _ 6 alkylcarbonyl, C 1 _ 6 haloalkylcarbonyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 cyanoalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl, C 2-6 cyanoalkynyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, C 1 _ 6 alkylsulfonyl, C 1 _ 6 al
  • HET is a 5- or 6-membered heteroaryl, wherein the ring member atoms of the heteroaryl include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from N, 0 and S, and wherein the heteroaryl is unsubstituted or carries 1, 2, 3 or 4 identical or different groups R 8 ;
  • R 8 represents hydrogen, halogen, nitro, cyano, hydroxyl, formyl, substituted or unsubstituted amino, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 1 _ 6 haloalkoxy C 1 _ 6 alkyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, C 1 _ 6 cyanoalkyl, C 1 _ 6 cyanoalkoxy, C 2-6 alkenyl, C 2-6 haloalkenyl, C 2-6 cyanoalkenyl, C 2-6 alkynyl, C 2-6 haloalkynyl, C 2-6 cyanoalkynyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl, C 3
  • radicals R 8 that are bound to adjacent ring member atoms of the Het group may form together with said ring member atoms a fused ring system, in such a case, HET is fused with 5-, 6- or 7-membered saturated, partially unsaturated or aromatic heterocycle, wherein the ring member atoms of the fused heterocycle include besides carbon atoms 1, 2, 3 or 4 heteroatoms selected from the group of N, 0 and S, or with a substituted or unsubstituted aryl and wherein the fused carbocycle or heterocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different radicals groups R 8 ;
  • X represents oxygen or sulfur
  • n an integer of 0 to 2.
  • Item 4 The amide compound or the salt thereof according to Item 2, wherein HET is substituted or unsubstituted pyrazole, substituted or unsubstituted thiazole or substituted or unsubstituted pyridine .
  • R 3 represents halogen
  • R 4 represents hydrogen, C 1 _ 6 alkyl, or C 1 _ 6 alkylcarbonyl
  • R 5 and R 6 are identical or different and each represent hydrogen, halogen, or C 1 _ 6 alkyl
  • X represents 0 or S
  • X 1 , X 2 , and X 3 are identical or different and each represent halogen
  • HET represents pyrazolyl, thiazolyl, pyridyl, or imidazolyl, wherein the pyrazolyl, thiazolyl, pyridyl, and imidazolyl are unsubstituted or carry 1, 2, 3, or 4 identical or different groups R 8 ;
  • R 8 represents hydrogen, halogen, nitro, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkylthio, C 1 _ 6 haloalkylthio, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, the groups represented as R 8 may optionally be further substituted;
  • R 8 that are bound to adjacent ring member atoms of the Het group may form together with said ring member atoms a fused ring system, in such a case, HET is fused with a substituted or unsubstituted aryl and wherein the fused carbocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different groups R 8 ; and
  • n an integer of 0 to 2.
  • R 5 and R 6 are identical or different and each represent hydrogen, fluorine, chlorine, bromine, or C 1 _ 6 alkyl.
  • R 5 and R 6 are identical or different and each represent hydrogen, fluorine, chlorine, or C 1 _ 6 alkyl.
  • X 1 , X 2 , and X 3 are identical or different and each represent fluorine, chlorine, or bromine.
  • X 1 , X 2 , and X 3 are identical or different and each represent fluorine or chlorine.
  • n 0 or 1.
  • n 0.
  • R A1 , R A4 , and R A5 are identical or different and each represent hydrogen, halogen, nitro, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, pyridyl, or phenyl, wherein the pyridyl and phenyl are unsubstituted or substituted with one to three substituents selected from the group consisting of halogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkoxy, and C 1 _ 6 alkylthio; and
  • R A2 and R A3 are identical or different and each represent hydrogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, nitro, pyridyl, or thienyl;
  • R A6 , R A7 , R A8 , R A9 , R A1 °, and R A12 are identical or different and each represent hydrogen, halogen, C 1 _ 6 alkyl, or C 1 _ 6 haloalkyl;
  • R A11 and R A13 are identical or different and each represent hydrogen, halogen, nitro, C 1 _ 6 alkyl, or C 1 _ 6 haloalkyl;
  • k represents an integer of 0 to 4.
  • n an integer of 0 to 4.
  • R represents halogen
  • R 4 represents hydrogen, methyl, or ethyl
  • R 5 and R 6 are hydrogen, fluorine, methyl, or ethyl
  • X 1 , X 2 , and X 3 represent fluoro
  • R A1 represents nitro, chloro, cyano, bromo, trifluoromethyl, trifluoromethyl-substituted phenyl, trifluoromethoxy-substituted phenyl or fluoro-substituted phenyl;
  • R A2 and R A3 represent hydrogen, methyl, trifluoromethyl, ethyl, isopropyl, tert-butyl, or pyridyl;
  • R A4 represents halogen, 3, 5-dichlorophenyl, 3-chlorophenyl, 3- trifluoromethoxyphenyl, or 3-trifluoromethylphenyl;
  • R A5 represents hydrogen, halogen, C 1 _ 6 haloalkyl, unsubstituted phenyl, trifluoromethyl-substituted phenyl, or trifluoromethoxy- substituted phenyl;
  • R A6 , R A7 , and R A8 represent hydrogen
  • n an integer of 0 to 2.
  • R 3 represents halogen
  • R 4 represents hydrogen or methyl
  • R 5 and R 6 are hydrogen; X represents 0;
  • X 1 , X 2 , and X 3 represent fluoro
  • R al represents trifluoromethoxy-substituted phenyl or fluoro- substituted phenyl
  • R A2 and R A3 represent methyl
  • R A4 represents halogen
  • R A5 represents thienyl
  • R A6 , R A7 , and R A8 represent hydrogen
  • n an integer of 0 to 2.
  • An amide compound selected from the group consisting of compounds 1A -1-2, lA-1-3, 1A -1- 8, 1A- 1-9, lA-1- 10, lA-1- 11, lA-1-
  • An amide compound selected from the group consisting of compounds lA-1-24, lA-1-122, lA-1-177, and lA-1-204, or a salt thereof .
  • R 3 represents halogen
  • R 4 represents hydrogen or C 1 _ 6 alkyl
  • R 5 and R 6 are identical or different and each represent hydrogen or C 1 _ 6 alkyl
  • X represents 0 or S
  • X 1 , X 2 , and X 3 are identical or different and each represent halogen
  • n represents 0 or 1.
  • X 1 , X 2 , and X 3 are identical or different and each represent fluorine, chlorine, or bromine.
  • X 1 , X 2 , and X 3 are identical or different and each represent fluorine or chlorine.
  • n 0.
  • R 3 represents halogen
  • R 4 represents hydrogen, methyl, ethyl, n-propyl, or isopropyl; R 5 and R 6 are hydrogen;
  • X 1 , X 2 , and X 3 represent fluoro
  • R B3 is fluoro and R B1 , R B2 , R B4 , and R B5 are hydrogen, or
  • R B1 , R B2 , R B3 , and R B5 is chloro and the others are hydrogen, or R B2 is trifluoromethyl, trifluoromethoxy, trifluoromethylthio, 2- trifluoromethylphenyl, 3-trifluoromethylphenyl, 4- trifluoromethylphenyl, 3-trifluoromethoxyphenyl, or 4- trifluoromethoxyphenyl, and R B1 , R B3 , R B4 , and R B5 are hydrogen, or R B3 is trifluoromethyl, trifluoromethoxy, methylthio, trifluoromethylthio, 3-chlorophenyl, 2-trifluoromethylphenyl, 3- trifluoromethylphenyl, 4-trifluoromethylphenyl, 3- trifluoromethoxyphenyl, 4-trifluoromethoxyphenyl, pentafluorophenyl, 2 , 4-dichlorophenyl, 2,4-di- (trifluor
  • n 0 or 1.
  • R 4 represents hydrogen, methyl, ethyl, n-propyl, or isopropyl; R 5 and R 6 are hydrogen;
  • X 1 , X 2 , and X 3 represent fluoro
  • R B1 , R B2 , R B3 , R B4 , and R B5 are chloro and the others are hydrogen, or
  • R B3 represents hydrogen, halogen, methoxy, trifluoromethyl, trifluoromethoxy, methylthio, trifluoromethylthio, trifluoromethyl-substituted phenyl, or trifluoromethoxy- substituted phenyl and R B1 , R B2 , R B4 , and R B5 are hydrogen; and n represents 0 or 1.
  • Item 37 :
  • R represents halogen
  • R 4 represents hydrogen, methyl, or ethyl
  • R 5 and R 6 are hydrogen
  • X 1 , X 2 , and X 3 represent fluoro
  • R B1 , R B2 , R B3 , R B4 and R are chloro and the othe hydrogen, or
  • R B2 represents trifluoromethyl-substituted phenyl and R B1 ( R B3 R B4 and R B5 are hydrogen; and
  • n 0 or 1.
  • R represents halogen
  • R 4 represents hydrogen
  • R 5 and R 6 are hydrogen
  • X 1 , X 2 , and X 3 represent fluoro; two of R B1 , R B2 , R B3 , R B4 , and R B5 are chloro and the others are hydrogen, or
  • R B3 represents hydrogen, methoxy, or trifluoromethoxy and R B1 , R B2 , R B4 , and R B5 are hydrogen;
  • n 0 or 1.
  • R 3 represents halogen
  • R 4 represents hydrogen or C 1 _ 6 alkyl
  • X represents 0 or S
  • X 1 , X 2 , and X 3 are identical or different and each represent halogen
  • R 7 represents C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, substituted or unsubstituted pyridyl, or substituted or unsubstituted phenyl.
  • Item 48 The amide compound or the salt thereof according to any one of the preceding items, wherein X 1 , X 2 , and X 3 are identical or different and each represent fluorine, chlorine, or bromine.
  • X 1 , X 2 , and X 3 are identical or different and each represent fluorine or chlorine.
  • R 7 represents C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, pyridyl, or phenyl, wherein the phenyl is substituted with one to five substituents selected from the group consisting of halogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkoxy, C 1 _ 6 alkylthio, and C 1 _ 6 haloalkylthio .
  • a method for producing the amide compound or the salt thereof according to any one of the preceding items comprising at least one step selected from the group consisting of following steps (d) and (e) :
  • Step (d) obtaining the sulfide compound represented by Formula ( ⁇ -a) by reacting a thiol compound represented by Formula (6) with an alkylating reagent represented by Formula (7) :
  • R 1 , R 2 , R 3 , R% R 5 , R 6 , X and HET are as defined above and G represents a leaving group
  • Step (e) obtaining an amide compound represented by Formula ( ⁇ -b) by reacting the sulfide compound represented by Formula ( ⁇ -a) with an oxidizing agent:
  • n' represents 1 or 2.
  • step (c) The method for producing the amide compound or the salt thereof according to any one of the preceding items, further comprising the following step (c) :
  • Step (c) obtaining a thiol compound represented by Formula (6) by reacting a sulfonylchloride compound represented by Formula (5) with a reducing agent:
  • R 2 , R 3 , R 4 , R 5 , R 6 , X and HET are as defined above.
  • step (b) The method for producing the amide compound or the salt thereof according to any one of the preceding items, further comprising the following step (b) :
  • Step (b) obtaining the sulfonylchloride compound represented by Formula (5) by chlorosulfonylating a heteroaryl acetamide compound represented by Formula (4) :
  • step (a) The method for producing the amide compound or the salt thereof according to any one of the preceding items, further comprising the following step (a) :
  • Step (a) obtaining the heteroaryl acetamide compound represented by Formula (4) by reacting an aniline compound represented by Formula (2) with a heteroarylalkyl carbonyl compound represented by Formula (3) :
  • R 2 , R 3 , R 4 , R 5 , R 6 , X and HET are as defined above and Y represents a leaving group or hydroxyl group.
  • a pesticide containing the amide compound or the salt thereof according to any one of the preceding items is not limited to any one of the preceding items.
  • a mxticide containing the amide compound or the salt thereof according to any one of the preceding items is not limited to the preceding items.
  • the amide compound or the salt thereof according to the present invention achieves an excellent miticidal effect with a small amount thereof.
  • the amide compound and the salt thereof can simply be produced with an excellent yield.
  • a new type of miticide containing the amide compound or the salt thereof according to the present invention can be provided.
  • the present invention is directed to a compound represented by Formula (1) :
  • R 1 , R 2 , R 3 , Q and n are as defined above.
  • the number of substituents of a group defined by “optionally substituted” or “substituted” is not particularly limited if it is substitutable, and is one or plural.
  • the description for each group is also applied when the group is one part of or a substituent on other groups .
  • C 1 _ 6 alkyl means a linear or branched, saturated hydrocarbon group having one to six carbon atoms .
  • C 1 -4 alkyl means a linear or branched, saturated hydrocarbon group having one to four carbon atoms .
  • C 2-6 alkenyl means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and containing one to three double bonds .
  • C 2-6 alkynyl means a linear or branched, unsaturated hydrocarbon group having two to six carbon atoms and containing one triple bond.
  • C 3 _ 8 cycloalkyl means a cyclic alkyl having three to eight carbon atoms, and includes those cyclic alkyl having a partially bridged structure.
  • C 1 _ 6 alkoxy refers to a “C 1 _ 6 alkyloxy group", and the “C 1 _ 6 alkyl” moiety is defined the same as the above-described "C 1 _ 6 alkyl”.
  • Aryl means a monocyclic or polycyclic aromatic hydrocarbon.
  • 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.
  • C 1 _ 6 alkyl include, but are not particularly limited to, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, n-hexyl, and like C 1 _ 6 straight- chain or branched-chain alkyl.
  • C 1 _ 6 haloalkyl examples include, but are not particularly limited to, fluoromethyl, chloromethyl, bromomethyl, iodomethyl, difluoromethyl, 2, 2-difluoroethyl, trifluoromethyl, 2,2,2- trifluoroethyl, pentafluoroethyl, 3, 3, 3-trifluoropropyl, 4,4,4- trifluorobutyl, heptafluoroisobutyl, and like C 1 _ 6 straight-chain or branched-chain alkyl substituted with 1 to 9, and preferably 1 to 5, halogen atoms.
  • C 1 _ 6 alkoxy examples include, but are not particularly limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, isobutoxy, sec-butoxy, tert-butoxy, and like C 1 _ 6 straight-chain or branched-chain alkoxy.
  • C 1 _ 6 haloalkoxy examples include, but are not particularly limited to, fluoromethoxy, chloromethoxy, bromomethoxy, iodomethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2- trifluoroethoxy, pentafluoroethoxy, 3, 3, 3-trifluoropropoxy, 4, 4, 4-trifluorobutoxy, heptafluoroisobutoxy, and like C 1 _ 6 straight-chain or branched-chain alkoxy substituted with 1 to 9, preferably 1 to 5, halogen atoms.
  • C 1 _ 6 alkoxy C 1 _ 6 alkyl examples include, but are not particularly limited to, methoxymethyl, ethoxymethyl, n- propoxymethyl, isopropoxymethyl, n-butoxymethyl, isobutoxymethyl, sec-butoxymethyl, tert-butoxymethyl, methoxyethyl, ethoxyethyl, methoxy-n-propyl, methoxy-n-butyl, and like alkoxyalkyl in which C 1 _ 6 straight-chain or branched-chain alkyl is substituted with C 1 _ 6 straight-chain or branched-chain alkoxy.
  • C 1 _ 6 haloalkoxy C 1 _ 6 alkyl examples include, but are not particularly limited to, fluoromethoxymethyl, chloromethoxymethyl, bromomethoxymethyl, iodomethoxymethyl, difluoromethoxymethyl, trifluoromethoxymethyl, 2, 2, 2-trifluoroethoxymethyl, and like straight-chain or branched-chain alkoxyalkyl substituted with 1 to 9, preferably 1 to 5, halogen atoms.
  • C 3 _ 8 cycloalkyl examples include, but are not particularly limited to, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and the like.
  • C 3 _ 8 cycloalkyl C 1 _ 6 alkyl examples include, but are not particularly limited to, cyclopropylmethyl, cyclobutylethyl, cyclopentylmethyl, cyclohexylmethyl, 1-cyclohexylethyl (i.e., CH(C 6 Hii) -CH 3 ) , and the like.
  • C 1 _ 6 alkylcarbonyl examples include, but are not particularly limited to, methylcarbonyl (acetyl) , ethylcarbonyl (propionyl) , n-propylcarbonyl (butyryl) , isopropylcarbonyl (isobutyryl) , n-butylcarbonyl (valeryl) , isobutylcarbonyl (isovaleryl) , see-butylcarbonyl, tert-butylcarbonyl, and like C 1 _ 6 straight-chain or branched-chain alkylcarbonyl groups.
  • C 1 _ 6 haloalkylcarbonyl examples include, but are not particularly limited to, fluoromethylcarbonyl, chloromethylcarbonyl, bromomethylcarbonyl, iodomethylcarbonyl, dichloromethylcarbonyl, trichloromethylcarbonyl, difluoromethylcarbonyl, trifluoromethylcarbonyl, chlorodifluoromethylcarbonyl, bromodifluoromethylcarbonyl, dichlorofluoromethylcarbonyl, 2, 2, 2-trichloroethylcarbonyl,
  • arylcarbonyl examples include, but are not particularly limited to, benzoyl, tert-butylbenzoyl, and like substituted or unsubstituted benzoyl group; 1-naphthoyl, 2- naphthoyl, and the like substituted or unsubstituted naphthoyl group.
  • aryloxycarbonyl examples include, but are not particularly limited to, phenoxycarbonyl, 4- diaminophenoxycarbonyl, 4-fluorophenoxycarbonyl, 4-tert- butylphenoxycarbonyl, and like substituted or unsubstituted phenoxycarbonyl group; 1-naphthoxycarbonyl, 2-naphthoxycarbonyl, and the like substituted or unsubstituted naphthoxycarbonyl group.
  • C 1 _ 6 alkoxycarbonyl examples include, but are not particularly limited to, methoxycarbonyl, ethoxycarbonyl, n- propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, and like C 1 _ 6 straight-chain or branched-chain alkoxycarbonyl groups.
  • C 1 _ 6 haloalkoxycarbonyl examples include, but are not particularly limited to, fluoromethoxycarbonyl, chloromethoxycarbonyl , bromomethoxycarbonyl , iodomethoxycarbonyl , dichloromethoxycarbonyl , trichloromethoxycarbonyl , difluoromethoxycarbonyl, trifluoromethoxycarbonyl, 2,2,2- trifluoroethoxymethyl, pentafluoroethoxycarbonyl, 3,3,3- trifluoropropoxycarbonyl, 4 , 4 , 4-trifluorobutoxycarbonyl, heptafluoroisopropoxycarbonyl, and like C 1 _ 6 straight-chain or branched-chain alkoxycarbonyl substituted with 1 to 9, preferably 1 to 5, halogen atoms.
  • cyano C 1 _ 6 alkyl examples include, but are not particularly limited to, cyanomethyl, cyanoethyl, cyano-n-propyl, cyano-isopropyl, cyano-n-butyl, cyano-isobutyl, cyano-sec-butyl, cyano-tert-butyl, cyano-n-hexyl, and like C 1 _ 6 straight-chain or branched-chain alkyl substituted with a cyano group.
  • cyano C 1 _ 6 alkoxy examples include cyanomethoxy, cyanoethoxy, cyano-n-propoxy, cyano-isopropoxy, cyano-n-butoxy, cyano-iso-butoxy, cyano-sec-butoxy, cyano-tert-butoxy, cyano- hexyloxy, and like C 1 _ 6 straight-chain or branched-chain alkoxy substituted with a cyano group.
  • C 2-6 alkenyl examples include, but are not particularly limited to, vinyl, allyl, 2-butenyl, 3-butenyl, 1-methylallyl, and the like.
  • C 2-6 haloalkenyl examples include, but are not particularly limited to, 2, 2-dichlorovinyl, 2, 2-dibromovinyl, 2, 2-difluorovinyl, 3, 3-difluoro-2-allyl, 4, 4-difluoro-3-butenyl, 4 , 4 , 4-trifluoro-2-butenyl, and the like.
  • C 2-6 alkynyl examples include, but are not particularly limited to, ethynyl, 2-propynyl (propargyl) , l-methyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1, l-dimethyl-2-propyn-l-yl (i.e., -C (CH 3 ) 2 -CCH) , and the like.
  • C 2-6 haloalkynyl examples include, but are not particularly limited to, fluoroethynyl, bromoethynyl, chloroethynyl, iodoethynyl, 3, 3, 3-trifluoro-l-propynyl, and the like.
  • C 2-6 cyanoalkenyl 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, 4 , 4 , 4-tricyano-2-butenyl, and the like.
  • C 2-6 cyanoalkynyl examples include, but are not particularly limited to, cyanoethynyl, 3-cyano-l-propynyl, 3,3,3- trifluoro-l-propynyl, and the like.
  • C 1 _ 6 alkylsulfonyl examples include, but are not particularly limited to, methylsulfonyl, ethylsulfonyl, n- propylsulfonyl, isopropylsulfonyl, n-butylsulfonyl, isobutylsulfonyl, sec-butylsulfonyl, tert-butylsulfonyl, and like C 1 _ 6 straight-chain or branched-chain alkylsulfonyl groups.
  • C 1 _ 6 haloalkylsulfonyl examples include, but are not particularly limited to, fluoromethylsulfonyl, chloromethylsulfonyl, bromomethylsulfonyl, iodomethylsulfonyl, dichloromethylsulfonyl, trichloromethylsulfonyl, difluoromethylsulfonyl, trifluoromethylsulfonyl, chlorodifluoromethylsulfonyl, bromodifluoromethylsulfonyl, dichlorofluoromethylsulfonyl, 2,2, 2-trichloroethylsulfonyl,
  • C 1 _ 6 alkylsulfinyl examples include, but are not particularly limited to, methylsulfinyl, ethylsulfinyl, n- propylsulfinyl, isopropylsulfinyl, n-butylsulfinyl, isobutylsulfinyl, sec-butylsulfinyl, tert-butylsulfinyl, and like C 1 _ 6 straight-chain or branched-chain alkylsulfinyl groups.
  • C 1 _ 6 haloalkylsulfinyl examples include, but are not particularly limited to, fluoromethylsulfinyl, chloromethylsulfinyl, bromomethylsulfinyl, iodomethylsulfinyl, dichloromethylsulfinyl, trichloromethylsulfinyl, difluoromethylsulfinyl, trifluoromethylsulfinyl, chlorodifluoromethylsulfinyl, bromodifluoromethylsulfinyl, dichlorofluoromethylsulfinyl, 2,2, 2-trichloroethylsulfinyl,
  • C 1 _ 6 alkylthio examples include, but are not particularly limited to, methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio, sec-butylthio, tert-butylthio, and like C 1 _ 6 straight-chain or branched-chain alkylthio.
  • C 1 _ 6 haloalkylthio examples include, but are not particularly limited to, fluoromethylthio, chloromethylthio, bromomethylthio, iodomethylthio, dichloromethylthio, trichloromethylthio, difluoromethylthio, trifluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, dichlorofluoromethylthio, 2, 2, 2-trichloroethylthio, 2,2,2- trifluoroethylthio, pentafluoroethylthio, and like C 1 _ 6 straight- chain or branched-chain alkylthio substituted with 1 to 9, and preferably 1 to 5, halogen atoms.
  • C 3 _ 8 cycloalkylsulfonyl examples include, but are not particularly limited to, cyclopropylsulfonyl, cyclobutylsulfonyl, cyclopentylsulfonyl, cyclohexylsulfonyl, and the like.
  • C 3 _ 8 cycloalkylsulfinyl examples include, but are not particularly limited to, cyclopropylsulfinyl, cyclobutylsulfinyl, cyclopentylsulfinyl, cyclohexylsulfinyl, and the like.
  • C 3 _ 8 cycloalkylthio examples include, but are not particularly limited to, cyclopropylthio, cyclobutylthio, cyclopentylthio, cyclohexylthio, and the like.
  • C 3 _ 8 cycloalkyl C 1 _ 6 alkylsulfonyl examples include, but are not particularly limited to, cyclopropylmethylsulfonyl, 2- cyclopropylethylsulfonyl, 3-cyclopropylpropylsulfonyl, cyclohexylmethylsulfonyl, and the like.
  • C 3 _ 8 cycloalkyl C 1 _ 6 alkylsulfinyl include, but are not particularly limited to, cyclopropylmethylsulfinyl, 2- cyclopropylethylsulfinyl, 3-cyclopropylpropylsulfinyl, cyclohexylmethylsulfinyl, and the like.
  • Examples of C 3 _ 8 cycloalkyl C 1 _ 6 alkylthio include, but are not particularly limited to, cyclopropylmethylthio, 2- cyclopropylethylthio, 3-cyclopropylpropylthio, cyclohexylmethylthio, and the like.
  • C 1 _ 6 alkoxy C 1 _ 6 alkylthio examples include, but are not particularly limited to, methoxymethylthio, ethoxymethylthio, n- propoxymethylthio, isopropoxymethylthio, n-butoxymethylthio, sec- butoxymethylthio, tert-butoxymethylthio, 2-methoxyethylthio, and like alkoxyalkylthio in which C 1 _ 6 straight-chain or branched- chain alkylthio is substituted with C 1 _ 6 straight-chain or branched-chain alkoxy.
  • C 2-6 alkenyloxy examples include, but are not particularly limited to, vinyloxy, 1-propenyloxy, isopropenyloxy, allyloxy, 2- butenyloxy, 3-butenyloxy, 1-methylallyloxy, and the like.
  • 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, 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, l-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-l-propynyloxy, and the like.
  • C 1 _ 6 alkylsulfonyloxy examples include, but are not particularly limited to, methylsulfonyloxy, ethylsulfonyloxy, n- propylsulfonyloxy, isopropylsulfonyloxy, n-butylsulfonyloxy, isobutylsulfonyloxy, sec-butylsulfonyloxy, tert-butylsulfonyloxy, and like C 1 _ 6 straight-chain or branched-chain alkylsulfonyl groups .
  • C 1 _ 6 alkylsulfinyloxy examples include, but are not particularly limited to, methylsulfinyloxy, ethylsulfinyloxy, n- propylsulfinyloxy, isopropylsulfinyloxy, n-butylsulfinyloxy, isobutylsulfinyloxy, see-butylsulfinyloxy, tert-butylsulfinyloxy, and like C 1 _ 6 straight-chain or branched-chain alkylsulfinyloxy groups .
  • substituted or unsubstituted amino examples include, but are not particularly limited to, amino, monoalkylamino, dialkylamino, monoacylamino, and the like.
  • alkyl examples include C 1 _ 6 alkyl mentioned above, and the like.
  • acyl examples include C 1 _ 6 alkoxycarbonyl, haloalkoxycarbonyl, arylcarbonyl mentioned above, and the like.
  • aryl examples include, but are not particularly limited to, phenyl, 1-naphthyl, 2-naphthyl, and the like.
  • aryl C 1 _ 6 alkyl examples include, but are not particularly limited to, benzyl, phenylethyl, phenyl-n-propyl, 1-methyl-l- phenyl-ethyl (i.e., -C (CH 3 ) 2 -C 6 H 5 ) , and the like. These aryl C 1 _ 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 C 1 _ 6 alkoxy examples include, but are not particularly limited to, benzyloxy, phenylethoxy, phenyl-n- propoxy, phenyl-n-butoxy, 1-naphthylmethoxy, 2-naphthylmethoxy, and like.
  • heteroaryloxy examples include, but are not particularly limited to, pyridinyloxy, pyrimidinyloxy, pyrazolyloxy, and the like.
  • heteroaryl C 1 _ 6 alkoxy examples include, but are not particularly limited to, pyridinylmethoxy, pyridinylethoxy, pyrimidinylethoxy, pyrazolylmethoxy, and like.
  • arylsulfonyl examples include, but are not particularly limited to, phenylsulfonyl, 1-naphthylsulfonyl, 2- naphthylsulfonyl, and the like.
  • arylsulfinyl examples include, but are not particularly limited to, phenylsulfinyl, 1-naphthylsulfinyl, 2- naphthylsulfinyl, and the like.
  • arylthio examples include, but are not particularly limited to, phenylthio, 1-naphthylthio, 2-naphthylthio, and the like.
  • arylsulfonyloxy examples include, but are not particularly limited to, phenylsulfonyloxy, 1-naphthylsulfonyloxy, 2-naphthylsulfonyloxy, and the like.
  • arylsulfinyloxy examples include, but are not particularly limited to, phenylsulfinyloxy, l ⁇ naphthylsulfinyloxy, 2-naphthylsulfinyloxy, and the like.
  • aryl C 1 _ 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.
  • HET which is basically a 5- or 6-membered heteroaryl
  • HET which is basically a 5- or 6-membered heteroaryl
  • examples of HET which is basically a 5- or 6-membered heteroaryl include, but are not particularly limited to, thienyl, furyl, pyrrolyl, oxazolyl, isoxazolyl, thiazolyl, isothiazolyl, pyrazolyl, imidazolyl, oxadiazolyl, thiadiazolyl, triazolyl, tetrazolyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, triazinyl, tetrazinyl, indolyl, isoindolyl, indazolyl, quinazolinyl, carbazolyl, benzoxazolyl, benzisoxazolyl, benzothiazolyl, benzisothiazolyl,
  • heteroaryl examples are similar but not limited to those mentioned above in HET examples.
  • heteroaryl C 1 _ 6 alkyl examples include, but are not particularly limited to, pyrazolylmethyl, thiazolylmethyl, oxazolylmethyl, 2-pyridylmethyl, 3-pyridylmethyl, 2- pyrazinylmethyl, pyrimidinylmethyl, 2-quinolinylmethyl, and the like. These heteroaryl C 1 _ 6 alkyl can be further substituted at both the parts alkyl as well as heteroaryl.
  • All the Aryls, Aryl C 1 _ 6 alkyls, Heteroaryls and Heteroaryl C 1 _ 6 alkyls, mentioned above may optionally be further substituted.
  • Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
  • heterocyclic group examples include, but are not particularly limited to, thienyl, furyl, tetrahydrofuryl, dioxolanyl, dioxanyl, pyrrolyl, pyrrolinyl, pyrrolidinyl, oxazolyl, isoxazolyl, oxazolinyl, oxazolidinyl, isoxazolinyl, thiazolyl, isothiazolyl, thiazolinyl, thiazolidinyl, isothiazolinyl, pyrazolyl, pyrazolidinyl, imidazolyl, imidazolinyl, imidazolidinyl, oxadiazolyl, oxadiazolinyl, thiadiazolinyl, triazolyl, triazolinyl, triazolidinyl, tetrazolyl, tetrazolinyl, pyridyl, dihydrox
  • heterocyclic groups include those substituted at any substitutable position with an oxo or thioketone group. All the heterocyclics mentioned above may optionally be further substituted. Examples of the number of substituents include, but are not particularly limited to, 1 to 20 (preferably 1 to 10, and more preferably 1 to 5) .
  • R 5 and R 6 taken together with the carbon atom to which they bond, may bond to each other to form a 3- to 8-membered ring via or not via at least one heteroatom.
  • hetero atom in the specification include, but are not particularly limited to, an oxygen atom, a sulfur atom, a nitrogen atom, and the like.
  • 3- to 8-membered ring include: but are not particularly limited to, cyclopropane, cycloheptane, and the like C 3 _ 8 cycloalkyl; tetrahydropyran, piperidine, and the like heterocyclic.
  • substituted or substituted include: but are not particularly limited to, the halogen, nitro, cyano, hydroxyl, formyl, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 1 _ 6 haloalkoxy C 1 _ 6 alkyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, C 1 _ 6 alkylcarbonyl, C 1 _ 6 haloalkylcarbonyl, arylcarbonyl, aryloxycarbonyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, C 1 _ 6 cyanoalkyl, C 1 _ 6 cyanoalkyl, C 1 _ 6 cyanoalkyl, C 1 _
  • preferable substituents are halogen, nitro, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkylsulfonyl, C 1 _ 6 haloalkylsulfonyl, C 1 _ 6 alkylsulfinyl, C 1 _ 6 haloalkylsulfinyl, C 1 _ 6 alkylthio, C 1 _ 6 haloalkylthio, substituted or unsubstituted amino, aryl, and heterocyclic, and more preferable substituents are fluorine, chlorine, nitro, methyl, ethyl, trifluoromethyl, methoxy, and trifluoromethoxy .
  • Preferable substituted aryl groups are halogen-substituted aryl, C 1 _ 6 alkyl-substituted aryl, C 1 _ 6 haloalkyl-substituted aryl, halogen and C 1 _ 6 haloalkyl-substituted aryl, C 1 _ 6 alkoxy- substituted aryl, C 1 _ 6 haloalkoxy-substituted aryl, and C 1 _ 6 alkylthio-substituted aryl.
  • More preferable substituted aryl groups are chlorine-substituted aryl, fluorine-substituted aryl, trifluoromethyl-substituted aryl, chlorine- and trifluoromethyl- substituted aryl, trifluoromethoxy-substituted aryl, and methoxy- substituted aryl, and methylthio-substituted aryl.
  • Preferable substituted heteroaryl groups are halogen- substituted heteroaryl, C 1 _ 6 alkyl-substituted heteroaryl, C 1 _ 6 haloalkyl-substituted heteroaryl, halogen and C 1 _ 6 haloalkyl — substituted heteroaryl, C 1 _ 6 alkoxy-substituted heteroaryl, C 1 _ 6 haloalkoxy-substituted heteroaryl, and C 1 _ 6 alkylthio-substituted heteroaryl.
  • More preferable substituted heteroaryl groups are chlorine-substituted heteroaryl, fluorine-substituted heteroaryl, trifluoromethyl-substituted heteroaryl, chlorine- and trifluoromethyl-substituted heteroaryl, trifluoromethoxy- substituted heteroaryl, and methoxy-substituted heteroaryl, and methylthio-substituted heteroaryl .
  • Preferable substituted heterocyclic groups are halogen- substituted heterocyclic, C 1 _ 6 alkyl-substituted heterocyclic, C 1 _ 6 haloalkyl-substituted heterocyclic, C 1 _ 6 alkoxy-substituted heterocyclic, C 1 _ 6 haloalkoxy-substituted heterocyclic, and C 1 _ 6 alkylthio-substituted heterocyclic.
  • More preferable substituted heterocyclic groups are chlorine-substituted heterocyclic, fluorine-substituted heterocyclic, trifluoromethyl-substituted heterocyclic, trifluoromethoxy-substituted heterocyclic, methoxy- substituted heterocyclic, and methylthio-substituted heterocyclic.
  • the salts of the compounds represented by Formula (1) may be any type of salts as long as they are agriculturally acceptable.
  • the salts include a hydrochloride salt, a sulfate salt, a nitrate salt, and like inorganic acid salts; an acetate salt, a methanesulfonic acid salt, and like organic acid salts; a sodium salt, a potassium salt, and like alkali metal salts; a magnesium salt, a calcium salt, and like alkaline earth metal salts; dimethylammonium, triethylammonium, and like quaternary ammonium salts; and the like.
  • X represents oxygen or sulfur.
  • n an integer of 0 to 2.
  • a preferable compound is a compound in which HET is 5- or 6- membered heteroaryl
  • a more preferable compound among 1 and 1A is a compound in which HET is substituted or unsubstituted pyrazole, substituted or unsubstituted thiazole, substituted or unsubstituted pyridine, substituted or unsubstituted imidazole, or substituted or unsubstituted benzimidazole
  • a further preferable compound among 1 and 1A is a compound in which HET is substituted or unsubstituted pyrazole or substituted or unsubstituted thiazole or substituted or unsubstituted pyridine.
  • a preferable compound is a compound in which R 7 is C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, substituted or unsubstituted aryl, substituted or unsubstituted aryl C 1 _ 6 alkyl, and a more preferable compound among 1 and IB is a compound in which R 7 is optionally substituted aryl or optionally substituted aryl C 1 _ 6 alkyl.
  • substituents are chloro, bromo, fluoro, methyl, trifluoromethyl, trifluoromethoxy, methylthio, trifluoromethylthio, or substituted aryl.
  • aryl C 1 _ 6 alkyl preferable aryl substituents are same as those described above, wherein C 1 _ 6 alkyl is preferably substituted with halogen, or C 1 _ 6 alkyl.
  • a preferable compound is a compound in which R 1 is C 1 _ 6 haloalkyl, and a more preferable compound among 1, 1A and IB is a compound in which R 1 is trifluoroethyl .
  • a preferable compound is a compound in which R 2 is hydrogen, halogen, or C 1 _ 6 alkyl, and a more preferable compound (1) is a compound in which R 2 is fluorine, chlorine, bromine, or methyl.
  • a preferable compound is a compound in which R 3 is hydrogen, halogen, or C 1 _ 6 alkyl, and a more preferable compound (1) is a compound in which R 3 is fluorine, chlorine, bromine, or methyl.
  • a preferable compound is a compound in which R 4 is hydrogen, C 1 _ 6 alkyl, C 2-6 alkenyl, C 2-6 alkynyl, C 1 _ 6 haloalkyl, or C 1 _ 6 alkylcarbonyl and a more preferable compound (1) is a compound in which R 4 is hydrogen, methyl, ethyl, n-propyl, i-propyl or acetyl.
  • a preferable compound is a compound in which R 5 and R 6 are identical or different and each represents hydrogen, halogen, or C 1 _ 6 alkyl, and a more preferable compound (1) is a compound in which R 5 and R 6 are hydrogen, fluorine, or methyl.
  • a preferable compound is a compound in which R 1 is CH 2 C(X 1 ) (X 2 ) (X 3 ) wherein X 1 , X 2 , and X 3 are identical or different and each represent halogen; a more preferable compound (1) is a compound in which X 1 , X 2 , and X 3 are identical or different and each represent fluorine, chlorine, or bromine; a further more preferable compound (1) is a compound in which X 1 , X 2 , and X 3 are identical or different and each represent fluorine or chlorine; and a most preferable compound (1) is a compound in which X 1 , X 2 , and X 3 are fluorine.
  • a preferable compound is a compound in which R 2 is methyl .
  • a preferable compound is a compound in which R 3 is halogen; a more preferable compound is a compound in which R 3 is fluorine, chlorine, or bromine; a further more preferable compound is a compound in which R 3 is fluorine or chlorine; and a most preferable compound is a compound in which R 3 is fluorine.
  • a preferable compound is a compound in which R 4 is hydrogen, C 1 _ 6 alkyl, or C 1 _ 6 alkylcarbonyl; a more preferable compound (1) is a compound in which R 4 is hydrogen, methyl, or ethyl; a more preferable compound (1) is a compound in which R 4 is hydrogen or methyl; and a most preferable compound (1) is a compound in which R 4 is hydrogen.
  • a preferable compound is a compound in which R 5 and R 6 are identical or different and each represent hydrogen or C 1 _ 6 alkyl; a more preferable compound (1) is a compound in which R 5 and R 6 are identical or different and each represent hydrogen or methyl; and a most preferable compound (1) is a compound in which R 5 and R 6 are hydrogen.
  • a preferable compound is a compound in which X is oxygen or sulfur
  • a more preferable compound (1) is a compound in which X is oxygen
  • a preferable compound is a compound in which n is 0.
  • a preferable compound is a compound in which R 8 represents hydrogen, halogen, nitro, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkylthio, C 1 _ 6 haloalkylthio, substituted or unsubstituted aryl, or substituted or unsubstituted heteroaryl, the groups represented as R 8 may optionally be further substituted; or two radicals R 8 that are bound to adjacent ring member atoms of the Het group may form together with said ring member atoms a fused ring system, in such a case, HET is fused with a substituted or unsubstituted aryl and wherein the fused carbocycle is unsubstituted or carries 1, 2, 3 or 4 identical or different groups R 8 .
  • a preferable compound is a compound in which HET represents
  • R A1 , R A4 , and R A5 are identical or different and each represent hydrogen, halogen, nitro, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, pyridyl, or phenyl, wherein the pyridyl and phenyl are unsubstituted or substituted with one to three substituents selected from the group consisting of halogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkoxy, and C 1 _ 6 alkylthio; and
  • R A2 and R A3 are identical or different and each represent hydrogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, nitro, pyridyl, or thienyl;
  • R' A6 R A7 R A8 R A9 R A10 and R A12 are identical or different and each represent hydrogen, halogen, C 1 _ 6 alkyl, or C 1 _ 6 haloalkyl;
  • R A11 and R A13 are identical or different and each represent hydrogen, halogen, nitro, C 1 _ 6 alkyl, or C 1 _ 6 haloalkyl;
  • k represents an integer of 0 to 4.
  • n an integer of 0 to 4.
  • a preferable compound is a compound in which R 7 is a group of the formula:
  • R B1 , R B2 , R B3 , R B4 , and R BS are identical or different and each represents hydrogen, halogen, C 1 _ 6 alkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkoxy, C 1 _ 6 alkylthio, C 1 _ 6 haloalkylthio, or phenyl, wherein the phenyl is substituted with one to five substituents . selected from the group consisting of halogen, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 haloalkoxy, and C 1 _ 6 alkylthio.
  • a preferable compound is a compound in which R 7 represents C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, substituted or unsubstituted pyridyl, or substituted or unsubstituted phenyl.
  • any of the isomers and mixtures thereof are included within the scope of the compound (1) .
  • the compound (1) has optical isomers
  • the optical isomer separated from a racemic body is also included within the scope of the compound (1) .
  • Each of such isomers may be obtained as a single compound by known synthesis and separation means (e.g., concentration, solvent extraction, column chromatography, recrystallization, etc.).
  • a heteroarylacetamide compound (hereinafter may be referred to as "compound (4)") represented by Formula (4) can be produced by reacting an aniline compound (hereinafter may be referred to as “compound (2)”) represented by Formula (2) with a heteroarylalkylcarbonyl compound (hereinafter may be referred to as "compound (3)”) represented by Formula (3) (Reaction Scheme 2) :
  • R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above.
  • Y represents a leaving group or a hydroxyl group
  • the leaving group include: halogen such as chlorine, bromine, and iodine; substituted or unsubstituted C 1 _ 6 alkyl sulfonate; and substituted or unsubstituted aryl sulfonate.
  • the substituent include the aforementioned substituents such as halogen and C 1 _ 6 haloalkyl.
  • Step 1A (when Y is a leaving group)
  • a heteroarylacetamide compound (4) can be produced by reacting the aniline compound (2) with a heteroarylalkylcarbonyl compound (hereinafter may be referred to as "compound (3A)”) represented by Formula (3A) (Reaction Scheme 3) :
  • R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above.
  • Y' represents a leaving group and examples of the leaving groups are same as those described above.
  • heteroarylalkylcarbonyl compound (3A) examples include, but are not particularly limited to, heteroarylacetyl chloride, heteroarylacetyl bromide, and the like substituted or unsubstituted heteroarylacetyl halide; and ethyl heteroarylacetate, methyl heteroarylacetate, and the like substituted or unsubstituted heteroarylacetic acid esters.
  • a used ratio of the aniline compound (2) and the heteroarylalkylcarbonyl compound (3A) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the aniline compound (2) , typically approximately 1 to 5 moles of the heteroarylalkylcarbonyl compound (3A) and preferably approximately equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a base.
  • the reaction is performed preferably under the presence of the base.
  • a conventionally known base can widely be used, and examples of the base include but not particularly limited to are: sodium carbonate, potassium carbonate, cesium carbonate, potassium bicarbonate, sodium bicarbonate, and the like alkali metal carbonates; sodium hydroxide, potassium hydroxide, and the like alkali metal hydroxides; alkali metal hydrides such as sodium hydride and potassium hydride, and the like inorganic bases; sodium methoxide, sodium ethoxide, potassium tert-butoxide, and the like alkali metal alkoxides; pyridine, triethylamine, diethylamine, dimethylamine, methylamine, imidazole, benzimidazole, diisopropylethylamine, 4-dimethylaminopyridine, piperidine, and the like organic bases. Any separate one of these bases or
  • Relative to 1 mole of the aniline compound (2) typically approximately 1 to 10 moles of the base and preferably approximately 1 to 5 moles thereof may excessively be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: n- hexane, cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1, 2-dichloroethane, chloroform, and carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, tetrahydrofuran (THF) , 1,4-dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; N, N
  • 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 25 °C. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours. Step IB (when Y is a hydroxy1 group)
  • the compound (4) can be produced by reacting the aniline compound (2) with a heteroarylacetic acid compound (hereinafter may be referred to as "compound (3B)”) represented by Formula (3B) (Reaction Scheme 4):
  • a used ratio of the aniline compound (2) and the heteroarylacetic acid compound (3B) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the aniline compound (2) , typically approximately 1 to 5 moles of the heteroarylacetic acid compound (3B) and preferably approximately equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a condensing agent.
  • the aforementioned reaction is preferably performed under the presence of the condensing agent.
  • the condensing agent a conventionally known condensing agent can be used, and examples of the condensing agent include l-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDCI.HC1), 1-hydroxybenzotriazole (HOBT) , 1- [bis (dimethylamino) methylene] -lH-1, 2, 3-triazolo [4,5-b] pyridinium-3-oxide hexafluorophosphate (HATU) , bis (2-oxo-3- oxazolidinyl) phosphine acid chloride (BOP-C1) , propylphosphonic acid anhydride (T3P) , and the like. Any separate one of these condensing agents or a combination of two or more types thereof is used
  • Relative to 1 mole of the aniline compound (2) typically 1 to 10 moles of the condensing agent and preferably approximately 1 to 3 moles thereof can excessively be used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • a solvent include: n- hexane, cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1 , 2-dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, and 1,4-dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; DMF and the like amide solvents; and di
  • 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 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • the aforementioned reaction can be performed under presence of a base.
  • a base any of the same bases as those described above can be used, and preferable examples of the base include triethylamine, pyridine, di-isopropylamine, 4- diisopropylethylamine, 4-dimethylaminopyridine, lutidine, and the like organic bases, and this base can also much excessively be used to act as a reaction solvent.
  • halogenation reagent includes, but are not particularly limited to, P0C1 3 , POBr 3 , S0C1 2 , S0 2 C1 2 , oxalyl chloride .
  • Relative to 1 mole of the aniline compound (2) typically 1 to 10 moles of the halogenation reagent and preferably approximately 1 to 5 moles thereof can be used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent .
  • the solvent no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • a solvent any one of those solvents described above, alone or a combination of two or more types thereof can be used when necessary.
  • 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 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • the heteroarylacetic acid compound (3B) , and heteroarylacetic acid halide compound (3C) used as starting materials in Step 1 are known compounds or compounds that can easily be produced by a known method.
  • the compound (4) obtained by the method shown in Step 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 chromatography, etc.
  • the compound (4) can be provided for next reaction without being isolated from the reaction system.
  • a sulfonyl chloride compound (hereinafter may be referred to as "compound (5)") represented by Formula (5) can be produced by chlorosulfonating the heteroarylacetamide compound (4) (Reaction Scheme 5) :
  • R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above.
  • a reagent used for the chlorosulfonation is not particularly limited, and for example, include chlorosulfonic acid, and the like.
  • the step can be carried out in one step.
  • a two-step method including sulfonation and then chlorination can be used.
  • the sulfonyl chloride compound (5) can be produced by reacting the heteroarylacetamide compound (4) with a sulfonation reagent to produce an HOS0 2 -substituted amide compound and then reacting the H0SC>2-containing amide compound with a chlorination agent .
  • the reagent used for the sulfation is not particularly limited, and for example, chlorosulfonic acid, sulfuric acid, etc can be used.
  • Examples of the chlorinating agent used for the chlorination include, but are not particularly limited to, chlorine, P0C1 3 , S0C1 2 , S0 2 C1 2 , and oxalyl chloride.
  • a used ratio between the heteroarylacetamide compound (4) and the chlorosulfonic acid in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the heteroarylacetamide compound (4), typically approximately 1 to 50 moles of chlorosulfonic acid and preferably approximately 1 to 20 moles thereof is used.
  • a used ratio between the sulfonation reagent, the chlorinating agent and the heteroarylacetamide compound (4) in the reaction is not particularly limited and can appropriately be selected from a wide range.
  • Relative to 1 mole of the heteroarylacetamide compound (4) typically approximately 1 to 50 moles of the sulfonation reagent and preferably approximately 1 to 20 moles thereof is used.
  • a used ratio between the two in the reaction between the heteroarylacetamide compound (4) and the chlorinating agent is not particularly limited, and can appropriately be selected from a wide range.
  • Relative to 1 mol of the heteroarylacetamide compound (1) typically approximately 1 to 50 moles of the chlorinating agent and preferably 1 to 20 moles thereof is used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • the solvent no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • the same solvents as those described above are listed. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between - 20°C and a boiling point of the solvent used, preferably -10°C to 150 °C, and more preferably 0 to 100 °C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
  • the sulfonyl chloride compound (5) obtained by the method shown in Step 2 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 chromatography, etc.
  • the sulfonyl chloride compound (5) can be provided for next reaction without being isolated from the reaction system.
  • a thiol compound (hereinafter may be referred to as "compound (6)") represented by Formula (6) can be produced by reacting the sulfonyl chloride compound (5) with a reducing agent (Reaction Scheme 6) :
  • R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above.
  • a used ratio between the sulfonyl chloride compound (5) and the reducing agent in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the sulfonyl chloride compound (5) , typically approximately 1 to 50 moles of the reducing agent and more preferably approximately 1 to 20 moles thereof is used.
  • any of conventionally known reducing agents can widely be used, and examples of the reducing agent include: triphenylphosphine and the like phosphorous compounds; reducing agents containing metal and acid such as zinc and acid, tin (II) and acid, and iron and acid; and reducing agent red phosphorus, iodine, dichlorodimethylsilane-zinc-dimethylacetamide, lithium aluminum hydride, and the like specific reducing agents.
  • the acid include acetic acid and the like organic acids; and hydrochloric acid, sulfuric acid, and the like inorganic acids.
  • the aforementioned reaction is performed in an appropriate solvent. No limitations are placed on the solvent as long as the solvent is inactive with respect to the reaction.
  • the same solvents as those described above are listed. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between - 20 °C and a boiling point of the solvent used, preferably -10 °C to 150°C, and more preferably 20 to 120°C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
  • the thiol compound (6) obtained by the method shown in Step 3 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 chromatography, etc.
  • the thiol compound (6) can be provided for next reaction without being isolated from the reaction system.
  • Examples of the method for producing the sulfide compound represented by Formula ( ⁇ -a) include, but are not limited to, a production route 1, a production route 2, a production route 3, a production route 4, described below, and the like.
  • Production route 1 (Step 4) is not limited to, a production route 1, a production route 2, a production route 3, a production route 4, described below, and the like.
  • a sulfide compound ( ⁇ -a) can be produced by reacting the thiol compound (6) with an alkyl reagent (hereinafter may be referred to as "alkyl reagent ⁇ !”) represented by Formula (7) (Reaction Scheme 7) :
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above, and G represents a leaving group.
  • a used ratio between the thiol compound (6) and the alkyl reagent (7) in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the thiol compound (6), typically approximately 1 to 10 moles of the alkyl reagent (7) and preferably approximately 1 to 5 moles thereof is used.
  • alkyl reagent (7) examples include, but are not particularly limited to, methyl iodide, ethyl bromide, and the like C 1 _ 6 alkyl halides; trifluoromethyl iodide, trifluoromethyl bromide, trifluoroethyl iodide, trifluoroethyl bromide, and the like C 1 _ 6 haloalkyl halides, and the like.
  • the aforementioned reaction can be performed under absence or presence of a base.
  • the aforementioned reaction is preferably performed under the presence of the base.
  • conventionally known bases can widely be used, and any of the same bases as those described above can be used.
  • Relative to 1 mole of the thiol compound (6) typically 1 to 10 moles of the base and preferably approximately 1 to 3 moles thereof can be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction can be performed by further adding a radical starting agent.
  • a radical starting agent include, but are not particularly limited to, sulfurous acid, a sulfurous acid salt, Rongalit (product name, sodium- formaldehyde-sulfoxylate) , and the like sulfurous acid adducts.
  • the base and the radical starting agent can be used in combination.
  • radical starting agent when used, as an additive amount thereof, relative to 1 mole of the thiol compound (6), typically 0.1 to 10 moles of the radical starting agent and preferably approximately 0.1 to 5 moles thereof can be used.
  • the aforementioned reaction is performed in an appropriate solvent.
  • the solvent include: n-hexane, cyclohexane n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2- dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, 1,4- dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like ester-based solvents; acetonitrile; DMF, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, and the like amide-based solvents; dimethyl sulfoxide and the like sulfoxide- based solvents; alcohol-based
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between - 20 °C and a boiling point of the solvent used, preferably -10 °C to 60 °C, and more preferably 0 to 50 °C.
  • Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
  • Step 4 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 chromatography, etc.
  • the sulfide compound (lA-a) can be provided for next reaction without being isolated from the reaction system.
  • a sulfide compound (hereinafter may be referred to as "compound (lA-d)”) represented by Formula (lA-d) can be produced by reacting a sulfide compound (hereinafter may be referred to as "compound (lA-c)”) represented by Formula (lA-c) with a compound (hereinafter may be referred to as "compound ⁇ !')”) represented by Formula (V): R 4 '-G (Reaction Scheme 8):
  • R 1 , R 2 , R 3 , R 5 , R 6 , HET, and X are as defined above, and R 4 ' represents formyl, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, C 1 _ 6 alkylcarbonyl, C 1 _ 6 haloalkylcarbonyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, cyano C 1 _ 6 alkyl, C 2-6 alkenyl, C 2-6 haloalkenyl, cyano C 2-6 alkenyl, C 2-6 alkyn
  • a used ratio between the sulfide compound (lA-c) and the compound (V ) in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
  • the aforementioned reaction can be performed under presence of a base.
  • a base conventionally known bases can be used and any of the same bases as those described above can be used.
  • a stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction is performed in an appropriate solvent.
  • the solvent include: n-hexane, cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2- dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, 1,4- dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; DMF, N,N- dimethylacetamide, N-methyl-2-pyrrolidone, and the like amide- based solvents; dimethyl sulfoxide and the like sulfoxide-based solvents; alcohol-based solvents
  • Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between - 20°C and a boiling point of the solvent used, preferably -10°C to 60°C, and more preferably 20 to 50°C.
  • Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
  • the sulfide compound ( ⁇ -d) obtained by the method shown in Reaction scheme 8 is easily isolated from a reaction mixture to be purified by use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc.
  • the sulfide compound ( ⁇ -d) can be provided for next reaction without being isolated from the reaction system.
  • the sulfide compound (lA-c) can be produced in accordance with not only what have been mentioned above but also production routes 3, 4, and 5.
  • the sulfide compound (lA-c) can be produced by reacting an aniline compound (hereinafter may be referred to as "compound (8)") with a heteroarylalkylcarbonyl compound (3) (Reaction Scheme 9) :
  • the sulfide compound (lA-c) can be produced by reacting the aniline compound (8) with a heteroarylalkylcarbonyl compound (3A) (Reaction Scheme 10) :
  • heteroarylalkylcarbonyl compound (3A) examples include, but are not particularly limited to, the same compounds as those of Step 1A.
  • the aniline compound (8) used as a starting material is a known compound or can be produced according to methods described
  • a used ratio between the aniline compound (8) and the heteroarylalkylcarbonyl compound (3A) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 5 moles of the latter and preferably approximately equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a base.
  • the aforementioned reaction is preferably performed under the presence of the base.
  • the base any of the same bases as those shown above in Step 1 can be used. Any separate one of these bases or a combination of two or more types thereof is used.
  • a stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can excessively be used.
  • Preferably one to five times of the base may excessively be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • any of the same solvents as those shown above in Step 1 can be used. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between - 20 °C and a boiling point of the solvent used and preferably 0 to 50 °C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.5 to 24 hours.
  • the sulfide compound (lA-c) 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 chromatography, etc.
  • the sulfide compound (lA-c) can be provided for next reaction without being isolated from the reaction system.
  • the compound (lA-c) can be produced by reacting the aniline compound (8) with a heteroarylacetic acid compound (3B) (Reaction Scheme 11) :
  • a used ratio between the aniline compound (8) and the heteroarylacetic acid compound (3B) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 5 moles of the latter and preferably equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a condensing agent.
  • the aforementioned reaction is preferably performed under the presence of the condensing agent.
  • the condensing agent the same condensing agents as those shown in Step IB. Any separate one of these condensing agents or a combination of two or more types thereof is used.
  • a stoichiometric amount of the condensing agent or an excessive amount thereof over the aforementioned amount can be used. Preferably approximately one to five times of the condensing agent may excessively be used.
  • the aforementioned reaction can be performed under absence or presence of a base. Among the above, the aforementioned reaction is preferably performed under the presence of the base. As the base, any of the same bases as those shown in Step 1 above can be used. Any separate one of these bases or a combination of two or more types thereof is used.
  • a stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can be used.
  • Preferably approximately 1 to 5 times of the base can excessively be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • any of the same solvents as those shown in Step 1 above can be used. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between - 20 °C and a boiling point of the solvent used and preferably 0 to 25 °C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.5 to 24 hours.
  • the aforementioned reaction can be performed under presence of a base.
  • a base any of the same bases as those described above can be used, and preferable examples of the base include triethylamine, pyridine, di-isopropylamine, 4- diisopropylethylamine, 4-dimethylaminopyridine, lutidine, and the like organic bases.
  • the bases can much excessively be used to be also used as reaction solvents.
  • halogen reagent examples include, but are not particularly limited to, P0C1 3 , POBr 3 , S0C1 2 , S0 2 C1 2 , and oxalyl chloride.
  • Relative to 1 mole of the aniline compound (2) typically 1 to 10 moles of the halogenation reagent and preferably approximately 1 to 5 moles thereof can be used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • the aforementioned solvents are listed. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • 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 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • the sulfide compound (lA-c) 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 chromatography, etc.
  • the sulfide compound (lA-c) can be provided for next reaction without being isolated from the reaction system.
  • the sulfide compound ( ⁇ -a) can be produced by reacting a sulfide compound (hereinafter may be referred to as "compound (9)”) with an amide compound (hereinafter may be referred to as “compound (10)”) represented by Formula (10) (Reaction Scheme 12) :
  • R 1 , R 2 , R 3 , R 4 , R 5 , R 6 , HET, and X are as defined above, and Z represents a leaving group.
  • a used ratio between the sulfide compound (9) and the heteroacetamide compound (10) in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a Pd-catalyst and a ligand. Among the above, the aforementioned reaction is preferably performed under the presence of the Pd-catalyst and a ligand.
  • the Pd-catalyst any of known Pd-catalyst can be used.
  • Pd- catalyst examples include palladium acetate, Pd(0Ac)2, tetrakis (triphenylphosphine) palladium (0) , Pd(PPh 3 ) 4 , bis (triphenylphosphine) palladium (II) dichloride, PdCl 2 (PPh 3 ) 2 , [1,1' -bis (diphenylphosphino) ferrocene] palladium (II ) dichloride, and the like.
  • Examples of the ligands but not particularly limited to are, 2-dicyclohexylphosphino-2 ' , 6 ' -dimethoxybiphenyl (S-Phos) and 2-dicyclohexylphosphino-2 ' , 4 ' , 6 ' - triisopropylbiphenyl (X-Phos) , 2-di-tert-butylphosphino-3, 4, 5, 6- tetramethyl-2 ' , 4 ' , 6 ' -triisopropyl-1, 1 ' -biphenyl, 4, 7-dimethoxy- 1, 10-phenanthroline, and the like.
  • a used ratio between the sulfide compound (9) , Pd-catalyst and the ligand in the reaction there between is not particularly limited and can appropriately be selected from a wide range.
  • the aforementioned reaction can be performed under absence or presence of a base. Among the above, the aforementioned reaction is preferably performed under the presence of the base.
  • the base any of the same bases as those shown in Step 1 above can be used. Any separate one of these bases or a combination of two or more types thereof is used.
  • Relative to 1 mole of the aniline compound (9) typically 1 to 10 moles of the base and preferably approximately 1 to 5 moles thereof is used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • any of the same solvents as those shown in the Step 1 above can be used. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • 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 between 0°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.5 to 24 hours.
  • the sulfide compound (9) used as a starting material can be produced according to methods described in EP3002279 and WO2012/176856.
  • the sulfide compound (1-1) 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 chromatography, etc.
  • the sulfide compound (lA-a) can be provided for next reaction without being isolated from the reaction system.
  • the aforementioned reaction can be performed under presence of the oxidizing agent.
  • the oxidizing agent any of known oxidizing agents can be used as long as the oxidizing agent can achieve oxidization of sulfide into sulfoxide or sulfone, and examples of the oxidizing agent include but not particularly limited to are: performic acid, peracetic acid, pertrifluoroacetic acid, perbenzoic acid, m-chloroperbenzoic acid (mCPBA) , o-carbonylperbenzoic acid, and the like peracids; hydrogen peroxide, t-butylhydroperoxide, cumene hydroperoxide, and the like alkyl hydroperoxides; and titanium tetraisopropoxide and the like titanium tetraalkoxides; sodium dichromate, potassium dichromate, and the like dichromate salts; sodium permanganate, potassium permanganate, and the like permanganates; potassium peroxymonosulfate
  • a used ratio between the amide compound ( ⁇ -a) and the oxidizing agent in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
  • the aforementioned reaction can further be performed by adding a catalyst.
  • the aforementioned reaction is performed in an appropriate solvent.
  • the solvent include: n-hexane, cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2- dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, 1,4- dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; DMF, N,N- dimethylacetamide, N-methyl-2-pyrrolidone, and the like amide- based solvents; dimethyl sulfoxide and
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between - 20°C and a boiling point of the solvent used, preferably -10°C to 60 °C, and more preferably 20 to 50 °C.
  • Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • the compound (lA-b) obtained by the method shown in Step 5 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, chromatography, etc.
  • Each compound (1A) obtained after the completion of the reactions shown in Reaction Scheme 1 to Reaction Scheme 13 may be easily isolated from the reaction mixture and purified by known isolation and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography .
  • each regioisomer may be separated by a usual separation step, such as silica gel chromatography .
  • An amide compound (hereinafter may be referred to as
  • compound (lB-a) represented by Formula ( ⁇ -a) can be produced by reacting an arylcarbonyl compound (hereinafter may be referred to as "compound (11)”) represented by Formula (11) with an amine compound (hereinafter may be referred to as “compound (12)”) represented by Formula (12) (Reaction Scheme 15) :
  • G represents a leaving group or a hydroxyl group, and examples of the leaving group include: halogen such as chlorine, bromine, and iodine; substituted or unsubstituted C X - 6 alkyl sulfonate; and substituted or unsubstituted aryl sulfonate.
  • substituent include the aforementioned substituents such as the halogen and the C 1 _ 6 haloalkyl.
  • Examples of the amine compound (12) include, but are not particularly limited to, substituted or unsubstituted C 1 _ 6 alkyl amines and the like, substituted or unsubstituted C 3 _ 8 cycloalkyl amines and the like, substituted or unsubstituted C 3 _ 8 cycloalkyl C 1 _ 6 alkyl amines and the like, substituted or unsubstituted anilines and the like, substituted or unsubstituted aryl C 1 _ 6 alkyl amines and the like, substituted or unsubstituted heteroaryl amines and the like, substituted or unsubstituted heteroaryl C 1 _ 6 alkyl amines and the like.
  • An amide compound ( ⁇ -a) can be produced by reacting the arylcarbonyl compound (hereinafter may be referred to as "compound (11A)") represented by Formula (11A) with an amine compound (12) as represented by Reaction Scheme 16:
  • a used ratio of the arylcarbonyl compound (11A) and the amine compound (12) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the arylcarbonyl compound (11A) , typically approximately 1 to 5 moles of the amine (12) and preferably approximately equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a base.
  • the reaction is performed preferably under the presence of the base.
  • any of conventionally known bases can be used, examples of known bases are similar as mentioned in Step 1A of production Method 2A.
  • Relative to 1 mole of the arylcarbonyl compound (11A) typically approximately 1 to 10 moles of the base and preferably approximately 1 to 5 moles thereof may excessively be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • the solvent no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • Examples of solvents are similar as mentioned in Step 1A of production Method 2A. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • 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 25 °C. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.
  • An amide compound ( ⁇ -a) can also be produced by reacting the arylcarboxylic acid compound (hereinafter may be referred to as "compound (11B)") represented by Formula (11B) with the amine compound (12), (Reaction Scheme 17):
  • a used ratio of the aryl carboxylic acid compound (11B) and the amine compound (12) in the reaction there between is not particularly limited and thus can appropriately be selected from a wide range. Relative to 1 mole of the aryl carboxylic acid compound (11B) typically approximately 1 to 5 moles of the amine compound (12) and preferably approximately equimolar to 1.2 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a condensing agent.
  • the aforementioned reaction is preferably performed under the presence of the condensing agent.
  • the condensing agent a conventionally known condensing agent can be used, and examples of the condensing agent include l-ethyl-3- (3-dimethylaminopropyl) carbodiimide (EDCI-HC1) , 1-hydroxybenzotriazole (HOBT) , 1- [bis (dimethylamino) methylene] -lH-1, 2, 3-triazolo [4,5-b] pyridinium-3-oxide hexafluorophosphate (HATU) , bis (2-oxo-3- oxazolidinyl) phosphine acid chloride (B0P-C1) , propylphosphonic acid anhydride (T3P) , and the like. Any separate one of these condensing agents or a combination of two or more types thereof
  • Relative to 1 mole of the aryl carboxylic acid compound (11B) typically 1 to 10 moles of the condensing agent and preferably approximately 1 to 3 moles thereof can excessively be used.
  • the aforementioned reaction can be performed under absence or presence of a base. Among the above, the reaction is performed preferably under the presence of the base.
  • the base any of conventionally known bases can be used, examples of known bases are similar as mentioned in Step 1A of production Method 2A.
  • Relative to 1 mole of the aryl carboxylic acid compound (11B) typically approximately 1 to 10 moles of the base and preferably approximately 1 to 5 moles thereof may excessively be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent .
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • the solvent no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • Examples of solvents are similar as mentioned in Step 1A of production Method 2A. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • 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 25 °C. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.5 to 24 hours.
  • the aforementioned reaction can be performed under presence of a base.
  • a base any of the same bases as those described above can be used, and preferable examples of the base include triethylamine, pyridine, di-isopropylamine, 4-diisopropylethyl amine, 4-dimethylaminopyridine, lutidine, and the like organic bases, and this base can also much excessively be used to act as a reaction solvent.
  • halogenation reagent includes, but are not particularly limited to, P0C1 3 , POBr 3 , S0C1 2 , S0 2 C1 2 , oxalyl chloride .
  • Relative to 1 mole of the arylcarboxylic acid compound (11B) typically 1 to 10 moles of the halogenation reagent and preferably approximately 1 to 5 moles thereof can be used.
  • the aforementioned reaction is performed in an appropriate solvent or without any solvent.
  • the aforementioned reaction is carried out in the solvent, no limitations are placed on the solvent as long as the solvent is inactive with respect to the aforementioned reaction.
  • the aforementioned solvents are listed. Any one of these solvents can be used alone or a combination of two or more types thereof can be used when necessary.
  • 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 within a range between -5°C and the boiling point of the solvent. Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • Compound (lB-d) An amide compound represented by Formula ( ⁇ -d) can be produced by reacting a sulfide compound (hereinafter may be referred to as “compound (lB-c)”) represented by Formula (lB-c) with a compound (7') R4'-G (Reaction Scheme 18):
  • R 1 , R 2 , R 3 , R 4' , R 7 , and X are as defined above.
  • R 4' represents formyl, cyano, C 1 _ 6 alkyl, C 1 _ 6 haloalkyl, C 1 _ 6 alkoxy, C 1 _ 6 haloalkoxy, C 1 _ 6 alkoxy C 1 _ 6 alkyl, C 3 _ 8 cycloalkyl, C 3 _ 8 cycloalkyl C 1 _ 6 alkyl, C 1 _ 6 alkylcarbonyl, C 1 _ 6 haloalkylcarbonyl, C 1 _ 6 alkoxycarbonyl, C 1 _ 6 haloalkoxycarbonyl, arylcarbonyl, aryloxycarbonyl, cyano C 1 _ 6 alkyl, 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 1 _ 6 alky
  • a used ratio between the sulfide compound (lB-c) and the compound (T ) in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
  • the aforementioned reaction can be performed under absence or presence of a base.
  • the aforementioned reaction is preferably performed under the presence of the base.
  • the base conventionally known bases can be used and any of the same bases as those described above can be used.
  • a stoichiometric amount of the base or an excessive amount thereof over the aforementioned amount can be used.
  • triethylamine, pyridine, or like an organic base it can be used in large excess to serve also as a reaction solvent.
  • Reaction temperature for the aforementioned reaction is not particularly limited and is typically within a range between - 20°C and a boiling point of the solvent used, preferably -10°C to 60 °C, and more preferably 20 to 50 °C. Reaction time varies depending on, for example, the reaction temperature and the reaction typically ends in approximately 0.25 to 24 hours.
  • the compounds ( ⁇ -a), (lB-c) and ( ⁇ -d) obtained by the methods shown in Production routes 5 to 8 are easily isolated from a reaction mixture and can be purified by the use of typical isolation means and purification means, for example, filtration, solvent extraction, distillation, recrystallization, column chromatography, etc. After end of the reaction, the sulfide compound ( ⁇ -a), (1B- c) and ( ⁇ -d) can be provided for next reaction without being isolated from the reaction system.
  • the amine compounds (12), used as starting compound as mentioned above are known compounds or compounds that can be easily synthesized by various known methods.
  • the aryl carbonyl compounds (11A and 11B) used as a starting material can be produced according to various available known methods .
  • An arylcarboxamide compound represented by Formula (lB-b) can be produced by reacting a sulfide compound represented by Formula (IB-a) with an oxidizing agent (Reaction Scheme 19) :
  • the aforementioned reaction can be performed under presence of the oxidizing agent.
  • the oxidizing agent any of known oxidizing agents can be used as long as the oxidizing agent can achieve oxidization of sulfide into sulfoxide or sulfone, and examples of the oxidizing agent include but not particularly limited to: performic acid, peracetic acid, pertrifluoroacetic acid, perbenzoic acid, m-chloroperbenzoic acid (mCPBA) , o- carbonylperbenzoic acid, and the like peracids; hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, and the like alkyl hydroperoxides; and titanium tetraisopropoxide and the like titanium tetraalkoxides; dichromate, sodium dichromate, potassium dichromate, and the like dichromate salts; sodium permanganate, potassium permanganate, and the like permanganates; potassium peroxymonosul
  • a used ratio between the amide compound ( ⁇ -a) and the oxidizing agent in the reaction there between is not particularly limited and can appropriately be selected from a wide range. Relative to 1 mole of the former, typically approximately 1 to 10 moles of the latter and preferably approximately equimolar to 5 moles thereof is used.
  • the aforementioned reaction can further be performed by adding a catalyst.
  • the aforementioned reaction is performed in an appropriate solvent.
  • the solvent include: n-hexane, cyclohexane, n-heptane, and the like fatty acid or alicyclic hydrocarbon-based solvents; benzene, chlorobenzene, toluene, xylene, and the like aromatic hydrocarbon-based solvents; methylene chloride, 1,2- dichloroethane, chloroform, carbon tetrachloride, and the like halogenated hydrocarbon-based solvents; diethyl ether, THF, 1,4- dioxane, and the like ether-based solvents; methyl acetate, ethyl acetate, and the like esters solvents; acetonitrile; DMF, N,N- dimethylacetamide, N-methyl-2-pyrrolidone, and the like amide- based solvents; dimethyl sulfoxide and the like sulfoxide-based solvents; alcohol-based solvents
  • Reaction temperature for the aforementioned reaction is not particularly limited, and is typically within a range between - 20 °C and a boiling point of the solvent used, preferably -10 °C to 60°C, and more preferably 20 to 50°C.
  • Reaction time varies depending on, for example, the reaction temperature, and the reaction typically ends in approximately 0.25 to 24 hours.
  • the sulfide compound ( ⁇ -b) obtained by the method shown in Step 2 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, chromatography, etc.
  • typical isolation means and purification means for example, filtration, solvent extraction, distillation, recrystallization, chromatography, etc.
  • Each compound (IB) obtained after the completion of the reactions shown in Reaction Scheme 14 to Reaction Scheme 19 may be easily isolated from the reaction mixture and purified by known isolation and purification techniques, such as filtration, solvent extraction, distillation, recrystallization, and column chromatography.
  • each regioisomer may be separated by a usual separation step, such as silica gel chromatography .
  • Compound (1) of the present invention may be used as an active ingredient of a pest-controlling agent.
  • pest- controlling agents include agents (agricultural and horticultural insecticide, miticides, nematicides, or soil insecticides) for controlling pests, mites, nematode, or soil pests that all cause problems in the agricultural and horticultural fields; animal- ectoparasite-controlling agents (e.g., pulicide, ixodicide, and pedivulicideon) , and the like.
  • compound (1) of the present invention For use as an active ingredient of a pest-controlling agent, it is possible to use compound (1) of the present invention as is with no additional components. However, it is usually preferable to use the compound by combining with a solid carrier, liquid carrier, or gaseous carrier (propellant) , and optionally with a surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms such as oil solutions, emulsions, wettable powders, flowable preparations, granules, dusts, aerosols, fumigants, or the like, according to known preparation methods.
  • a solid carrier liquid carrier, or gaseous carrier (propellant)
  • surfactant and other adjuvants for pharmaceutical preparation, and formulating the resulting mixture into various forms such as oil solutions, emulsions, wettable powders, flowable preparations, granules, dusts, aerosols, fumigants, or the like, according to known preparation methods.
  • Compound (1) of the present invention is usually contained in these formulations in a proportion of 0.01 to 95 wt%, and preferably 0.1 to 50 wt%.
  • solid carriers usable in the formulations include solid carriers in a fine powder or granular form, such as clay (e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay, and acid clay) , talc, ceramic, other inorganic minerals (e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica) , and chemical fertilizers (e.g., ammonium sulfate, ammonium phosphate, ammonium nitrate, urea, and ammonium chloride) ; and the like.
  • clay e.g., kaolin clay, diatomaceous earth, synthetic hydrated silicon dioxide, bentonite, Fubasami clay, and acid clay
  • talc ceramic
  • other inorganic minerals e.g., celite, quartz, sulfur, active carbon, calcium carbonate, and hydrated silica
  • chemical fertilizers e.g., ammonium sulfate, am
  • liquid carriers examples include water, alcohols (e.g., methanol and ethanol) , ketones (e.g., acetone and methylethylketone) , aromatic hydrocarbons (e.g., benzene, toluene, xylene, ethylbenzene, and methylnaphthalene) , aliphatic hydrocarbons (e.g., hexane, cyclohexane, kerosene, and light oil), esters (e.g., ethyl acetate and butyl acetate), nitriles (e.g., acetonitrile and isobutyronitrile) , ethers (e.g., diisopropyl ether and dioxane) , acid amides (e.g., N, N-dimethylformamide and N, W-dimethylacetamide) , halogenated hydrocarbons (e.g., dich
  • gaseous carriers examples include butane gas, LPG (liquefied petroleum gas) , dimethyl ether, carbon dioxide gas, and the like.
  • surfactants include alkyl sulfates, alkyl sulfonates, alkylaryl sulfonates, alkyl aryl ethers, polyoxyethylene adducts thereof, polyethylene glycol ethers, polyhydric alcohol esters, sugar alcohol derivatives, and the like.
  • adjuvants for pharmaceutical preparation include fixing agents, dispersants, stabilizers, and the like.
  • fixing agents and dispersants examples include casein, gelatin, polysaccharides (e.g., starch, gum arabic, cellulose derivatives, and alginic acid) , lignin derivatives, bentonite, sugars, and water-soluble synthetic polymers (e.g., polyvinyl alcohol, polyvinyl pyrrolidone, and polyacrylic acids) .
  • stabilizers examples include PAP (acidic isopropyl phosphate), BHT (2, 6-di- tert-butyl-4-methylphenol) , BHA (mixture of 2- tert-butyl-4-methoxyphenol and 3- tert-butyl-4-methoxyphenol) , vegetable oils, mineral oils, fatty acids, and fatty acid esters, and the like.
  • PAP acidic isopropyl phosphate
  • BHT 2, 6-di- tert-butyl-4-methylphenol
  • BHA mixture of 2- tert-butyl-4-methoxyphenol and 3- tert-butyl-4-methoxyphenol
  • vegetable oils mineral oils, fatty acids, and fatty acid esters, and the like.
  • the pest-controlling agent of the present invention it is preferable to use compound (1) as is, or by diluting it with water or the like.
  • the pest-controlling agent of the present invention may be used by mixing with, for example, other pest- controlling agents, such as known insecticides, nematicides, acaricides, fungicides, herbicides, plant-growth-controlling agents, synergists, soil conditioners, animal feeds, and the like, or it may be used simultaneously with these agents without mixing.
  • the amount of the pest-controlling agent of the invention is not limited, and may be suitably selected from a wide range according to various conditions such as the concentration of active ingredient, the form of preparation, type of disease or pest to be treated, type of plant, severity of disease, time for application, method for application, chemicals to be used in combination (insecticide, nematicide, miticide, fungicide, herbicide, plant growth control agent, synergist, soil conditioner, etc.), and amount and type of fertilizer.
  • compound (1) of the present invention When used as a pesticide, compound (1) of the present invention is usually used in an amount of 0.01 to 500 g/100 m 2 , and preferably 1 to 200 g/100 m 2 .
  • compound (1) of the present invention When used as a miticide, compound (1) of the present invention is usually used in an amount of 0.1 to 500 g/100 m 2 , and preferably 1 to 200 g/100 m 2 .
  • compound (1) of the present invention When used as an aphicide, compound (1) of the present invention is usually used in an amount of 0.1 to 500 g/100 m 2 , and preferably 1 to 200 g/100 m 2 .
  • the concentration is 0.1 to 1,000 ppm, and preferably 1 to 500 ppm.
  • the granules, dusts, or the like can be used as is without dilution.
  • Compound (1) of the present invention is characterized by having a particularly excellent miticidal activity and a broad spectrum of activity.
  • Compound (1) of the present invention is effectively used as an agricultural and horticultural insecticide, miticide, nematicide, or a soil insecticide.
  • compound (1) of the present invention is effective for controlling pests, such as green peach aphids, cotton aphids, and like aphids; diamondback moths, cabbage armyworms, common cutworms, codling moths, bollworms, tobacco budworms, gypsy moths, rice leafrollers, smaller tea tortrix moths, Colorado potato beetles, cucurbit leaf beetles, boll weevils, plant hoppers, leafhoppers, scales, bugs, whiteflies, thrips, grasshoppers, anthomyiid flies, scarabs, black cutworms, cutworms, ants, and agricultural pest insects; slugs, snails, and like gastropods; rat mite, cockroaches, houseflies, house mosquitoes, and like hygiene-harming insects; angoumois grain moths, adzuki bean weevils, red flour beetles, mealworms, and like stored
  • mites such as two-spotted spider mites, carmine spider mites, citrus red mites, Kanzawa spider mites, European red mites (fruit tree spider mites) , broad mites, pink citrus rust mites, bulb mites, and like plant-parasitic mites; Tyrophagus putrescentiae, Dermatophagoides farinae, Chelacaropsis moorei, and like house dust mites; and the like, and
  • soil pests such as root-knot nematodes, cyst nematodes, root- lesion nematodes, white-tip nematode, strawberry bud nematode, pine wood nematode, and like plant parasitic nematodes; pill bugs, sow bugs, and like isopods; and the like.
  • the pest-controlling agent of the present invention is also effective for controlling various pests resistant to chemicals such as organophosphorus agents, carbamate agents, synthetic pyrethroid agents, and neonicotinoid agent.
  • the crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.07 g of the title compound 6-(lA-l-234) as a light yellow solid.
  • the combined organic layer was washed with distilled water, dried over sodium sulfate, filtered and concentrated under reduced pressure to obtain a crude product.
  • the crude product thus obtained was purified by column chromatography on silica gel with a mixture of ethyl acetate and n-hexane as an eluent to obtain 0.06 g of the title compound 1A- 1-234 as a white solid.
  • Tables 1, 2 and 3 show 1 H-NMR data of the thus obtained compounds of the present invention.
  • F fluoro
  • CI chloro
  • Br bromo
  • Me methyl
  • Et ethyl
  • n-Pr normal-propyl
  • i-Pr isopropyl
  • n-Bu normal-butyl
  • t-Bu tert- butyl
  • n-Pent normal-pentyl
  • Ac acetyl
  • CF 3 trifluoromethyl
  • OMe methoxy
  • OEt ethoxy
  • OCF 3 trifluoromethoxy
  • SCF 3 trifluoromethylthio
  • 4 ⁇ N, N-Me 2 N-Ph 4- (N, N-dimethylamino) phenyl
  • SMe methylthio
  • NH 2 amino
  • NO 2 nitro
  • Ph phenyl
  • S sulfur atom
  • 0 oxygen atom.
  • each compound of the invention was mixed with 20 parts of water containing 3 parts of polyoxyethylene tristyrylphenyl ether phosphoric acid ester triethanolamine and 0.2 parts of Rhodorsil 426R.
  • the mixtures were subjected to wet pulverization with a DYNO-Mill, and mixed with 60 parts of water containing 8 parts of propylene glycol and 0.32 parts of xanthan gum to give 20% suspensions in water.
  • Test Examples are given below to demonstrate that the compounds of the invention are useful as an active ingredient for miticides .
  • Test Example 1 Mitsubishi test on Two-Spotted Spider Mites
  • a piece of non-woven fabric (4.5> ⁇ 5.5cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid.
  • a kidney bean leaf (about 3.5x4.5 cm) was then placed on the sufficiently soaked, non-woven fabric.
  • Another kidney bean leaf with two-spotted spider mites (about 30 mite samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25+2° C and a humidity of 40% overnight. Next morning the top leaf was removed as the mite population had already moved to the lower leaf.
  • Miticidal formulations containing the compound of the invention were prepared by adding an aqueous solution (100 ppm) of Sorpol 355 (manufactured by Tobo Kagaku Co. Ltd.) to a methanol solution of the compound of the invention.
  • the compounds (from Table 1) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • the compounds (from Table 2) that exhibited the mortality rate of 50% or more at 200 ppm are as follows: 1B- • 1-1, lB-1-2, IB-l--3, lB-1-7, lB-1-8, IB-l- ⁇ 12, lB-1--14,
  • the compounds (from Table 3) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • 1B-2-3 1B-2-5, 1B-2-6, 1B-2-7, 1B-2-18, 1B-2-21, 1B-2-25, 1B-2-29, 1B-2-31, 1B-2-32, 1B-2-33, 1B-2-37, 1B-2-38, 1B-2-49, 1B-2-50, 1B-2-51, 1B-2-52, 1B-2-59, 1B-2-60.
  • a piece of non-woven fabric (4.5x5.5cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid. A kidney bean leaf (about 3.5x4.5 cm) was then placed on the sufficiently soaked, non-woven fabric. Twenty female adults of two-spotted spider mite were placed on the top of the leaf, and the fabric and leaf were placed in a thermostatic chamber having a temperature of 25 ⁇ 2° C and a humidity of 40% and 16L8D.
  • the compounds (from Table 2) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • the compounds (from Table 3) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • Test Example 3 (Aphicidal test on cotton aphid)
  • a piece of non-woven fabric (4.5 x 5.5cm) was suspended inside a plastic cup through an incision made in the lid of the plastic cup. After water was poured into the cup, the cup was covered with the lid.
  • a cucumber leaf (about 3.5x4.5 cm) was then placed on the sufficiently soaked, non-woven fabric.
  • Another cucumber leaf with cotton aphid (about 30 aphid samples) was placed on top of the first leaf, and the fabric and leaves were placed in a thermostatic chamber having a temperature of 25 ⁇ 2° C and a humidity of 40% overnight. Next morning the top leaf was removed as the aphid population had already moved to the lower leaf.
  • Aphicidal formulations containing the compound of the invention were prepared by adding an agueous solution (100 ppm) of Sorpol 355 (manufactured by Tobo Kagaku Co. Ltd.) to a methanol solution of the compound of the invention.
  • the compounds (from Table 1) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • the compounds (from Table 2) that exhibited the mortality rate of 50% or more at 200 ppm are as follows:
  • Sphaerotheca fuliginea is cultured on intact cucumber plants.
  • Infected leaves with spores were washed with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain l> ⁇ 10 6 cfu spore per ml.
  • the solution of the compound of the invention (200ppm) was sprayed on fresh healthy two week old cucumber plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension.
  • the inoculated plants were then placed in green house (25° C, a humidity of 60% and 16L8D) .
  • the percent disease control was assessed 12 days after from leaf disease area compared to control .
  • the mycelium of Phytophthora infestans was washed with distilled water from four day old potato slice culture box and filtered through tissue paper. The filtrate was diluted with distilled water to obtain 1*10 6 sporangia per ml.
  • the solution of the compound of the invention (200ppm) was sprayed on fresh healthy tomato plant at least at the three leaf stage.
  • the plants were air-dried and inoculated with freshly prepared sporangia suspension.
  • the inoculated plants were then placed in a dew chamber (20° C and a humidity of 100%) .
  • One day after inoculation the plants were shifted to thermostatic chamber (20° C, a humidity of 80%, and 16L8D) .
  • the percent disease control was assessed five days after from leaf disease area compared to control .
  • Test example 3 Fungicidal test on Pyricularia oryzae
  • a small bit of mycelium of Pyricularia oryzae was taken from a culture tube and transferred onto an oat meal agar plate aseptically.
  • the inoculated plate was kept for 7 days at 25°C.
  • plates were incubated at 25 °C for 5 days under exposure to black light blue, 16L8D.
  • After five days the plates were fully covered with spores of fungus .
  • the spores were washed from the plate with 0.01% Tween 20 solution and were passed through tissue paper. Then the filtrate was diluted with the 0.01% Tween 20 solution to obtain lxl0 6 cfu spore per ml.
  • the solution of the compound of the invention (200ppm) was sprayed on fresh healthy two week old rice plants.
  • the plants were air-dried and inoculated with freshly prepared spore suspension.
  • the inoculated plants were then placed in a dew chamber (25° C and a humidity of 100%) .
  • a dew chamber 25° C and a humidity of 100%
  • One day after inoculation the plants were shifted to a thermostatic chamber (25° C, a humidity of 80%, and 16L8D) .
  • the percent disease control was assessed 5-7 days after from leaf disease area compared to control .
  • the present invention provides novel amide compounds, methods for producing the same, and miticides, ovicides, and aphicides, and thus the present inventions are particularly useful in the agricultural industry.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)

Abstract

Un objet de la présente invention est de fournir un composé amide ou un sel de celui-ci pouvant lutter contre un acarien. La présente invention concerne un composé amide représenté par la formule (1) : ou un sel de celui-ci, où R1 représente alkyle C1-6 ou haloalkyle C1-6; R2 et R3 sont identiques ou différents et représentent chacun hydrogène, halogène, cyano, nitro, alkyle C1-6, ou analogue; R4 représente hydrogène, alkyle C1-6, acétyl ou analogue; R5 et R6 sont identiques ou différents et représentent chacun hydrogène, halogène, ou alkyle C1-6, ou analogue; HET représente hétéroaryle à 5 ou 6 chaînons, R7 représente alkyle C1-6, haloalkyle C1-6, cycloalkyle C3-8, alkyle C1-6 cycloalkyle C3-8, aryle substitué ou non substitué, alkyle C1-6 aryle substitué ou non substitué; X représente oxygène ou soufre; et n représente un nombre entier de 0 à 2.
PCT/IB2017/055542 2016-09-15 2017-09-14 Nouveau composé amide, son procédé de production et miticide WO2018051252A2 (fr)

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CN111978226A (zh) * 2018-06-05 2020-11-24 沈阳化工大学 一种三氟乙基硫醚（亚砜）取代苯类化合物及其用途
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CN112166105B (zh) * 2018-06-05 2022-03-04 沈阳化工大学 一种三氟乙基硫醚(亚砜)取代苯类化合物及其用途
CN110028431A (zh) * 2018-06-05 2019-07-19 沈阳化工大学 一种三氟乙基硫醚（亚砜）取代苯类化合物及其用途
CN111978225B (zh) * 2018-06-05 2022-03-04 沈阳化工大学 一种三氟乙基硫醚（亚砜）取代苯类化合物及其用途
CN112142646A (zh) * 2019-06-26 2020-12-29 沈阳中化农药化工研发有限公司 一种吡咯并芳环类化合物及其应用
CN112142646B (zh) * 2019-06-26 2022-08-09 沈阳中化农药化工研发有限公司 一种吡咯并芳环类化合物及其应用
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WO2021056922A1 (fr) 2019-09-23 2021-04-01 山东康乔生物科技有限公司 Sulfure d'aryle contenant une structure de benzylamine, son procédé de synthèse et son utilisation
CN115701423A (zh) * 2021-08-02 2023-02-10 沈阳化工大学 三氟乙基硫醚（亚砜）取代苯类化合物的制备方法及其中间体

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