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WO2003000659A1 - Composes heterocyclo-iminophenyle et fungicides et insecticides destines a l'agriculture et l'horticulture - Google Patents

Composes heterocyclo-iminophenyle et fungicides et insecticides destines a l'agriculture et l'horticulture Download PDF

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Publication number
WO2003000659A1
WO2003000659A1 PCT/JP2002/006424 JP0206424W WO03000659A1 WO 2003000659 A1 WO2003000659 A1 WO 2003000659A1 JP 0206424 W JP0206424 W JP 0206424W WO 03000659 A1 WO03000659 A1 WO 03000659A1
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Prior art keywords
optionally substituted
alkyl
substituted
alkoxy
phenyl
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PCT/JP2002/006424
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English (en)
Japanese (ja)
Inventor
Toshio Niki
Takashi Mizukoshi
Hiroaki Takahashi
Jun Satow
Tomoyuki Ogura
Kazuhiro Yamagishi
Hiroyuki Suzuki
Fumio Hayasaka
Original Assignee
Nissan Chemical Industries, Ltd.
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Publication of WO2003000659A1 publication Critical patent/WO2003000659A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—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
    • C07D213/02—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
    • 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
    • C07D213/72—Nitrogen atoms
    • C07D213/75—Amino or imino radicals, acylated by carboxylic or carbonic acids, or by sulfur or nitrogen analogues thereof, e.g. carbamates
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3

Definitions

  • the present invention relates to a novel heterocyclic iminophenyl compound and a salt thereof, and a fungicide and an insecticide containing one or more selected from the heterocyclic iminophenyl compound and a salt thereof as an active ingredient.
  • heterocyclic iminophenyl compound of the compound of the present invention is a novel compound not described in the literature.
  • the present inventors have conducted various studies in order to find an excellent fungicide, and as a result, a novel heterocyclic iminophenyl compound and a salt thereof have remarkable activity as a fungicide or insecticide, The fe finds that it is safe for the target crop, and leads to the present invention.
  • the present invention relates to the following [1] to [12].
  • V a, V b, V c and V d are each independently a carbon atom, a nitrogen atom, an oxygen atom or a sulfur atom
  • V e is a carbon atom, a nitrogen atom, an oxygen atom, a sulfur atom or a single bond.
  • Va, Vb, Vc, Vd, and Ve is a nitrogen atom, an oxygen atom, or a sulfur atom.
  • V a-V b, Vb- Vc, V c- Vd, Vd- V e may be a single bond or a double bond, respectively.
  • a hydrogen atom or Y may be bonded on each atom
  • A represents a quinolone ring
  • the nitrogen atom in the quinolone ring is at the ⁇ -position of the imino bond
  • the imino bond is in the pyrimidine ring, thiazoline ring or thiazolidine ring.
  • G is G 1 to G 16
  • G, G 7 1 Q, NR , Q,
  • G 13 G 14 : represents a group selected from:
  • Z is one OR ', one S R' is or a NR2R 3,
  • a z is optionally substituted by R a phenyl, from R a in an optionally substituted pyridyl or A 2 a ⁇ 2 ⁇
  • Y is Y '— D— (CH P — (however, when Y is 2 or more, it may be the same or different), or by two Y substituted on the same carbon atom of A Containing 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms together with the carbon atoms Or form a 3- to 7-membered ring or C-Q ', or two substituents Y on Va and Vb, Vb and Vc, Vc and Vd, or Vd and Ve are joined together, V a and V b, V b and V c, V c and V d or V d and V e together with one or more kinds of the same or different atoms selected from a carbon atom, a nitrogen atom, an oxygen atom and a sulfur atom, Forms a 5- or 6-membered ring which may be substituted by Y,
  • Q 6 is one S— or one O—
  • X is halogen, C, ⁇ C s alkyl, C, ⁇ C, mouth alkyl, C 1 -C 6 alkoxy, ( ⁇ ⁇ . ⁇ ⁇ alkoxy, C, ⁇ C 6 alkylthio, C, ⁇ C 6 alkylamino , (C, ⁇ C S alkyl) 2 Amino, N0 2, CN, formyl, OH, SH, NU'U 2, Ci ⁇ C s alkoxy force Ruponiru, C 1 -C 6 alkylcarbonyl, C, -C S Haroaru kill carbonyl, R a phenylene which may be substituted with Rukaruponiru or C, ⁇ C 6 alkyl Cal Poni Ruo carboxymethyl (but replacing, in the case of two or more may be different to the same or another. ),
  • R ′, R 2 and R 4 are each independently a hydrogen atom, C, to C S alkyl, C, to C 6 haloalkyl, C 3 to C 6 cycloalkyl, C! ⁇ Cs alkoxy C! Cs alkyl, C, ⁇ C 6 alkyl sulphates enyl ⁇ ⁇ 0 6 alkyl, into which may be substituted by R a may phenyl Ci be substituted by Cs alkyl or R a Teroari Ichiru C, and -C 6 al kill Yes,
  • R 3 is a hydrogen atom, C, -C 6 alkyl, C, -C 6 A alkyl, C 3 -C 6 cycloalkyl, C, -C 6 alkoxyalkyl, C, -C 5 alkylsulfenyl C, -C 6 alkyl, R a with substituted optionally phenyl, have Hue sulfonyl ⁇ good optionally substituted by R a, ⁇ C 6 alkyl or Teroari Ichiru C to optionally substituted with R a , ⁇ C 6 alkyl,
  • R 5 and R 6 are each independently halogen, C, -C 5 alkyl, C, ⁇ C S Haroaru kill, C 3 ⁇ C 6 cycloalkyl, C, -C S alkoxy, C, ⁇ C 6 alkoxy C !
  • R 6 may be a hydrogen atom
  • R 7 is a hydrogen atom, C,-(: 6 alkyl, C 1 -C 6 noroalkyl, C 3 -C 6 cycloalkyl Alkyl,, C, -C 6 alkoxy Omicron, Omicron beta alkoxy C! Cs alkyl, c, to c 5 Al Kirusurufueniru C, ⁇ C S alkyl, C, ⁇ C S alkylsulfonyl, Ji!
  • R 8 and R 9 are each independently a hydrogen atom, halogen, C, to (: 6 alkyl, C, to C 6 alkoxy, C, to alkylsulfenyl, C: to C 6 alkenyl, N 0 :, CN, formyl or C, a -C S alkoxy Cal Poni Le,
  • R ′ ° is a hydrogen atom, a halogen, R ′ 4 , one O R ′ 4 , one S R ′ 4 , —S ⁇ R I4 , or one S 0 2 R ′ 4 ,
  • R " is a hydrogen atom, R 14 or CN
  • R ' 2 is a hydrogen atom or R' 4 ,
  • R '3 represents a hydrogen atom, halogen, C, -C 5 alkyl, C, ⁇ C 6 haloalkyl, Ca2 Ji 6 cycloalkyl, C, ⁇ C s alkoxy C, ⁇ C s alkyl, C 2 -C 6 alkenyl Or C 2 -C 6 alkynyl;
  • R '4 is, C 1 -C S alkyl, C, ⁇ C 6 eight-necked alkyl, C 2 -C 6 alkenyl, C 2 ⁇ C 6 eight Roarukeniru, C 2 ⁇ C s alkynyl, C: ⁇ C 6 haloalkynyl C 3 -C S cycloalkyl, c, -c 5 alkylcarbonyl or c, -c 6 alkoxyl propyl, Y 'is halogen, R b may be substituted with C' C alkyl, R b in an optionally substituted C 3 ⁇ Cs cycloalkyl, R b in optionally substituted C 2 even though ⁇ Cn alkenyl , optionally substituted with R b C 2 to Cn alkynyl, optionally substituted with R b C, -C 12 alkoxy, optionally substituted with R b C, -C 6 alkoxy C, ⁇ C 5
  • R ' may be substituted by phenyl, R may be substituted with e phenoxy, R e phenyl optionally substituted with C, -C e alkyl , iT optionally substituted by phenyl Cl ⁇ c 6 alkoxy, optionally phenylalanine alkylsulfonyl optionally substituted with R e, R e which may be Hue Nils sulfide El substituted with substituted with R e Good phenylsul Eniru, optionally phenyl C be substituted by Re, ⁇ C 6 alkyl sulphates enyl, phenyl optionally substituted by R c C, -C 6 alkylsulfinyl, optionally substituted with R Hue n
  • Ra is halogen,. ,. 5 alkyl, C, -C 6 haloalkyl, C 3 -C 6 Shikuroa alkyl, C, -C 6 alkoxy, C, -C S alkoxy C, ⁇ C 5 alkyl, C, -C S Al Kirusurufueniru C, ⁇ C 5 alkyl, C, -C 6 Nono Roarukoki ⁇ , C, -C S alkyl Surufueniru, Ji, ⁇ 6 alkylsulfinyl, C, -C 6 alkylsulfonyl, C, ⁇ C s eight necked alkyl sulphates enyl, C 1 -C S eight-neck alkyl sulfide El, C, ⁇ C 6 eight-neck alkylsulfonyl, C 2 ⁇ C 6 7 alkenyl, C 2 ⁇ C 6 eight Roarukeniru, C! ⁇
  • C 2 -C 6 haloalkynylsulfonyl N 0 2 , CN, formyl, SH, SH, SCN, C, -C s alkoxyl-proponyl, C, -C 6 -alkyl-proponyl, ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ ⁇ mouth alkyl power, C, ⁇ C 6 alkyl power phenyl, phenyl or one NU'U 2 , wherein the number of R a to be substituted is 1 to 5 (where R a is 2 In the case of more than one, they may be the same or different from each other),
  • R b is, /, androgenic, C 3 ⁇ C 6 cycloalkyl, C 'Cs alkoxy, C, -C 6 Al Kokishi c, ⁇ c 6 alkoxy, c, to c 6 alkyl sulphates enyl c, to c 6 alkoxy,
  • Nono Roarukokishi C, ⁇ Cs alkyl sulphates enyl, Ci ⁇ Cs alkylsulfamoyl Fier, C, -C 5 alkylsulfonyl, C, ⁇ C s Nono b alkylsulfamoyl phenylalanine, C, ⁇ .
  • R e is halogen, optionally substituted with R b C, ⁇ C, 2 alkyl, optionally substituted with R b C 3 -C S consequent opening alkyl, optionally substituted by R b good C 2 ⁇ C l2 ⁇ Alkenyl, optionally substituted with R b C 2 ⁇ C, 2 alkynyl, optionally substituted with R b C, ⁇ C u alkoxy, optionally substituted with R b C, ⁇ C 6 alkoxy C, -C 6 alkoxy, optionally substituted with R b C 2 ⁇ C 6 7 Rukeniruokishi, optionally substituted with R b C 2 -C 6 Arukiniruokishi, optionally substituted with R b good C, -C 6 alkyl sulphates enyl, optionally substituted with R b C 2 ⁇ C 6 Arukenirusuru phenyl, optionally substituted with R b C 2 ⁇ C 6 al
  • R may phenyl C be substituted by a, -C S alkyl force Ruponiru, R a phenyl optionally substituted with C, ⁇ C s alkylcarbonyl O alkoxy, Teroari one to optionally substituted with R 3 Rukaru Poniru, R a at heteroaryl force Ruponiruokishi to optionally substituted, R a in replacement are optionally heteroarylalkyl O carboxymethyl force Ruponiru also to good, R Teroari to optionally substituted with a Ichiru ⁇ ⁇ Ji 6 alkyl force Ruponiru, to which may be substituted by R a Teroariru. , ⁇ ⁇ . Alkyl Cal Poni Ruo carboxymethyl or a NU'U 2, the number of you substituents R e is 1-5 amino acids (provided that if R 'is 2 or more may be different in the same or other),
  • Facial 'and U 2 each independently represent a hydrogen atom, C, -C 6 alkyl, Ji, ⁇ (: 6 Ha port al kill, C' 3 ⁇ C 6 cycloalkyl, C 1 - C 6 alkoxy C ⁇ C 6 alkyl, C, -C 6 ⁇ Rukirusurufue sulfonyl ⁇ ⁇ ;!
  • n represents the number of substituents and is from 0 to 4,
  • P represents the number of repetitions and ranges from 0 to 2.
  • d is the number of substituents, from 0 to 2
  • e is the number of substituents, from 0 to 3
  • f is the number of substituents, from 0 to 4
  • G represents the number of substituents, from 0 to 5
  • h represents the number of substituents, from 0 to 6
  • i represents the number of substituents and is from 0 to 1
  • j represents the number of substituents and is from 0 to 7,
  • k represents the number of substituents and is from 0 to 8,
  • Y a, Y b and Y are independently Y '-D each other - (CH 2) P - a either (but, when Y or Y a is two or more, Y a How or Y How to one another May be the same or different.),
  • Y may further represent a hydrogen atom.
  • Q represents an oxygen atom, a sulfur atom or N-Yb
  • Y, Ya, Yb, d, f and i have the same meanings as in (2), wherein (1) or (2) A heterocyclic iminophenyl compound or a pesticidally acceptable salt thereof.
  • Y ' is halogen, optionally substituted with R b C, ⁇ C 12 alkyl, optionally substituted with R b C, ⁇ C I2 alkoxy, optionally substituted with R fc C , To C, 2 alkylsulfenyl, optionally substituted by R b C> to Cn alkylsulfinyl, optionally substituted by R b C, to C 12 alkylsulfonyl, substituted by R E Phenyl which is optionally substituted or heteroaryl optionally substituted with R.
  • heterocyclic iminophenyl compound or a pesticidally acceptable salt thereof according to any one of [1] to [4].
  • G is G ', G G' 5 or a B 2.
  • Y ′ is phenyl substituted with at least one IT or heteroaryl substituted with at least one Re, and at least one of Re is trifluoromethyl, wherein G is G ′.
  • n is 1 or more, and the heterocyclic iminophenyl compound or a pesticidally acceptable salt thereof according to any one of [1] to [7].
  • salt (9) the salt according to any of (1) to (8), wherein the salt acceptable as a pesticide is hydrochloride, hydrobromide, hydroiodide, formate, acetate or oxalate Salts of heterocyclic iminophenyl compounds.
  • An agricultural chemical comprising, as an active ingredient, at least one selected from the heterocyclic iminophenyl compounds according to any one of [1] to [9] and salts thereof which are acceptable as agricultural chemicals.
  • a fungicide comprising, as an active ingredient, at least one selected from the heterocyclic iminophenyl compounds according to any one of [1] to [9] and salts thereof which are acceptable as pesticides.
  • An insecticide comprising, as an active ingredient, at least one selected from the heterocyclic iminophenyl compounds according to any one of [1] to [9] and salts thereof that are acceptable as pesticides.
  • Me is a methyl group
  • Et is an ethyl group
  • Pr is a propyl group
  • Bu is a butyl group
  • Pen is a pentyl group
  • Hex is a hexyl group
  • Hep is a heptyl group
  • Oct is an octyl group
  • Non is a nonyl group
  • Dec is a decyl group
  • Undec is a decyl group
  • Dodec is a dodecyl group.
  • C 6 alkyl in the definition of RR 2 , R 3 , R 4 , R s , R 6 , R 7 , R 8 , R s , R 13 , R 14 , R a , X, U 1 and U 2 is directly As chain or branched alkyl, methyl, ethyl, n-propyl, 1-propyl, n-butyl, i-butyl, t-butyl, s-butyl, II-pentyl, n-hexyl, 2-ethylpropyl, 2 , 2-dimethylpropyl, 1,2-dimethylpropyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1 -Methylbutyl, 2-methylbutyl, 3-methylbutyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl,
  • Examples of the halogen atom in the definition of R 5 , R 6 , R 8 , R 9 , R 10 , R 13 , R a , RR c , X and Y ′ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. can give.
  • fluoro or methyl is a straight or branched haloalkyl.
  • RR 2 , R 3 , R 4 , R 5 , R 6 , R 7 , R 13 , R 14 , R a , RU 1, and C 3 to C 6 cycloalkyl in the definition of U 2 include cyclopropyl, cyclobutyl And cyclopentyl and cyclohexyl.
  • C, -C 6 alkoxy includes methoxy, ethoxy, n-propoxy, i. -Propoxy, n-butoxy, tributoxy, S-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, 1, tridimethylpropoxy, 1,2-dimethylpropoxy, 2,2-dimethylpropoxy, 1- Ethylpropoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethylpropoxy, triethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy 1-methylbutoxy, 2-methylbutoxy, 3 -Methylbutoxy, ethoxybutoxy, 2-ethylbutoxy, 1,2-dimethylbutoxy, 1,2-dimethylbutoxy, 1.3-dimethylbutoxy, 2,2-dimethylbutoxy, 2,3-dimethylbutoxy, 3,3
  • Examples of the C 1 -C 6 haloalkoxy in the definition of R 5 , R 6 , R a , R b and X include Ci Ce linear or branched haloalkoxy, and include fluoromethoxy, chloromethoxy, promomethoxy, Methoxy, dichloromethoxy, trichloromethoxy, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, bromodifluoromethoxy, dichlorofluoromethoxy, 1-chloromouth ethoxy, tribromoethoxy, triodoethoxy, trifluoroethoxy 2-chloro ethoxy, 2-bromoethoxy, 2-odoethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2,2,2-trichloroethoxy Kishi, Penyu Fluoroethoxy, 2,2,2-Trifluoro mouth ethoxy,
  • R s , R 6 , R 8 , RRR b and X as C, - ⁇ 6 alkylsulfenyl, straight-chain or branched alkylsulfenyl is methylthio, ethylthio, n-propylthio, tripropylthio, n -Butylthio, i-butylthio, s-butylthio, t-butylthio, n-pentylthio, n-hexylthio and the like.
  • C 6 alkylsulfinyl in the definition of R s , R 6 , R a and R b includes methylsulfinyl, ethylsulfinyl, n-propylsulfinyl, i-propylsulfinyl, and n-propyl as straight-chain or branched alkylsulfinyl Butylsulfinyl, i-butylsulfinyl, S-butylsulfinyl, t-butylsulfinyl, n-pentylsulfinyl, n-hexylsulfinyl and the like
  • C i Cs alkylsulfonyl includes methylsulfonyl, ethylsulfonyl, n-propylsulfonyl, i.e., linear or branched alkylsulfonyl, i -Propylsulfonyl, n-butylsulfonyl, i-butylsulfonyl, S-butylsulfonyl, t-butylsulfonyl, n-pentylsulfonyl, n-hexylsulfonyl and the like.
  • RR 2, R 3, R 4 , R 5, R 6, R 7, R 13, R a as CCS alkoxy d Cs alkyl that put the definition of U 1 and U 2 are main Tokishimechiru, Etokishime chill, 11- Proboxymethyl, tripropoxymethyl, n-butoxymethyl, i-butoxymethyl, S-butoxymethyl, t-butoxymethyl, n-pentyloxymethyl, I-methoxyl, 3-ethoxypropyl and 3-methoxypropyl Etc.
  • C i Ce alkoxy C in the definition of R b Alkoxy includes methoxy methoxy, ethoxy methoxy, n-propoxy methoxy, i-propoxy methoxy, n-butoxy methoxy, thobutoxy methoxy, s-butoxy methoxy, t-butoxy methoxy, n-pentyloxy methoxy, 2-Methoxyxoxy, 3-ethoxypropoxy and 3-methoxypropoxy.
  • alkylsulfenyl ⁇ -alkyl is straight-chain or branched alkylsulfenylalkyl, methylthiomethyl, ethylthiomethyl, ⁇ -propylthiomethyl, i-propylthiomethyl, n-butylthiomethyl, i- Butylthiomethyl, s-butylthiomethyl, t-butylthiomethyl, n-pentylthiomethyl, 2-methylthioethyl, 3-ethylthiopropyl, 3-methylthiopropyl and the like.
  • R b as -C 6 alkyl sulphates enyl C I ⁇ C 6 alkoxy, Mechiruchiome butoxy, Edjiruchiome butoxy, n- Puropiruchiome butoxy, i- flop port Piruchiome butoxy, n - Petit thio methoxy, i- Petit Examples thereof include ruthiomethoxy, S-butyl thiomethoxy, t-butylthiomethoxy, n-pentylthiomethoxy, 2-methylthioethoxy, 3-ethylthiopropoxy and 3-methylthiopropoxy.
  • haloalkylsulfenyl include linear or branched haloalkylthio such as fluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, trifluoromethylthio, trichloromethylthio, 2,2, 2-Trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2-fluoroethylthio, pennofluorethylthio and 1-fluoro-i-propylthio, etc.
  • haloalkylsulfenyl include linear or branched haloalkylthio such as fluoromethylthio, chlorodifluoromethylthio, bromodifluoromethylthio, trifluoromethylthio, trichloromethylthio, 2,2, 2-Trifluoroethylthio, 1,1,2,2-tetrafluoroethylthio, 2-fluoroeth
  • Cs haloalkylsulfyl includes fluormethylsulfinyl, chlorodifluoromethylsulfinyl, and chloromethylsulfinyl as linear or branched octaalkylsulfinyl Difluoromethylsulfinyl, trifluoromethylsulfinyl, trichloromethylsulfinyl, 2,2,2-trifluoroethylsulfiel, 1,1,2,2-tetrafluoroethylsulfinyl, 2-full And fluorethylsulfinyl, penfluorofluorethylsulfinyl and 1-fluoro-i-propylsulfinyl.
  • C s haloalkylsulfonyl in the definition of R s , RR 7 , RR b , U 1 and U 2 includes, as linear or branched haloalkylsulfonyl, fluoromethylsulfonyl, chlorodifluoromethylsulfonyl, Promodifluoromethylsulfonyl, trifluoromethylsulfonyl, trichloromethylsulfonyl Nyl, 2,2,2-trifluoroethylsulfonyl, 1,1,2,2-tetrafluoroethylsulfonyl, 2-fluoroethylsulfonyl, penfluorofluorethylsulfonyl and ⁇ 1-fluoro Mouth-i-propylsulfonyl and the like.
  • C 2 -C 6 alkenyloxy includes linear or branched alkenyloxy such as 1-methylethenyloxy, 2-propenyloxy, trimethyl.
  • C 2 -C 6 haloalkenyloxy includes 2-chloroethenyloxy as linear or branched haloalkenyloxy, 2 -Promothenyloxy, 2,2-dichloroethenyloxy, 3-chloro-2-propenyloxy, 3-fluoro-2-propenyloxy, 3-bromo-2-propenyloxy, 3-odo 2-propenyloxy, 3,3-dichloro-2-propenyloxy, 3,3-difluoro-2-propenyloxy, 4-chloro-2-butenyloxy, 4,4-dichloro-3-butenyloxy And 4,4-difluoro-3-butenyloxy.
  • C 2 -C 6 alkenylsulfenyl includes 1-methylethenylthio and 2-prodyl as linear or branched alkenylsulfenyl.
  • Nylthio 1-methyl-2-propenylthio, 2-butenylthio ', 3-butenylthio, 2-methyl-2-probenzylthio and the like.
  • C 2 -C 6 alkenylsulfinyl includes linear or branched alkenylsulfinyl as 1-methylethenylsulfinyl, 2-provenylsulfinyl, 1- Methyl-2-proenylsulfinyl, 2-butenylsulfinyl, 3-butenylsulfinyl, 2-methyl-2-propenylsulfyl and the like.
  • loalkenylsulfenyl are straight-chain or branched haloalkenylsulfenyl, such as Lucio, 2,2-dichloroethenylthio, 3-chloro-2-propenylthio, 3-fluoro-2-propylenylthio, 3-bromo-2-propenylthio, 3-hydride- 2-propenylthio, 3,3-dichloro-2-propenylthio, 3,3-difluoro-2-propenylthio, 4-chloro-2-butenylthio, 4,4-dichloro-3-butenylthio and And 4,4-difluoro-3-butenylthio.
  • Lucio 2,2-dichloroethenylthio
  • 3-chloro-2-propenylthio 3-fluoro-2-propylenylthio
  • 3-bromo-2-propenylthio 3-hydride- 2-propenylthi
  • C 2 -C 6 noloalkenylsulfinyl includes 2-chloroethenylsulfiel, 2-bromoethenylsulfiel as a straight-chain or branched octaalkenylsulfinyl , 2,2-dichloroethenylsulfinyl, 3-chloro-2-phenylenylsulfinyl, 3-fluoro-2-phenylenylsulfiel, 3-bromo-2-proenylsulfinyl, 3-chloride 2-propenylsulfinyl, 3,3-dichloro-2-propenylsulfinyl, 3,3-difluoro-2-propenylsulfinyl, 4-chloro-2-butenylsulfinyl, 4,4-dichloro -3-butenylsulf
  • C 2 -C 6 octaalkenylsulfonyl includes 2-chloroethenylsulfonyl, 2-bromoethenylsulfonyl, as a straight-chain or branched haloalkenylsulfonyl, 2,2-dichloroethenylsulfonyl, 3-chloro-2-propylenylsulfonyl, 3-fluoro-2-proenylsulfonyl, 3-bromo-2-proenylsulfonyl, 3-node- 2-Probenylsulfonyl, 3,3-dichloro-2-propylenylsulfonyl, 3,3-difluoro-2- 2-proenylsulfonyl, 4-chloro-2-butenylsulfonyl, 4,4-dichloro
  • C 2 -Ce haloalkynyl in the definition of R 5 , R 6 , R 14 and R a , chloroethynyl, promoethynyl, chloroethynyl, 3-chloro-2-propynyl, 3 -Bromo-2-propynyl, 3-odo-2- And propynyl, 4-bromo-3-butynyl, 4-hydrodo-3-butynyl and 6-hydrodo-5-hexynyl.
  • C to C alkynyloxy in the definition of R 5 , R 6 , R a and R b ethynyloxy, 2-propynyloxy, 1-methyl-2-propynyloxy, as linear or branched alkynyloxy, 1,2-dimethyl-2-propynyloxy, trimethyl-1-ethyl-2-propynyloxy, 2-butynyloxy, 3-butynyloxy, trimethyl-2-butynyloxy, 1,1-dimethyl-2-butynyloxy , 1-pentynyloxy, 2-pentynyloxy, 3-pentynyloxy, 4-pentynyloxy and hexynyloxy.
  • C 2 -C 6 octaalkynyloxy includes chloroethynyloxy, buguchi moetinyloxy, and chloroethynyloxy as linear or branched haloalkynyloxy.
  • C 2 -C 6 octaalkynyloxy includes chloroethynyloxy, buguchi moetinyloxy, and chloroethynyloxy as linear or branched haloalkynyloxy.
  • C 2- (: 6 alkynylsulfer is a straight-chain or branched alkynylsulfenyl such as ethynylthio, 2-propynylthio, 1-methyl 2-propynylthio, 1, tridimethyl-2-propynylthio, 1-methyl-1-ethyl-2-propynylthio, 2-butynylthio, 3-butynylthio, trimethyl-2-butynylthio, 1 , Dimethyl-2-butynylthio, 1-pentynylthio, 2-pentynylthio, 3-pentynylthio, 4-pentynylthio and hexynylthio.
  • C 2 -C 6 alkynylsulfenyl is ethynylsulfinyl, 2-propynylsulfinyl, 1-methyl-2 as a linear or branched alkynylsulfinyl -Propynylsulfinyl, 1,1-dimethyl-2-propynylsulfinyl, trimethyl-1-ethyl-2-propynylsulfinyl, 2-butynylsulfinyl, 3-butynylsulfinyl, 1-methyl-2- Butynyl sulfinyl, 1,2-dimethyl-2-butynylsulfinyl, topentinylsulfinyl, 2-pentynylsulfinyl, 3-pentynylsulfenyl, 4-pentynyls Luf
  • C 2 -C 6 alkynylsulfonyl in the definition of R s , R 6 , R a and R b includes ethynylsulfonyl, 2-propylvinylsulfonyl and trimethyl-2- as linear or branched alkynylsulfonyl Propynylsulfonyl, 1, tridimethyl-2-propynylsulfonyl, trimethyl-1-ethyl-2-propynylsulfonyl, 2-butynylsulfonyl, 3-butynylsulfonyl, 1-methyl-2-butynylsulfonyl, 1, Examples include dimethyl-2-butynylsulfonyl, topentinylsulfonyl, 2-pentynylsulfonyl, 3-pentynylsulfonyl, 4-pentynylsulfonyl
  • C 2 -C 6 haloalkynylsulfenyl is a straight-chain or branched haloalkynylsulfenyl such as ethynylthio or bromoethynylthio. 4-ethynylthio, 3-chloro-2-propynylthio, 3-bromo-2-propynylthio, 3-bromo-2-propynylthio., 4-bromo-3-butynylthio, 4-phenyl Examples include -3-butynylthio and 6-node-5-hexynylthio.
  • R 5 , R 6 As the C 2 -C 6 haloalkynyl sulfiel in the definition of Ra and R b , chloroethynyl sulfinyl, bromoethynyl sulfinyl, and chloroethynyl sulfinyl are used as linear or branched haloalkynyl sulfiels.
  • C 2 -C 6 haloalkynylsulfonyl includes chloroethynylsulfonyl, bromoethynylsulfonyl and eodoethynyl as a straight-chain or branched haloalkynylsulfonyl Sulfonyl, 3-chloro-2-propynylsulfonyl, 3-bromo-2-propynylsulfonyl, 3-prop-2-propynylsulfonyl, 4-bromo-3-butynylsulfonyl, 4-odo-3- Butynylsulfonyl and 6-hydroxy-5-hexylsulfonyl and the like.
  • -C alkoxycarbonyl includes methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, i-propoxycarbonyl, n-butoxycarbonyl, i-butoxycarbonyl, s-butyl Examples include toxicalponyl, t-butoxycarbonyl, n-pentyloxycarbonyl, and n-hexyloxycarbonyl.
  • R 5 , R 6 , R 7 , R 14 , R 3 , R b , X, C 1 to C 6 alkylcarbonyl in the definition of U 1 and U 2 include acetyl, straight-chain or branched alkyl carbonyl Examples thereof include propionyl, n-propyl carbonyl, n-propyl carbonyl, n-butyl carbonyl, i-butyl carbonyl, s-butyl carbonyl, t-butyl carbonyl, n-pentyl carbonyl and II-hexyl carbonyl.
  • C i -C 6 haloalkylcarbonyl is a straight-chain or branched haloalkylcarbonyl, chloroacetyl, fluoroacetyl, chlorofluoroacetyl, chlorodifluroacetyl, dichloroacetyl. , Difluoroacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl, penfluorofluoropropionyl and the like.
  • Ci Ce alkyl carboxy includes linear or branched alkylcarbonyloxy such as acetyloxy, propionyloxy, and n-propyl-propionyloxy. , I-propyl carbonyloxy, n-butylcarbonyloxy, i-butylcarbonyloxy, s-butylcarbonyloxy, t-butylcarbonyloxy, n-pentylcarbonoxy, and n-hexylcarbonyloxy And the like.
  • R ⁇ R 2, R 3, in R 4, the R 5, R 6, R 7 and R e defined, as good Hue sulfonyl ⁇ I ⁇ C beta alkyl optionally substituted by R a represents a linear Or benzyl, 2-chlorobenzyl, 3-bromobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-1-butylpentyl, 2-methylbenzyl, 2-methoxybenzyl, as branched phenylalkyl Triphenylethyl, 1- (3-chlorophenyl) ethyl, 2-phenylethyl, trimethyl-1-phenylethyl, 1- (4-chlorophenyl) -1-methylethyl, 1- (3-chlorophenyl)- Trimethylethyl, triphenylpropyl, 2-phenyl Mouth pill, 3-phenylpropyl, triphenylbutyl, 2-phenylbutyl, 3-phenylbutyl
  • Phenyl which may be substituted by Ra in the definitions of R 3 , R 5 , R 6 , R 7 , R b and R e includes Ph, 2-Cl-Ph, 3-CI-Ph, 4- Cl-P, 2-F-Ph.
  • R 5 , R 6 , R 7 , R b and R e a heteroaryl which may be substituted with Ra , a heteroarylsulfonyl which may be substituted with R a, which is substituted with R a defined by Teroari one Rukaruponiru also to be in, the heteroaryl may be substituted by R a, 5-chloro Chio phen - 2-I le, 3,5-dimethyl furans - 2-I le, 3-cyanopyrrol-1-yl, oxazol-2-yl, 2-methylsulfenyloxazole-1-yl, 4-methylthiazole-2-yl, 2-trifluoromethyluimidazole-1 -Yl, isoxazole-3-yl, 3-chloroisoxazole-4-yl, 3-methylisothiazol-5-yl, 3-phenylvirazol-1-yl, tolmeti Rubirazol-5-yl, 2-methylsulfonyl-1,
  • R 5 , R 6 , R 7 , R ⁇ R e and X may be substituted with Ra Optionally substituted with Nirusuruhoniru and R a are defined in good phenylene Rukaruponiru as good phenyl optionally substituted with R a, phenyl, 2-Furuorofu Eniru, 3-fluorophenyl, 4-fluorophenyl, 2-Chlorophenyl, 3-Chlorophenyl, 4-Chlorophenyl, 2-Bromophenyl, 3-Bromophenyl, 4-Bromophenyl, 4-Chlorophenyl, 2,4-Dichlorophenyl, 3,4 -Dichlorophenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl, 2-fluoro-4-chlorophenyl, 2,3,4,5,6-phenylfluorophenyl, 2-methylphenyl, 3-methylphenyl Methyl
  • R s , R 6 , R 7 , R b and scale In, optionally substituted with R a phenyl optionally substituted by C i ⁇ C 6 alkylsulfonyl and R a is also defined in good phenyl C i ⁇ C 6 alkyl force Ruponiru, optionally substituted with R a as also good phenyl C i to C 6 alkyl, benzyl, 2 - click every mouth benzyl, 3 - Pro benzyl, 4-click Rorobenjiru, 4-methylbenzyl, 4-1 - heptyl benzyl, 2-methylbenzyl, 2 - Methoxybenzyl, 1-phenylethyl, 1- (3-methylphenyl) ethyl, 2-phenylethyl, trimethyl-1-phenylethyl, 1- (4-phenylphenyl) -trimethylethyl, 1- (3 -Methylphenyl, triphenylpropyl
  • R 7 R b and R e, be substituted by R a may be substituted by phenoxy and R a is defined by the even better off enoki deer Lupo sulfonyl, optionally substituted with R a phenoxy
  • R a is defined by the even better off enoki deer Lupo sulfonyl, optionally substituted with R a phenoxy
  • Examples include phenoxy, 2-fluorophenoxy, 3-fluorophenoxy, 4-fluorophenoxy, 2-chlorophenoxy, 3-chlorophenoxy, 4-chlorophenoxy, 2-bromophenoxy, and 3-bromophenoxy , 4-bromophenoxy, 4-chlorophenoxy, 2,4-dichlorophenoxy, 3,4-dichlorophenoxy, 2,6-difluorophenoxy, 2,6-dichlorophenoxy, 2-fluoro- 4-chlorophenoxy, 2,3,4,5,6-pentafluorofluorophenoxy, 2-
  • R 7, R b Oyopi 1 £ in the definition of a good Hue sulfonyl ⁇ i -C alkoxy optionally substituted with R a represents a linear or branched phenylalanine alkoxy as Ben Jiruokishi, 2- Black Oral benzyloxy, 3-bromobenzyloxy, 4-chlorobenzyloxy, 4-methylbenzyloxy, 4-t-butylpentyloxy, 2-methylbenzyloxy, 2-methoxybenzyloxy, triphenyl Ethyloxy, 1- (3-chlorophenyl) ethylyl, 2-phenylphenylyloxy, trimethyl-1-phenylethylyloxy, 1- (4-phenylphenyl) -trimethylethyloxy , Tri (3-chlorophenyl) -trimethylethyloxy, 1-phenylpropyloxy, 2-phenylpropyloxy, 3-phenylpropyloxy, 1-pheny
  • R 7 R b and R e, is defined optionally substituted with R a Teroari one to optionally substituted with Ruoki shea and R a to good even heteroarylalkyl O alkoxycarbonyl, substituted by R a
  • optionally substituted arylaryloxy include 5-chlorothiophen-2-yloxy, 3,5-dimethylfuran-2-yloxy, 3-cyano-pyrrol-1-yloxy, and oxazole-2-yl.
  • R a with optionally substituted Fuenirusurufue cycloalkenyl, as defined in R a good phenylene Luca Lupo alkylsulfonyl optionally substituted by optionally substituted Hue Nils sulfinyl and R a at O alkoxy is a R a may phenyl optionally substituted with, phenyl, 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl phenyl-2-Clos port phenyl, 3- black port phenyl, 4-black port phenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 4-dodophenyl, 2,4-dichlorophenyl, 3,4-dichlorophenyl, 2,6-difluorophenyl, 2,6-dichlorophenyl , 2-fluoro-4-chlorophenyl, 2,3,4,5,
  • R c optionally substituted with R a in an optionally substituted phenyl C i ⁇ C 6 alkylsulfinyl Hue alkylsulfonyl, phenyl optionally substituted with R a C i ⁇ C 6 alkylsulfinyl and R a as good phenyl C 6 alkyl optionally substituted with even better phenyl C i to C alkyl force Lupo two are defined in Ruokishi R a, a linear or benzyl as branched-phenylalanine alkyl, 2- black port Benzyl, 3-bromobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-t-butylbenzyl, 2-methylbenzyl, 2-methoxybenzyl, 1-phenylethyl, 1- (3-chlorophenyl) ethyl , 2-phenylethyl, trimethyl-1-phenylethyl, 1_ (4-chloropheny
  • R c a heteroarylsulfinyl optionally substituted with Ra , a heteroarylsulfenyl optionally substituted with Ra, and a heteroarylcarbonyloxy optionally substituted with R a
  • R a 5-chloro Chio phen - 2-I le, 3, 5-dimethyl furans - 2 - I le, 3 Shianopiro Ichiru 1-I 2-oxyl-2-oxyl, 2-methylsulfenyloxazole-4-yl, 4-methylthiazol-2-yl, 2-trifluoromethylimidazole-1-yl, isoxazole-3 -Yl, 3-methylisothiazol-4-yl, 3-methylisothiazole-5-yl, 3-phenylpyrazole-1-yl, trimethylpyrazole-5-yl, 2- Methylsulfonyl-1,3,4-oxaziazol-5-yl, 2-promo-1,3,4
  • the heteroaryl C i to C 6 alkoxy optionally substituted with R a in the definition of R c includes pyridine-2-ylmethyloxy and 5-chlorothiophene as linear or branched heteroalkoxy.
  • R e Teroariru to optionally substituted with R a C i ⁇ C beta Arukirusu Rufueniru
  • R a Ichiru C Cs alkyl sulfates Fier optionally substituted with R a heteroaryl C t Ce alkylsulfonyl into good, as defined in Teroari Ichiru C i ⁇ C 6 alkyl Cal Poni Le Okishi to optionally substituted with R a, Teroariru C i to the optionally substituted with R a C 6 the Al kill, pyridine as terrorism ⁇ reel alkyl straight or bifurcated form of - 2 - Irumechiru, 5-chloro Chio phen - 2 - Irumechiru, Bok-methyl-3-black port pyrazole Ichiru 5 Irumechiru, 2 -(3-methylfuran-2-yl) ethyl, 3- (6-trifluoromethylpyr
  • Hue Nils Ruff enyl, optionally substituted with R e
  • Hue Nils sulfinyl, optionally substituted with R e phenylalanine sulfonyl, phenylene optionally substituted with Re Rukaruponiru and as good phenyl substituted with optionally substituted with R e are defined by good phenylene Rukarupo two Ruoki shea R e, Ph, 2-Cl -Ph, 3- Cl-Ph, 4-Cl- Ph, 2-F-Ph, 3-F-Ph, 4-F-Ph, 2-Me-Ph, 3-Me-Ph, 4-Me-Ph, 2-MeO-Ph, 3-MeO-Ph, 4-MeO- Ph, 4-Br-Ph, 2, 4-Cl 2 -Ph, 3, 4-Cl 2 -Ph, 2, 4, 6- CI 3 -P
  • phenyl which may be substituted by R c C i ⁇ C 6 alkyl, phenyl optionally substituted by R c C i ⁇ C 6 alkyl sulphates enyl, optionally substituted with R e in phenyl C i ⁇ C 6 alkylsulfinyl, phenyl optionally substituted with R ⁇ C i ⁇ C 6 alkylsulfonyl, phenylene optionally substituted with R e le C 1 -C 6 alkyl Cal Poni Le and R c
  • Optionally substituted phenyl C, -C e alkyl force defined as rubonyoxy, phenyl C, -C 6 alkyl optionally substituted with R e may be a linear or branched phenylalkyl As benzyl, 2-chlorobenzyl, 3-bromobenzyl, 4-chlorobenzyl, 4-methylbenzyl, 4-t-butyl
  • Rupentyloxy trimethyl-2-phenylpentyloxy, trimethyl-3-phenylpentyloxy, trimethyl-4-phenylpentyloxy, 2-methyl-2-phenylpentyloxy, 2- (4-clophenyl) -2 -Methylpentyloxy and 2-methyl-2- (3-methylphenyl) pentyloxy.
  • R e optionally substituted with R e may be substituted by phenoxy and R c are defined in good phenoxy force Ruponiru, a good off enoxy be substituted with R e it is phenoxy, 2- Fluorophenoxy, 3-fluorophenoxy, 4-fluorophenoxy, 2-chlorophenoxy, 3-chlorophenoxy, 4-chloro mouth Phenoxy, 2-bromophenoxy, 3-promophenoxy, 4-promophenoxy, 4-phenylphenoxy, 2,4-dichlorophenoxy, 3,4-dichlorophenoxy, 2,6-difluorophenoxy, 2,6 -Dichlorophenoxy, 2-Fluoro mouth-4-Chlorophenoxy, 2,3,4,5,6-Pentafluorophenoxy, 2-Methylphenoxy, 3-Methylphenoxy, 4-Methylphenoxy, 2,5- Dimethylphenoxy, 4-methyl-2,3,5,6-tetrafluorophenoxy, 2-me
  • heteroaryl optionally substituted with R e, Teroari one to optionally substituted with R c Rusurufiniru, R e in substituted Teroa Li one also to be optionally Rusurufue sulfonyl, R e in Teroari one Rusuruhoniru to optionally substituted, as defined in R Teroari one Luca Lupo sulfonyl to optionally substituted with Teroari one Rukaruponiru and R e to optionally substituted with c O alkoxy, R e
  • the heteroaryl which may be substituted with 2-fluorofuran-3-yl, 3-cyanovirol- ⁇ -yl, oxazole-2-yl, 2-methylsulfenyloxazolyl_4_yl, 2-Methylsulfonyl-1, 3,4-oxaziazol-5-yl, 2-bromo-1,3,4-thiadiazol-5-yl, 1,2,4-
  • Y ' to which may be substituted with R e heteroaryl C i ⁇ C 6 alkyl, into which may be substituted with R e Teroari - Le C, ⁇ C beta alkylsulfamoyl phenylalanine, is substituted with R c
  • R c Optionally substituted heteroaryl C i-C ⁇ alkylsulfinyl, heteroaryl optionally substituted with R c C 6 -C 6 alkylsulfonyl, heteroaryl optionally substituted with R 6-(: 6 alkylcarbonyl) and optionally be substitution by R e are defined by heteroaryl C 6 alkylcarbonyl O carboxymethyl also to good, as the Teroari Ichiru C i C e alkyl to optionally substituted with R 11, straight-chain or branched Pyridine-2-ylmethyl, 5-chlorothiophen-2-ylmethyl, 1-methyl-3-cyclohexylpyrazol-5-ylmethyl, 2-
  • Heteroaryl optionally substituted with R e as defined for heteroaryloxy optionally substituted with Rc and heteroaryloxycarbonyl optionally substituted with R c for Y ′
  • Examples of 1-hydroxy include 5-chlorothiophen-2-yloxy, 3,5-dimethylfuran-2-yloxy, 3-cyano-trimethylpyrrol-1-yloxy, oxazol-2-yloxy, and 2-methylsulfenyl.
  • R b are defined which may C -C 6 alkyl Cal Poniruokishi, substituted with R b is a good C -C 6 alkyl which may be straight-chain or branched methyl as alkyl, Echiru, n- propyl, i- propyl, n- butyl, i - heptyl, t- butyl, s- butyl , N-pentyl, n-hexyl, 2-ethylpropyl, 2,2-dimethylpropyl, 1,2-dimethylpropyl, 1'1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl- 1-methylpropyl, 2-ethylpropyl, 1-methylpropyl Butyl, 2-methylbutyl, 3-methylbutyl, 1,2-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,
  • ⁇ C alkenyl, linear or branched Eparu alkenyl, 1-propenyl, 2-propenyl, Bok butenyl, 2-butenyl, 3-butenyl, Bok pent two Le, 2-pentenyl, 3 -Pentenyl, 4-pentenyl, trihexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, 5-hexenyl, trimethyl-2-propenyl, 2-methyl-2-propenyl , 1,2-dimethyl-2-propenyl, 1,2-dimethyl-2-propenyl, 1-ethyl-2-propenyl, 1-methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl-3-butenyl, 3-methyl-3-butenyl, 1,1-dimethyl-2-butenyl, 1,1-dimethyl- 3-butenyl, 1,2-
  • R b in the optionally substituted C 2 -C Arukiniruokishi in Oyopi ⁇ ' which may be substituted by R b C 2 -C 6 alkylene Nils Ruff enyl, optionally substituted by R b good C 2 -C 6 alkynylsulfinyl, and optionally substituted with R b may be defined by a good C 2 ⁇ C beta alkynylsulfonyl, optionally substituted with R b
  • C to C alkynyl straight-chain or branched alkynyl such as ethynyl, tripropenyl, 2-propynyl, trimethyl-2-propynyl, 1,1-dimethyl-2-propynyl, 1-methyl-1-ethyl- 2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 1, trimethyl-2-butynyl, 1, 1-dimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, triethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3 -Butynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentyny
  • Oyobi ⁇ optionally substituted with R b in 'C is defined by -C 6 alkoxy force Lupo sulfonyl, a good C i ⁇ C 6 alkoxy optionally substituted with R b is Methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, tobutoxy, S-butoxy, t-butoxy, n-pentyloxy, n-hexyloxy, 1, Dimethylpropoxy, 1,2-dimethylpropoxy, ⁇ , 2-dimethylpropoxy, trethylpropoxy, 1,1,2-trimethylpropoxy, 1,2,2-trimethypropoxy, trethyl-1-methylpropoxy, 1-ethyl-2-methylpropoxy, trimethylbutoxy, 2-methylbutoxy, 3-methylbutoxy, tolueneethyloxy, 2-ethylbutoxy, 1,1-dimethylbutoxy, 1,2-dimethylbutoxy, 1.3-dimethylbutoxy,
  • C to C 12 alkyl which may be substituted with R b in the definition of ⁇ ⁇ ⁇ ⁇ is methyl, ethyl, II-propyl, i-propyl, n-butyl as straight-chain or branched alkyl.
  • a good C 2 -C 12 Arukini Le optionally substituted with R b in the definition of Oyobi ⁇ ', straight-chain or branched Edjiniru as alkynyl, Bok propynyl, 2 - Puropieru, 1-methyl-2- Propynyl, 1,1-dimethyl-2-propynyl, 1-methyl-1-ethyl-2-propynyl, 1-butynyl, 2-butynyl, 3-butynyl, trimethyl-2-butynyl, 1-methyl-3- Butynyl, 2-methyl-3-butynyl, 1,1-dimethyl-2-butynyl, 1, tridimethyl-3-butynyl, 1,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butane Tinyl, triethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1
  • R c and Y R b which may be the C ⁇ 1 2 alkoxy-substituted with in the definition of 'main butoxy a straight-chain or branched alkoxy, ethoxy, n- pro epoxy, i -!
  • R c and Y may be substituted in R b C in the definition of ', as the -C beta alkoxy C i C e alkoxy, main Tokishime butoxy, Etokishime butoxy, n- Provo Kishime butoxy, i - Purobokishime butoxy, n -Butoxymethoxy, tributoxymethoxy, s-butoxymethoxy, tributoxymethoxy, n-pentyloxymethoxy, 2-methoxyethoxy, 3-ethoxypropoxy, 3-methoxypropoxy, cyanomethoxyethoxy, 2- (2-nitroethoxy) Ethoxy) ethoxy, 3- (trimethylvirazol-5-ylmethoxy) propyloxy, 4- (3-cyano-2-methylpropyloxy) butoxy, 5-benzyloxypentyloxy and 5- (2- Trifluoromethylthiazole-5-yl) methoxyhexyloxy and the like.
  • a 3- to 7-membered ring which may contain 1 to 3 oxygen atoms, nitrogen atoms or sulfur atoms together with the carbon atom by two Y substituted on the same carbon of A in the definition of Y Examples include cyclopropyl, 2,2-dichlorocyclopropyl, cyclobutyl, oxetane and cyclopentyl.
  • R 2 and R 3 may contain a hetero atom from the 1 selected from nitrogen atom or a sulfur atom 4 of the 3 7-membered
  • the ring includes aziridine, morpholine, hexamethyleneimine, 4-benzylpiperazine and the like.
  • an oxygen atom from 1 selected from nitrogen or sulfur atom may contain four heteroatom
  • Examples of the 3- to 7-membered ring include aziridine, morpholine, hexamethyleneimine and 4-benzylpiperazine.
  • A is preferably 69 people I
  • Y, Ya, Yb, d, e, f, g, h, i, j, and k represent the same meaning as described above.
  • R 1 is preferably a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, 3-methylbutyl, n-hexyl and benzyl And more preferably methyl.
  • R 2 is preferably a hydrogen atom, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, n-pentyl, 3-methylbutyl, n-hexyl and Benzyl and the like, more preferably methyl.
  • the R 3, preferably a hydrogen atom, methyl, Echiru, base may be substituted by R a in phenyl optionally substituted and R a Njiru and the like, and more Preferably a hydrogen atom, a good phenyl and methyl optionally substituted with R a.
  • R 4 includes a hydrogen atom, methyl, ethyl, benzyl and the like, and more preferably methyl.
  • the R 5, a hydrogen atom, methyl, Asechiru, phenyl and base Njiru etc. elevation Gerare, more preferably methyl Contact Yopi Asechiru.
  • R 6 a hydrogen atom, a chlorine atom, methyl, Echiru, main butoxycarbonyl, methylsulfinyl phenylalanine, good phenyl and base Njiru like optionally substituted with R a and the like.
  • R 7 which may be substituted by R a phenyl, heteroaryl optionally substituted by R a, a hydrogen atom, methyl, Echiru, main butoxy, Benjiruokishi, optionally substituted with Asechiru and R a Good benzyl and the like.
  • R 8 and R 9 include a hydrogen atom, a chlorine atom, methyl, ethyl and benzyl.
  • Examples thereof include a hydrogen atom, a chlorine atom, methyl and methoxy.
  • R 12 examples include a hydrogen atom and methyl.
  • the R 13, a hydrogen atom, a chlorine atom, a bromine atom, and methyl and main butoxy can be mentioned up.
  • the R a preferably, a halogen atom, d- ⁇ Ce alkyl, C i Cs alkoxy, d Ce eight Roarukiru, C eight Roarukokishi, CN, nitro and
  • Ci Ce alkoxycarbonyl and the like and more preferably, Cl, F, Br, trifluoromethyl, methoxy, ethoxy, ethyl, propyl and methyl.
  • the R b preferably, a halogen atom, d- ⁇ Ce Teroariru alkoxy, d Cs ⁇ Ruki Rusuru phenylalanine, phenyl optionally substituted with R a, into which may be substituted by R a, CN, nitro and ⁇ ⁇ ⁇ 6 alkoxy force Ruponiru the like.
  • R c is preferably a halogen atom or a phenyl which may be substituted with Ra.
  • heteroaryl optionally substituted with R a which may be substituted by R a full Enirukaruponiru may phenylalanine alkylsulfonyl optionally substituted with R a, which may be substituted by R b C i Cs alkyl, substituted with 15 tee be Yoi (: 2-0 6 ⁇ Le Kenyir, R b in an optionally substituted C 2 ⁇ C 6 alkynyl, optionally Ct optionally substituted by R b Ce alkoxy, optionally substituted with R b C! ⁇ C 6 alkylsulfinyl phenyl, CN, nitro, OH, SH, include S CN and alkoxycarbonyl alkylsulfonyl, and the like.
  • the X preferably a halogen atom, Ci C alkyl, ( ⁇ ⁇ 4 alkoxy, Ci Cz haloalkyl, C! -C 2 haloalkoxy, CN, nitro, S- R, in NU'U 2, R a optionally substituted phenylene Rukaruponiru and C i ⁇ C 4 ⁇ Le Koki deer Lupo sulfonyl and the like, and more preferably, C l, F, I, B r, methemoglobin alkoxy, Echiru, n- propyl, ethoxy, n -Propoxy., Chlorodifluoromethyl, trifluoromethyl, trifluoromethoxy, difluoromethoxy, methoxypropyl, pendufluorethyl, ethoxycarponyl, CN, acetyl and methyl.
  • the Y ' preferably a hydrogen atom, a halogen atom, optionally substituted with R b Ct Ce alkyl, optionally substituted with R b C! ⁇ C 6 alkoxy, optionally substituted with R c Phenyl which may be substituted with R e , phenyl which may be substituted with R c , C! Cs alkyl, R. Heteroaryl, CN, nitrothio Ci-C 6 alkoxycarbonyl, etc. which may be substituted.
  • the U 1 and U 2 preferably a hydrogen atom, C, ⁇ C 4 alkyl, C. ⁇ C 2 haloalkyl, phenyl, Heteroariru, C i ⁇ C 4 alkylcarbonyl and d Ca alkoxycarbonyl, and the like, and more Preferably, H, methyl, phenyl, benzyl, acetyl, methoxycarbonyl are mentioned.
  • Q 6 is preferably 110 or 1 S—.
  • G includes G 1 , G 2 , G 3 , G 4 , G 5 , G 6 , GG 8 , G 15 and G 16 , and preferably G 1 , G 2 , G 3 , GG 1 S and G 16 , more preferably 0 1 and 0 15 .
  • B 1 preferably includes one N (OR 4 ) —, one N (R 5 ) one, one 0— and —S—, and more preferably, —N (OR 4 ) — and —N (R 5 ) — for example.
  • the A 2 preferably, include A 2 a.
  • n is preferably 0, 1 or 2.
  • P is preferably 0 or 1.
  • Salts of the heterocyclic iminophenyl compound of the present invention which are acceptable as pesticides include, for example, hydrochloride, hydrobromide, hydroiodide, formate, acetate, ammonium salt, isopropylamine salt and the like. Oxalate and the like.
  • the compound of the present invention does not change the imino bond of the formula (1) due to tautomerism.
  • plant diseases to be controlled by the present compound include:
  • Rice + rice blast (Pyr icularia oryzae), sesame leaf blight;) hei (Cochl iobolus miyabeanu s), sheath blight (Rhizoctonia solani),
  • Wheat powdery mildew (Erys iphe graminis, f.sp.hordei, f.sp.tritici), leaf spot (Pyrenophora graminea), net spot (Pyrenophora teres), red force, rust (G ibberel la zeae) ), Rust (Puccinia striiformis, P. graminis, P. recondi ta, P. hordei), snow rot (Typhula sp., Micronectriel la nivais), smut (Ustilago tritici, U.
  • Apple morilia disease (Sclerotinia mali), rot disease (Valsa mali), powdery mildew (Podosphaera leucotricha), spot rot (Al ternar ia mali), scab (Ventur ia inaequal is),
  • Pear scab (Ventur ia nashicola), black spot (Alternaria Kikuchiana), red scab (Gymnosporangium haraeanum),
  • Peach scab (Sclerotinia c inerea), scab (Cladosporium carpophi Ium), phomopsis rot (Phomopsis sp.),
  • Grape downy mildew (Plasmopara viticola), black rot (Elsinoe ampel ina), ⁇ rot (Glomerel la cingulata), powdery mildew (Unc inula necator), rust; / Hei (Phakopsora ampelopsidis),
  • Tomato plague (Phytophthora infestans), ring spot (Alternaria solani), leaf blight (Cladosporium fulvam),
  • Soybean purpura (Cercospora kikuchi i), black spot (Elsinoe glycines), black spot (Diaporthe phaseololum),
  • Black scab (Mycosphaerel la personatum;, Cercospora arac hidi cola),
  • Charcoal blight (Exobasidium ret iculatum), white scab (Elsinoe leucospi la), tano, scab (Al ternaria longipes), powdery mildew (Erys iphe cichoracea rum), anthracnose (Col letotrichum tabacum) ), Beet spot of sugar beet (Cercospora be t icola),
  • Rose scab (Diplocarpon rosae), powdery mildew (Sphaerotheca pannosa), chrysanthemum brown spot (Septoria chrysanthenii indici), white rust (Puccinia horiana),
  • Examples include gray rot of various crops (Botrytis cinerea) and sclerotium of various crops (Scleroti nia sclerotiorura).
  • the compound of the present invention is useful for so-called agricultural pests that infest agricultural and horticultural crops and trees, so-called livestock pests that infest livestock and poultry, and so-called sanitary pests that have various adverse effects on human living environments such as houses.
  • the so-called stored pests that injure stored grains and the like, as well as mites, nematodes, molluscs, and crustaceans that occur and injure in similar situations can be effectively controlled at low concentrations.
  • Insects, mites, nematodes, molluscs, and crustaceans that can be controlled using the compound of the present invention include, but are not limited to, the following.
  • Nikameiga Cho 10 suppressal is
  • Kopnomei sword Cnaphalocrocis medinal is
  • Phantaobogyaga Naerenga aenescens
  • Ichimondiseseri Parnara gut tata
  • Konaga Plutel la xylostel la
  • Yotodoka Mames tra scho, Mames tra sau bra) (Pier is rapae cruc i vora), Kabulaga (Agrotis segetum), Hasmontou (Spodptera litura), Shiroptimontoto (Spodptera ex igua), Helicoverpa armigera, Adrian oxophyes (Ad oxophyes) Jyanomaki (Homona magnanima), Peach peach (Carpos ina ni
  • Power bee (Athalis rosae ruf icornis), pine tree wasp (Neodiprion ser tifer), black beetle (Apethymust kuri), guntai ant, croatian ant (Camp onotus japonicus), fossu mesti (Vespa mandarina) Hymenoptera pests such as and pharaoh ant,
  • Thrips palmi Thrips tabaci
  • Thrips palm thrips (Frankliniella occidental is)
  • Yellowtail thrips (Frankliniella intonsa)
  • total thrips of Sci Rt s Eye pests
  • Reticulate pests such as black cockroaches (Periplaneta ful iginosa), black cockroaches (Periplaneta japonica), and German cockroaches (Blattella germanica); Orthopterous pests such as Locusta migratoria), Sorbus locust (Oxya yezoensis) and mackerel Kuttalibaba (Schistocerca gregaria)
  • Termite pests such as house termites (Coptotermes formosanus), mountain termites (Leucotermes sper atus) and evening termites (Odontotermes formosanus);
  • Isoptera pests such as cat flea (Ctenocephalides felis), human flea (Pulex irritans) and cape flea (Xenopsylla cheopis)
  • Louse pests such as white lice (Haematopinus eurys ternus), red lice (Haematopinus suis), white lice (Linognathus vituli) and white lice (Solenopotes capillatus), Species of pests, such as stag beetles (Ctenolepisma villosa)
  • Lepidopteran pests such as hiratachiya evening te (Liposcelis bos tryc ophi lus),
  • Mucodont pests such as the beetle mouth fly (Onychiuras pseudarmatus yagi i) and the white beetle (Onych iuridae),
  • Fucarid mites such as Citrus avidani (Aculops pelekassi), Aciens abundantii (Epi tr imerus pyri), Tulip rust mite (Acer ia tulipae), and Acaphy 11a theae
  • hocollida Two types of hocollida, such as 'Pyphagotarsonemus latus' and cyclamen hocollida
  • House mites such as the honeybee mite (Varroa jacobsoni)
  • Ticks such as the ticks (Boophilus niicroplus) and Haemaphysalis 1 ongicornis,
  • Sarcoptic mites such as sarcoptic mites (Sarcaptes scabiei)
  • Lip-bodied pods such as cubism cate, akasumka (Sclopendra subspinipes japonica), pheasant (The reuronema hi Igendorf i)
  • Diplopods such as black-crowned millipedes (Oxidus gracilis),
  • Nematodes such as walnut nematode (Pratylenchus vulnus), potato cyst nematode (Globodera ros tochiens is), and pine cypress (Bursaphelen chus xylophi lus),
  • Black mussels (Pomacea canaliculta), slugs (Inci lar pi pi 1 ineata), African snails (Achatina ful ica), scallops (Acusta despecta) Examples include molluscs such as Sieboldiana) and Misima mai (Euhadra pel iomphala), and crustaceans such as Omadan bug (Armadilliduim vulgara latreille).
  • the compound of the present invention exhibits an effect of preventing adhesion of organisms in water at a very low concentration.
  • aquatic organisms include shellfish and algae such as mussels, fusippo, oysters, hydramushi, hydra, serpula, sea squirts, bryozoans, fuscacobushi, tanishi, aza, aonori, and shiomidoro.
  • the compound of the present invention can effectively control pests and plant diseases of the Orthoptera, Hemiptera, Lepidoptera, Coleoptera, Hymenoptera, Diptera, Termites and Mite lice at low concentrations. Furthermore, the compound of the present invention can control the adhesion of various aquatic organisms to seawater structures in seawater and freshwater. On the other hand, the compounds of the present invention include extremely useful compounds having almost no adverse effects on mammals, fish, crustaceans and beneficial insects.
  • a 3 and A 4 are each independently: represent the same meanings as defined above A, provided that a ring having a nitrogen atom in the leaving group L 1 or Imino binding ⁇ -position, Alpha 5, the Alpha represent like meaning with the proviso that oxygen atoms, a sulfur atom or a nitrogen atom is a ring having the position ⁇ of C ⁇ M 1 or imino binding.
  • X and ⁇ the same meanings as defined above.
  • L 1 is A good leaving group such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy having 1 to 4 carbon atoms, phenoxy, an alkylamino having 1 to 4 carbon atoms, a dialkylamino having 1 to 4 carbon atoms, and having 1 carbon atom 4 to 4 alkylsulfonyloxy, 1 to 4 carbon atoms, alkylsulfonyloxy, benzenesulfonyloxy, toluenesulfonyl And 1-pyrazolyl or 1-imidazolyl.
  • a fluorine atom such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkoxy having 1 to 4 carbon atoms, phenoxy, an alkylamino having 1 to 4 carbon atoms, a dialkylamino having 1 to 4 carbon atoms, and having
  • L 2 and L 6 are good leaving groups, for example, alkoxy having 1 to 4 carbons, alkylthio having 1 to 4 carbons, phenoxy, alkylamino having 1 to 4 carbons, dialkylamino having 1 to 4 carbons, 1-pyrazolyl or 1-imidazolyl.
  • L 3 is each independently a good leaving group, for example, chlorine atom, bromine atom, iodine atom, alkoxy having 1 to 4 carbons, alkylthio having 1 to 4 carbons, phenoxy, alkylamino having 1 to 4 carbons, And dialkylamino having 1 to 4 carbon atoms, 1-pyrazolyl or 1-imidazolyl.
  • L 4 is a good leaving group such as chlorine atom, bromine atom, iodine atom, alkylsulfonyloxy having 1 to 4 carbon atoms, haloalkylsulfonyloxy having 1 to 4 carbon atoms, benzenesulfonyloxy or toluenesulfonyloxy Kishi and the like.
  • L 5 represents a good leaving group such as a chlorine atom or a bromine atom.
  • L 7 is an alkyl group having 1 to 4 carbon atoms, phenyl or tolyl group, or the like.
  • L 8 is a hydrogen atom, a trimethylsilyl group, a short butyldimethylsilyl group, a short butyldiphenylsilyl group, or the like.
  • L 9 and L ie are each independently, Y and or together a connexion represent the same meaning, it represents a one-imidazolyl, 1-pyrazolyl, 1 Pipe lysinyl or morpholino.
  • Y 1 represents an alkyl group having 1 to 6 carbon atoms or a benzyl group which may be substituted with Ra .
  • ⁇ 2 , ⁇ 9 and ⁇ 1 ⁇ each independently represent the same meaning as ⁇ .
  • ⁇ 3, ⁇ 4, ⁇ 7 , ⁇ 8 and Upsilon 11 are each independently, or hydrogen atom, the same meanings as Upsilon.
  • Upsilon 5 and Upsilon beta are each independently a hydrogen atom, carbon number 1-6 alkyl group or R a substituted by phenylene optionally Le group.
  • M represents an oxygen atom, a sulfur atom or N—Y 2 .
  • M 1 represents an oxygen atom or a sulfur atom.
  • M 2 represents an oxygen atom, a sulfur atom or N—Y 9 .
  • Ha represents a chlorine atom, a bromine atom, an iodine atom or a fluorine atom.
  • Ra has the same meaning as described above.
  • G has the same meaning as described above. )
  • Methods for producing the compound represented by the formula (9) from the nitro compound (3) include a method disclosed in European Patent Application Publication (EP-447118), Organic 'Functional Group Preparations (Organic). F unctiona 1 G roup P reparations) (Ac ad emic) Volume 1, 3 13 (1968), Journal 'Op-American Chemical- Society (J. Am. Chem. Soc.) Vol. 54, pp. 781 (1932), Chemical Review (Chem. Rev.) Vol. 55, pp. 181 (1955) can be used.
  • the nitro compound (3) is converted into an amino compound (4) by a reduction reaction, and then reacted with carbon disulfide in the presence of a base to convert the compound into a dithiol-rubamic acid compound (5).
  • the dithiolrubamic acid compound (5) is converted into an isothiocyanate compound (7) by reacting with the acid halide compound represented by the formula (6), and then the isothiocyanate compound (7) Is reacted with an amine compound represented by the formula (8) to produce a thioperia compound (9).
  • the thiourea compound (18) can be similarly produced by using ammonia as the amine compound.
  • the isothiocyanate compound (7) can also be produced by a method of reacting the amino compound (4) with a thiocarbonyl compound represented by the formula (10).
  • the thioperia compound (9) can also be produced by a method of reacting the amino compound (4) with the isothiocynate compound represented by the formula (11).
  • the thiourea compound (9) can be prepared by the method described in Synthetic Communication (Synth. Commun.), Vol. 25, No. 1, p. 43 (1995). By reacting with the halide compound (21), it can be converted to the carbodiimide compound (22).
  • the compounds (11-1) and (1-2) of the present invention were prepared from an amino compound (4) as a raw material in the form of Angevante 'Chemie, Vol. 80, p. 799 (1996). ) Or according to the method. That is, the compound (11) of the present invention is obtained by alkylating a compound represented by the formula (12) to obtain an ammonium salt represented by the formula (13) in a solvent, if necessary. Thus, it can be produced by reacting with an amino compound (4) in the presence of a catalyst. Similarly, the compound (112) of the present invention is obtained by converting a compound represented by the formula (14) into an oxodium salt or a thioxonium salt represented by the formula (15) in advance.
  • the compound can be produced by reacting the compound with an amino compound (4) in a solvent, if necessary, in the presence of a catalyst.
  • a solvent may be used as long as it is inert to the reaction.
  • halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc .
  • aromatic hydrocarbons such as benzene, xylene and toluene
  • aliphatic hydrocarbons such as pentane, hexane and cyclohexane
  • a mixed solvent thereof may, for example, be mentioned, and preferably, dichloromethane, chloroform, 1,2-dichloroethane and the like may be mentioned.
  • alkylating agent examples include alkyl octylides such as methyl iodide, engineered iodide, and benzyl bromide; sulfonic acid esters such as dimethyl sulfate, getyl sulfate, methyl trifluoromethanesulfonate; and trimethyl.
  • the catalyst examples include silver oxide and silver trifluoromethanesulfonate.
  • the reaction can be carried out at a temperature in the range of 180 ° C to the boiling point of the solvent, preferably in the range of 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 300 hours, preferably from 1 hour to 168 hours.
  • the equivalent of the alkylating agent can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, with respect to (12) or (14).
  • As the equivalent of the substrate (13) or (15) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, with respect to (4). .
  • the compound (1-3) of the present invention can be prepared by converting a dithiol rubamic acid compound (5) and a ketone compound represented by the formula (16) into a solvent, if necessary, in the presence of a base, if necessary.
  • the compound can be produced by converting into the dithiocarbamate compound (17) by reacting in the presence of a catalyst, and further reacting with a dehydrating agent in a solvent, if necessary, in the presence of a catalyst, if necessary.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene Perogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethyl Formamide, dimethylacetamide, N Amides such as monomethylpyrrolidone and N, N'-dimethylimidazolidinone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water; or a mixed solvent thereof.
  • ethers such as dimethyl ether, tetrahydrofuran, and dim
  • dichloromethane, chloroform, 1,2-dichloroethane and the like can be mentioned.
  • the base include organic bases such as triethylamine, tributylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the dehydrating agent concentrated sulfuric acid, dicyclohexylcar positimide, phosphorus pentachloride, phosphorus oxychloride or the like is used.
  • concentrated sulfuric acid can be used as a solvent.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 to the boiling point of the solvent, preferably from 0 ° C. to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 0.1 to 20 equivalents, based on (5).
  • the equivalent of the substrate (16) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (5).
  • the equivalent of the dehydrating agent can be used in the range of 0.1 to 100 equivalents to (17), and preferably in the range of 1 to 50 equivalents.
  • the compound (114) of the present invention is obtained by converting the thioperia compound (9) and the carbonyl compound represented by the formula (19) into a solvent, if necessary, in the presence of a base, if necessary, and optionally a catalyst. It can be produced by reacting in the presence.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene.
  • Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc .; esters such as ethyl acetate; ketones such as acetone and methyl ethyl ketone; nitriles such as acetonitrile and propionitrile; dimethylform Amides, such as amide, dimethylacetamide, N-methylpyrrolidone, and fats, such as pentane, hexane, and cyclohexane Examples thereof include aliphatic hydrocarbons, dimethyl sulfoxide or water, and a mixed solvent thereof, and preferably, ethanol, tetrahydrofuran, chloroform, and dimethylformamide.
  • the base examples include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • An inorganic base is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • (9) it can be used in the range of 0.1 to 50 equivalents, preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (19) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (9).
  • the compound (1-5) of the present invention is prepared by converting the thioperia compound (9) and the acid halide compound represented by the formula (20) in a solvent, if necessary, in the presence of a base, if necessary. It can be produced by reacting in the presence of a catalyst.
  • a solvent any solvent may be used as long as it is inert to the reaction.
  • ethers such as getyl ether, tetrahydrofuran, and dimethoxetane
  • aromatic hydrocarbons such as benzene, xylene, and toluene
  • dichloromethane Halogenated hydrocarbons such as 2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, and dimethylacetate
  • Halogenated hydrocarbons such as 2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, and dimethylacetate
  • Amides, amides such as N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, he
  • the base examples include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and hydrogenation. Inorganic such as sodium A base is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.1 to 50 equivalents to (9), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (20) is
  • the compound (1-6) of the present invention can be prepared by reacting the carbodiimide compound (22) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, and optionally a carbonyl compound.
  • any solvent may be used as long as it is inert to the reaction.
  • examples thereof include ethers such as diethyl ether, tetrahydrofuran, and dimethoxetane; aromatic hydrocarbons such as benzene, xylene, and toluene; dichloromethane; Halogenated hydrocarbons such as 2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, and dimethyl Amides such as acetoamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water; or a mixed solvent thereof, preferably dichloromethane, Examples include black form and 1,2-dichloroe
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, hydrogenation.
  • An inorganic base such as sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents to (22), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate is (2 3) Can be used in the range of 0.5 to 50 equivalents to (2 2), and 1 to 2
  • the compound (1-7) of the present invention can be obtained by reacting a thioperia compound (9) with an amide compound represented by the formula (24). That is, the thioperia compound
  • an amide compound represented by the formula (24) can be converted into a pseudothiourea compound (25) by reacting in a solvent, if necessary, in the presence of a catalyst, if necessary.
  • the pseudoidthiourea compound (25) can be converted into an imidoid laurel compound (26) by treating it with a halogenating agent in a solvent, if necessary, in the presence of a catalyst, if necessary.
  • (26) can be converted to the compound of the present invention (1-7) by reacting in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction. Examples thereof include lower alcohols such as methanol and ethanol, and ethers such as dimethyl ether, tetrahydrofuran, and dimethoxane.
  • Aromatic hydrocarbons such as benzene, xylene, toluene, etc., octogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, etc., esters such as ethyl acetate, acetone, methyl ethyl ketone, etc. Ketones, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and aliphatics such as pentane, hexane, and cyclohexane Preferred are hydrocarbons, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • Preferable examples include ethanol, tetrahydrofuran, chloroform, 1,2-dichloroethane, ethyl acetate, acetone, acetonitrile, dimethylformamide, and water.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the substrate (24) can be used in the range of 0.5 to 50 equivalents, and preferably 1 to 20 equivalents, relative to (9).
  • the solvent may be inert to the reaction.
  • lower alcohols such as methanol and ethanol
  • ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane
  • aromatic hydrocarbons such as benzene, xylene, and toluene, dichloromethane, chloroform
  • 1,2 Halogenated hydrocarbons such as dichlorobenzene
  • esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone
  • nitriles such as acetonitrile and propionitrile
  • dimethylformamide and dimethyl Amides
  • aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethyl sulfoxide or water, or Include a mixed solvent thereof
  • halogenating agent examples include tetrachloroethane / triphenylphosphine, phosphorus oxychloride, phosphorus pentachloride, phosphorus trichloride, oxalic acid dichloride, chlorine, and N-chloro succinic acid imid.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 ° C. to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the chlorinating agent can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 0.1 to 20 equivalents, based on (25).
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol; Ethers, aromatic hydrocarbons such as benzene, xylene, toluene, etc., octogenated hydrocarbons such as dichloromethane, 1,2-dichloroethane, etc., esters such as ethyl acetate, acetone, methyl ethyl ketone Ketones, such as acetonitrile, nitriles such as propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, amides such as N, N'-dimethylimidazolidinone, pentane, hexane , Aliphatic hydrocarbons such as cyclohexane, dimethyl sulfoxide or water, Or a mixed solvent thereof.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, and carbonate.
  • organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine
  • potassium carbonate sodium carbonate
  • carbonate sodium carbonate
  • An inorganic base such as thorium is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, preferably 0.1 to 20 equivalents, relative to (26).
  • the compound (111) of the present invention can be obtained by reacting the thioperia compound (9) with a ketone compound represented by the formula (16). That is, the thiourea compound (9) is reacted with the ketone compound represented by the formula (16) in a solvent, if necessary, in the presence of a catalyst, if necessary, to form the pseudothiourea compound (27). Can be converted. Furthermore, the pseudothiazole compound (27) can be converted to the hydroxythiazolidine compound (1-8) by reacting it in a solvent, if necessary, in the presence of an acid or a basic catalyst.
  • (1-8) can be converted to the compound (1-9) of the present invention by treating it with a dehydrating agent in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, if necessary. .
  • (1-9) can be converted to a free compound (1-10) by treating it with a base in a solvent if necessary.
  • (27) or (1-8) can be isolated without separating (1-8). 9) can also be obtained.
  • (1-10) can be obtained without isolating (27) or (118) or (1-9). ) Can also be obtained.
  • (1-10) By using a base in the reaction of (1-8) with a dehydrating agent, (1-10) can also be obtained without isolating (1-9).
  • the thiazoline compound (31) similarly obtained from the thiourea compound (18) is treated with an alkylating agent in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst. Can also be obtained.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, dimethyl ether, tetrahydrofuran, and dimethoxetane Ethers, aromatic hydrocarbons such as benzene, xylene, and toluene; dichloromethane, chloroform, halogenated hydrocarbons such as 1,2-dichloroethane, and esters such as ethyl acetate; Tones, ketones such as methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, hexane, cyclo Examples thereof include aliphatic hydrocarbons such as hexane, dimethyl sulfoxide or water, and a mixed solvent thereof.
  • ethanol tetrahydrofuran, chloroform, 1,2-dichloroethane, ethyl acetate, acetone, acetonitrile, Dimethylformamide, water and the like.
  • the acidic catalyst include hydrochloric acid, hydrobromic acid, hydroiodic acid, hydrofluoric acid, acetic acid, and tetrafluoroboric acid.
  • the basic catalyst include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • the reaction can be carried out at a temperature ranging from 180 t: to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • (16) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, with respect to (9).
  • any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol are used.
  • Ethers such as benzene, xylene, toluene, etc .; aromatic hydrocarbons such as benzene, xylene and toluene; halogenated hydrocarbons such as 1,2-dichloroethane; and acetic acid.
  • Esters such as ethyl, ketones such as acetone and methylethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N, N'-dimethylimidazolide
  • Amides such as nonone, fats such as pentane, hexane and cyclohexane Hydrocarbons, dimethylsulfoxide, or water, or a mixed solvent thereof and the like can be mentioned, preferably, dichloroethylene Rorometan, black hole Holm, 1, 2-Jikuroroetan and the like.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, and sodium carbonate.
  • organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, and sodium carbonate.
  • Inorganic bases such as lium, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide and sodium hydride are used.
  • pyridine or the like can be used as a solvent.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • methanesulfonyl chloride, toluenesulfonyl chloride, trifluoromethanesulfonic anhydride, concentrated sulfuric acid, dicyclohexylcarpoimide, phosphorus pentachloride, phosphorus oxychloride, or the like is used.
  • concentrated sulfuric acid can be used as a solvent.
  • the reaction can also be carried out by azeotropic dehydration using a solvent such as toluene, benzene, or xylene. The reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 0.1 to 20 equivalents, based on (1-8).
  • the equivalent of the dehydrating agent can be used in the range of 0.1 to 100 equivalents to (118), and preferably in the range of 1 to 50 equivalents.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, getyl ether, tetrahydrofuran and dimethyl ether Ethers such as toxetane, aromatic hydrocarbons such as benzene, xylene, toluene, etc., halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, acetone, Ketones such as methylethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, amides such as N, ⁇ '-dimethylimidazolidinone, pentane Aliphatic hydrocarbons such as hexane, cyclohexane, dimethyl sulfoxide and Is water, or a mixed solvent thereof.
  • aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, dimethylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, and sodium hydrogencarbonate.
  • organic bases such as triethylamine, triptylamine, pyridine, dimethylbiperidine, and 4-dimethylaminopyridine
  • potassium carbonate sodium carbonate
  • sodium hydrogencarbonate sodium hydrogencarbonate
  • Inorganic bases such as sodium hydroxide, potassium hydroxide, sodium hydride and the like are used.
  • the reaction can be carried out at a temperature ranging from 180 ° C. to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours. A range of 1 hour to 48 hours is preferred.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 0.1 to 20 equivalents, based on (1-9).
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, getyl ether, tetrahydrofuran, dimethyloxetane Ethers such as benzene, xylene, toluene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, acetone, methyl ester Ketones such as tyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N, N'-amides such as dimethylimidazolidinone, pentane, etc.
  • Aliphatic hydrocarbons such as xane and cyclohexane, dimethyl sulfoxide or water, Or a mixed solvent thereof.
  • the base include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, and sodium hydrogencarbonate.
  • organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, and sodium hydrogencarbonate.
  • Inorganic bases such as sodium hydroxide, potassium hydroxide and sodium hydride are used.
  • alkylating agent examples include alkyl halides such as methyl iodide, chloroiodide, and benzyl bromide; sulfonic acid esters such as dimethyl sulfate, getyl sulfate, and methyl trifluoromethanesulfonate; and trimethyloxodioxide.
  • Trialkyl oxo disalts such as dimethyl borosulfate and triethyl oxo dimethyl trafluoro borate, etc., and the like, and preferably trifluoro sulfonic acid methyl ester and the like are mentioned.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 0.1 to 20 equivalents, based on (31).
  • the equivalent of the alkylating agent can be used in the range of 0.01 to 50 equivalents, preferably 0.1 to 20 equivalents, based on (31).
  • the compounds (1-1-1) and (1-1-2) of the present invention can be produced by the following method. That is, represented by the isothiocyanate compound (7) and the formula (32)
  • the propargylamine compound is reacted with a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, if necessary, to give a propargylthiourea compound represented by the formula (33).
  • a solvent can be any solvent as long as it is inert to the reaction.
  • the solvent examples include lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran and dimethyloxetane, and aromatic hydrocarbons such as benzene, xylene and toluene.
  • Hydrogens halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water; or a mixed solvent thereof And the like, preferably tetrahydrofuran, Holm, acetone, Asetonitoriru and the like.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, sodium hydroxide, potassium hydroxide, and hydrogen.
  • An inorganic base such as sodium chloride is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the radical generator trifluoroacetic acid, oxygen, air, benzoyl peroxide, azobisisobutyronitrile and the like are used. Also, trifluoroacetic acid can be used as a solvent.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (7).
  • As the equivalent of the substrate, (32) can be used in the range of 0.5 to 50 equivalents to (7), and preferably in the range of 1 to 20 equivalents.
  • the compound of the present invention (111) can be prepared by converting the above-mentioned propargyl thiourea compound (33) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, It can be produced by treating with a halogenating agent.
  • the solvent only needs to be inert to the reaction.
  • examples include lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene.
  • Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethylsulfoxide or water, or a mixed solvent thereof And the like, preferably, dichloromethane, Lum, 1, 2-dichloroethane, ⁇ acetonitrile, and the like.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride. And the like.
  • organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the halogenating agent iodine, bromine, N-bromosuccinic acid imide, N-chloro succinic acid imid, N-iodosuccinic acid imid, tetrabutylammonium tribromide and the like are used.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents to (33), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the halogenating agent can be used in the range of 0.01 to 50 equivalents to (33), and preferably in the range of 1 to 20 equivalents.
  • the compound (1-14) of the present invention can be obtained by combining the above-mentioned compound (111) with an amine compound, an alcohol compound or a mercaptan compound represented by the formula (34) in a solvent, if necessary.
  • the reaction is carried out in the presence of a base, and in some cases, in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, getyl ether, tetrahydrofuran, Ethers such as methoxyethane, aromatic hydrocarbons such as benzene, xylene and toluene, dichloromethane, chloroform, halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, acetone and methylethyl Ketones such as ketones, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and aliphatics such as pentane, hexane and cyclohexane Examples thereof include hydrocarbons, dimethyl sulfoxide or water, and a mixed solvent thereof, and preferred examples include tetrahydrofuran, benzene, chloroform, 1,2-dichloroethane, and acetonit
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, diazabicycloundecene, N-methylbiperidine, 4-dimethylaminopyridine, cesium fluoride, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, sodium hydroxide, and the like.
  • An inorganic base such as potassium hydroxide or sodium hydride is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, based on (1-13). Also, the equivalent of the substrate
  • (34) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, with respect to (1-13).
  • the compounds (111) and (1-16-1) of the present invention can be produced by the following methods. That is, the isothiocyanate compound (7) is reacted with the arylamine compound represented by the formula (35) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst. Can be converted to an arylthiodiarea compound represented by the formula (36). Further, (36), in a solvent, if necessary, by treatment with radio local generator, if Y 2 is phenyl present invention compound (1 one 1 5), if Y 2 is other than phenyl The compound (111) of the present invention can be obtained.
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, dimethyl ether, tetrahydrofuran Ethers such as benzene, dimethoxane, aromatic hydrocarbons such as benzene, xylene, and toluene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and esters such as ethyl acetate.
  • Ketones such as acetone, methylethyl ketone, etc., nitriles such as acetonitrile, propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pen Examples thereof include aliphatic hydrocarbons such as tan, hexane and cyclohexane, dimethyl sulfoxide or water, and a mixed solvent thereof, and preferably, tetrahydrofuran, chloroform, acetone, and acetonitrile.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylpyridine, 4-dimethylaminopyridine, carbonated sodium, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, and sodium hydroxide.
  • An inorganic base such as hydrogenated sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the radical generator trifluoroacetic acid, oxygen, air, benzoyl peroxide, azobisisobutyronitrile and the like are used. Also, trifluoroacetic acid can be used as a solvent.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (7), preferably in the range of 1 to 20 equivalents.
  • As the equivalent of the substrate, (35) can be used in the range of 0.5 to 50 equivalents, and preferably 1 to 20 equivalents, with respect to (7).
  • the compound (111) of the present invention can be treated with the halogenating agent in the presence of the above-mentioned arylthiodiurea compound (36) in a solvent, if necessary, in the presence of a base, and optionally a catalyst.
  • a solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as getyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene.
  • Halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, ketones such as acetone, methylethyl ketone, etc., acetonitrile, propionitrile etc.
  • Amides such as nitriles, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane, cyclohexane, dimethyl sulfoxide or water, or a mixture thereof Solvents and the like are preferable, and dichloromethane, chloroform-form, 1,2-dichloroethane, acetonitrile and the like are preferable.
  • the base include organic bases such as trieduramine, tributylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and hydrogen.
  • An inorganic base such as sodium chloride is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the octaloginating agent iodine, bromine, N-bromosuccinic acid imide, N-chloro oral succinic acid imide and the like are used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents to (36), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the halogenating agent can be used in the range of 0.01 to 50 equivalents to (36), and preferably in the range of 1 to 20 equivalents.
  • the compound (1-18) of the present invention can be prepared by mixing the above-mentioned compound (1-17) with the amine compound, alcohol compound or mercapnone compound represented by the formula (34) in a solvent, if necessary.
  • the reaction is carried out in the presence of a base depending on the reaction conditions, and in some cases, in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene.
  • Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethyl
  • amides such as formamide, dimethylacetamide and N-methylpyrrolidone
  • aliphatic hydrocarbons such as pentane, hexane and cyclohexane
  • dimethylsulfoxide or water or a mixed solvent thereof.
  • tetrahydrofura Benzene chloroform, 1,2-dichloroethane, and acetonitrile.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, diazabicycloundecene, N-methylbiperidine, 4-dimethylaminopyridine, cesium fluoride, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, sodium hydroxide, and the like.
  • An inorganic base such as potassium hydroxide or sodium hydride is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 ° C. to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, preferably 1 to 20 equivalents, based on (1-17).
  • the equivalent of the substrate (34) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (1-17).
  • the compound (1-19) of the present invention can be produced according to the method described in Synthesis (page 896, 1981) or according to the method. That is, it can be obtained by reacting the isothiocyanate compound (7) and the olefin compound represented by the formula (37) in a solvent, if necessary, in the presence of a base, if necessary, and optionally in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatics such as benzene, xylene, and toluene.
  • Hydrocarbons such as dichloromethane, chloroform, 1,2-dichlorobenzene, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitrile, etc.
  • Amides such as nitriles, dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water; or Mixed solvents and the like are preferable.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents to (7), and preferably in the range of 1 to 20 equivalents.
  • a catalyst For example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180: to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (7).
  • the equivalent of the substrate can be used in the range of 0.5 to 50 equivalents, and preferably 1 to 20 equivalents, relative to (7).
  • the compound (112) of the present invention can be produced by the method described in West German Patent Application Publication (DE-3025559) or according to the method. That is, the thiosemicarbazide compound (39) is reacted by reacting the isothiocyanate compound (7) and the hydrazine compound represented by the formula (38) in a solvent, if necessary, in the presence of a catalyst, if necessary. ).
  • an acylthiosemicarbazide compound (41 ) by reacting the carbonyl compound represented by the formula (40) with a solvent, if necessary, in the presence of a base, if necessary, a catalyst in some cases, an acylthiosemicarbazide compound (41 ). Further, the compound (1-20) of the present invention can be obtained by treating the acylthiosemicarbazide compound (41) with a dehydrating agent in a solvent, if necessary, in the presence of a catalyst as necessary.
  • any solvent may be used as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, and dimethyl ether.
  • Ethers such as tetrahydrofuran and dimethoxetane; aromatic hydrocarbons such as benzene, xylene and toluene; halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; esters such as ethyl acetate; Ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, hexane, and cyclohexane Aliphatic hydrocarbons such as xane or dimethyl sulfoxy Or a mixed solvent thereof, and preferably, tetrahydrofuran, chloroform, 1,2-dichloromethane, acetone, acetonitrile, dimethylformamide and the like.
  • the catalyst for example, tetra-N-butyl
  • ammonium bromide is used as the catalyst.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the substrate (38) can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, with respect to (7).
  • any solvent may be used as long as it is inert to the reaction.
  • solvents include dimethyl ether, tetrahydrofuran, and dimethoxetane.
  • Aromatic hydrocarbons such as ters, benzene, xylene, toluene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichlorobenzene, etc., esters such as ethyl acetate, acetone, methyl Ketones such as ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, hexane, cyclohexane, etc. Aliphatic hydrocarbons or dimethyl sulfoxide or their mixed solvents, etc.
  • Is preferably tetrahydrofuran, black hole Holm, 1, 2-Jikuroroe Tan, acetone, Asetonitoriru, dimethyl ⁇ Seto Ami de like.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, diazabicycloundecene, N-methylbiperidine, 4-dimethylaminopyridine, cesium fluoride, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide. And inorganic bases such as potassium hydroxide and sodium hydride.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.01 to 50 equivalents to (39), and preferably in the range of 1 to 20 equivalents.
  • As the equivalent of the substrate, (40) can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (39).
  • the compound (111) of the present invention was obtained from the acylthiosemicarbazide compound (41).
  • any solvent may be used as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran and dimethoxyethane, benzene, xylene, and the like.
  • Aromatic hydrocarbons such as toluene, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, ketones such as acetone and methyl edulketone, acetonitrile, propionitrile Such as nitriles, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc .; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; or dimethyl sulfoxide or a mixture thereof.
  • Solvents, etc., preferably benzene, Sile emissions include black port Holm like.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the dehydrating agent concentrated sulfuric acid, dicyclohexylcarpoimide, 5. phosphorus chloride or phosphorus oxychloride and the like are used. Also, concentrated sulfuric acid can be used as a solvent.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the dehydrating agent the dehydrating agent can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, based on (41).
  • the compound (1-21) of the present invention can be produced according to the method described in the West German Patent Application Publication (DE-325559) or according to the method. That is, it is obtained by reacting the above-mentioned acylthiosemicarbazide compound (41) with an alkylating agent in a solvent, if necessary, in the presence of a base, if necessary, and optionally in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran and dimethoxyethane, benzene, xylene, toluene and the like.
  • Aromatic hydrocarbons dichloromethane, chloroform, octogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ketone, acetonitrile, propionitrile, etc.
  • Amides such as nitriles, dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; Examples thereof include rusulfoxide or water, or a mixed solvent thereof, and preferably, ethanol, tetrahydrofuran, chloroform, 1,2-dichloroethane, and dimethylacetamide.
  • alkylating agent examples include alkyl octides such as methyl iodide, thiolated iodide, and benzyl bromide; sulfonic acid esters such as dimethyl sulfate, getyl sulfate, and methyl trifluoromethanesulfonate; and trimethylo.
  • trialkyloxodium salts such as xoxodumtetrafluoroborate and triethyloxodonetetrafluoroborate.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be in the range of 5 minutes to 100 hours, preferably in the range of 1 hour to 48 hours.
  • the alkylating agent can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, based on (41).
  • the compound of the present invention (1-22) is prepared by converting the thiosemicarbazide compound (39) and the ketone compound represented by the formula (16) into a solvent, if necessary, in the presence of a base, if necessary. In some cases, it is obtained by reacting in the presence of a catalyst.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, and aromatic hydrocarbons such as benzene, xylene, and toluene.
  • Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile , Amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • ethanol tetrahi Rofuran, chloroform, 1, 2-dichloroethane, acetone, Asetonitoriru, Jimechiruho Rumuami de like.
  • the base include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, and sodium hydroxide.
  • Inorganic bases such as lithium, potassium hydroxide and sodium hydride are used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction temperature can be in the range of 180 ° C to the boiling point of the solvent, preferably in the range of 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (39), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (16) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (39).
  • the compound (1-23) of the present invention is obtained by reacting the isothiocyanate compound (7) with the hydrazine compound represented by the formula (42) in a solvent, if necessary, in the presence of a catalyst, if necessary.
  • a catalyst if necessary.
  • any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, dimethyl ether, Ethers such as tetrahydrofuran and dimethoxetane, aromatic hydrocarbons such as benzene, xylene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and esters such as ethyl acetate; Ketones such as acetone and methyl alcohol ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, hexane, cyclo Aliphatic hydrocarbons such as hexane or dimethyl sulfo Passes or a mixed solvent thereof and the like can be mentioned, preferably ethanol, as tetrahydrofuran, black hole Holm, Asetonitoriru and the like.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from -80 t to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours. (4 2) is equivalent to (7) On the other hand, it can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents.
  • any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol; Tetrahydrofuran, ethers such as dimethoxetane, aromatic hydrocarbons such as benzene, xylene, toluene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichlorobenzene, etc., and ethyl acetate Esters, such as acetone, ketones, such as acetone and methyl ethyl ketone, nitriles, such as acetonitrile and propionitrile, amides, such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and pentane.
  • ethers such as dimethoxetane
  • aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichlorobenzene,
  • Aliphatic hydrocarbons such as xane and cyclohexane, dimethyl sulfoxide or Examples thereof include water and a mixed solvent thereof, and preferred examples include tetrahydrofuran, benzene, xylene, chloroform, dimethylacetamide, and N-methylpyrrolidone.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, and potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • An inorganic base is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be in the range of 5 minutes to 100 hours, preferably in the range of 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (43), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (16) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (43).
  • the compound (1-2-4) of the present invention may be prepared by converting the thiosemicarbazide compound (43) and the carbonyl compound represented by the formula (19) in a solvent, if necessary, in the presence of a base, if necessary. Can be produced by reacting in the presence of a catalyst. Any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol
  • Ethers aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc.
  • esters such as ethyl acetate, acetone, methylethyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and aliphatic hydrocarbons such as pentane, hexane and cyclohexane , Dimethyl sulfoxide or water, or a mixed solvent thereof, and the like, and preferably, ethanol, tetrahydrofuran, chloroform, dimethylformamide and the like.
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride. And the like.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.1 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (43).
  • the equivalent of the substrate (1 9) is
  • (43) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents.
  • the compound (1-25) of the present invention can be produced according to the method described in Heterocycles, Vol. 50, p. 195 (1991), or according to the method. That is, the isothiocynate compound (7) and the mercaptan compound represented by the formula (44) are reacted in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst. The dithioacetal compound (45) is then treated with an alkylating agent in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, to give a dithioacetal compound (45). 2-1).
  • the dithioacetal compound (2-1) and the carbonyl compound represented by the formula (46) are reacted in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, if necessary. 2—2) and (1 A mixture of 25) is obtained.
  • (2-1) can also be obtained without isolating (45).
  • (1-2-5) can also be obtained for a long time or without heating without isolating (2-2).
  • the isolated (2-2) is reacted in a solvent as necessary, optionally in the presence of a base, and optionally in the presence of a catalyst, or is subjected to a heat treatment to obtain (1-2-5). Can also be converted to
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol
  • ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane
  • Aromatic hydrocarbons such as benzene, xylene, toluene, etc.
  • halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc.
  • esters such as ethyl acetate, acetone, methyl ethyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone, and aliphatic hydrocarbons such as pentane, hexane and cyclohexane , Dimethyl sulfoxide or water, or a mixed solvent thereof, and the like.
  • Mashiku include tetrahydrofuran, benzene, toluene, dichloromethane, black hole Holm, 1, 2-Jikuroroetan, acetone,
  • Asetonitoriru include Jimechiruase Bok Ami de like.
  • the base examples include organic bases such as triethylamine, tributylamine, pyridine, diazabicycloundecene, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, Inorganic bases such as potassium hydroxide and sodium hydride are used.
  • organic bases such as triethylamine, tributylamine, pyridine, diazabicycloundecene, N-methylbiperidine, and 4-dimethylaminopyridine
  • potassium carbonate sodium carbonate
  • sodium hydrogencarbonate sodium hydroxide
  • Inorganic bases such as potassium hydroxide and sodium hydride
  • Tetra N-butylammonium bromide or the like is used as Tetra N-butylammonium bromide or the like is used.
  • alkylating agent examples include alkyl octides such as methyl iodide, engineered iodide, and benzyl bromide, sulfonic acid esters such as dimethyl sulfate, getyl sulfate, methyl trifluoromethanesulfonate, and trimethylo.
  • trialkyloxodium salts such as xonium tetrafluoroborate and triethyloxodimotetrafluoroborate.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 t: to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, A range from 1 hour to 48 hours is preferred.
  • the equivalent of the base is (7)
  • the alkylating agent can be used in the range of 0.01 to 50 equivalents, preferably 1 to 20 equivalents, relative to (45).
  • the solvent may be any solvent as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, dimethyl ether, tetrahydrofuran, and dimethoxetane Ethers, such as benzene, xylene, toluene, etc .
  • aromatic hydrocarbons such as dichloromethane, chloroform
  • halogenated hydrocarbons such as 1,2-dichloroethane
  • esters such as ethyl acetate
  • acetone, methyle Ketones such as tyl ketone, nitriles such as acetonitrile and propionitrile
  • amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, hexane, cyclohexane, etc.
  • the base include organic bases such as trieduramine, triptyluamine, pyridine, diazabicycloundecene, N-methylpiperidine, 4-dimethylaminopyridine, cesium fluoride, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, and sodium hydroxide.
  • inorganic bases such as potassium hydroxide and sodium hydride.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature in the range from 180C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be in the range of 5 minutes to 100 hours, preferably in the range of 1 hour to 48 hours.
  • (2-1) it can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (46) can be used in the range of 0.01 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (2-1).
  • the compound (1-26) of the present invention can be prepared by the method described in JP-A-55-108869 and Chemistry Letters, p. 705 (1998), or a method similar thereto. Can be manufactured. That is, the isothionate compound (7) and the amine compound represented by the formula (47) can be converted to the thioperia compound (48) by reacting in a solvent, if necessary, in the presence of a catalyst, if necessary. .
  • the thiourea compound (48) is reacted with the ketone compound represented by the formula (16) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst, if necessary.
  • the compound (2-3) can be converted to the pseudopyodorea compound (2-3), and the compound (2-3) can be converted to the free compound (2-4) by treating with a base in a solvent if necessary.
  • (2-4) can be converted to the compound of the present invention (1-26) by treating it with an acid in a solvent, if necessary.
  • (2-4) can be obtained without isolating (2-3) by using an excess of a base in the reaction of the thiourea compound (48) with the ketones (16).
  • the (2-3) and (2-4) can be isolated without isolation by heating for a long time or by heating. 26) can also be obtained.
  • the solvent may be any solvent as long as it is inactive in the reaction.
  • lower alcohols such as methanol and ethanol, methyl ether, Ethers such as tetrahydrofuran and dimethoxetane, aromatic hydrocarbons such as benzene, xylene and toluene, halogenated hydrocarbons such as dichloromethane, chloroform and 1,2-dichlorobenzene, and ethyl acetate
  • esters ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitol, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and pentane
  • Hexane, cyclohexane and other aliphatic hydrocarbons or dimethyl sulfoxide Rui include a mixture of these solvents, preferably, tetrahydrofuran, black hole Holm, 1, 2-Jikuroroetan, acetic Echiru,
  • the reaction temperature can range from _80 ° C to the boiling point of the solvent, from 0 "C to the boiling point of the solvent. Is preferable.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol, getyl Ethers such as ether, tetrahydrofuran, dimethoxetane, and dioxane; aromatic hydrocarbons such as benzene, xylene, and toluene; octogenated hydrocarbons such as 1,2-dichloroethane; and acetic acid; Esters such as ethyl, ketones such as acetone and methylethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; Aliphatic hydrocarbons such as pentane, hexane, cyclohexane, and dimethyl sulfoxide Or water or a mixed solvent thereof, and preferably, tetrahydrofuran, chloroform, 1,2-dichloroethane, acetone, acetonitrile
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 ° C. to the boiling point of the solvent.
  • the reaction time may be in the range of 5 minutes to 100 hours, preferably in the range of 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (48), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate (16) can be used in the range of 0.5 to 50 equivalents, and preferably 1 to 20 equivalents, relative to (48).
  • L 11 , L 12 , L 13 and L 14 each independently represent C 1, C 4 alkyl, or L 11 and L 12 or L 13 and L 14 together form a piperazine ring, morpholine ring, pyrrolidine Ring, imidazole ring, pyrazolyl ring or piperidine ring.
  • a tetraalkylthiourea (48) and a ketone compound (16) are reacted in a solvent, if necessary, in the presence of a base, if necessary, to give an oxathiolenimimidine salt (49).
  • a base if necessary, to give an oxathiolenimimidine salt (49).
  • the compound (1-7) of the present invention can be obtained by reacting the obtained (49) with the amino compound (4).
  • any solvent may be used as long as it is inert to the reaction.
  • Esters such as acetone, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone and pentane, Examples thereof include aliphatic hydrocarbons such as hexane and cyclohexane, and mixed solvents thereof, and are preferably dioxane, tetrahydrofuran, benzene, xylene, toluene, dichloromethane, chloroform, 1,2-dichloroethane. Evening, acetonitrile, dimethylformamide and the like.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be in the range of 5 minutes to 100 hours, and preferably in the range of 1 hour to 48 hours.
  • (As the equivalent of the substrate, (16) is equivalent to (4 8) It can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents.
  • a solvent for example, ethers such as getyl ether, tetrahydrofuran, dimethoxetane, and dioxane; aromatic hydrocarbons such as benzene, xylene, and toluene; dichloromethane; Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitrile, etc.
  • Amides such as tolyls, dimethylformamide, dimethylacetamide, and ⁇ -methylpyrrolidone; or aliphatic hydrocarbons such as pentane, hexane, and cyclohexane; and mixed solvents thereof.
  • Examples of the base include triethylamine, triptylamine, pyridine, and the like.
  • Organic bases such as ⁇ —methylbiperidine and 4-dimethylaminopyridine
  • inorganic bases such as carbonated lime, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride are used.
  • the reaction can be carried out at a temperature in the range of 18 ° C. to the boiling point of the solvent, and preferably in the range of 0 ° C. to the boiling point of the solvent. This can be done in the range of 0 hours, preferably between 1 hour and 48 hunts.
  • the base can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (49).
  • (4) can be used in the range of 0.5 to 50 equivalents, and preferably 1 to 20 equivalents, relative to (49).
  • the oxathiolene imidium salt (49) is treated with a carbonyl compound and a ketone compound (16) to give a thiocarbamate compound (51). It can also be obtained by dehydration with sulfuric acid or tetrafluoroboric acid.
  • the reaction of obtaining an oxathioleniminium salt (52) from the amine compound (50) via the thiocarbamate compound (51) is carried out by the chemical 'and pharmacological' bulletin (Chem. Pharm. Bui 1 ;)
  • the method described in Vol. 20, p. 304 (1972) or a method according to the method can be used.
  • the compound of the present invention (1-3) is obtained by treating an amine compound (50) with carbon disulfide and a ketone compound (16) to give a dithiocarbamate compound (52), and then adding concentrated sulfuric acid or By dehydration with tetrafluoroboric acid, dithiolenimidium salt (53) can be obtained. Further, the compound (113) of the present invention can be obtained by reacting the obtained (53) with an amino compound (4).
  • the reaction of obtaining a dithioreniminium salt (53) from a diamine carbamate compound (52) via a dithiocarbamate compound (52) from a chemical amine compound (50) is based on the chemical 'and pharmacological' bulletin (Cheni. Pharma. Bui 1.) Vol. 7, pp. 924 (1969), Tetrahedron Letters (1), p. 37 (1971) and Chemical and Pharmaceutical T. Bulletin (Ch e m) P ha rm. Bui) can be carried out by the method described in Vol. 20, pp. 1711 (1972), or according to the method.
  • the solvent may be any as long as it is inert to the reaction.
  • dimethyl ether, tetrahydrofuran, dimethyloxetane, dioxane Such as ethers, aromatic hydrocarbons such as benzene, xylene, and toluene, dichloromethane, chloroform, Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide And amides such as N-methylpyrrolidone or aliphatic hydrocarbons such as pentane, hexane and cyclohexane, or a mixed solvent thereof.
  • dioxane tetrahydrofuran, benzene, xylene, and toluene are used.
  • Dichloromethane chloroform, 1,2-dichloroethane, acetonitrile, dimethylformamide and the like.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • pyridine or the like can be used as the solvent.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 to the boiling point of the solvent, preferably from 0 ° C. to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the base can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (53).
  • the equivalent of the substrate As the equivalent of the substrate,
  • (4) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, to (53).
  • the compound (117b) of the present invention can be obtained by reacting the oxathiolenimidine salt (49) obtained by (Production method 2) with an aminophenyl acetate compound (4a). Further, it can also be obtained by reacting (49) with aminophenylacetic acid (4b) to produce an iminophenylacetic acid compound (l-7a), followed by esterification.
  • the compound (13b) of the present invention can be obtained by reacting the dithioleneminium salt (53) obtained by the above method with an aminophenylacetic acid ester compound (4a). Further, it can also be obtained by reacting (53) with aminophosphenylacetic acid (4b) to give an iminophenylacetic acid compound (l-3a), followed by esterification.
  • Reaction of oxathioleniminium salt (49) with an aminophenyl acetate compound (4a) to give the compound (1-7b) of the present invention, oxathioleniminium salt (49) and aminophenyl A reaction to obtain an iminophenylacetic acid compound (1-7a) from the acetic acid compound (4b), and a compound of the present invention (13b) from the dithiolenimidium salt (53) and the aminophenylacetic acid ester compound (4a)
  • the solvent must be inert to the reaction.
  • ethers such as getyl ether, tetrahydrofuran, dimethoxetane, and dioxane
  • aromatic hydrocarbons such as benzene, xylene, and toluene
  • Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, and dimethylform Amides, such as amide, dimethylacetamide, and N-methylpyrrolidone
  • aliphatic hydrocarbons such as pentane, hexane, and cyclohexane; and mixed solvents thereof, and the like, preferably dioxane , Tetrahydrofuran, benzene, xylene, toluene, dichloromethane, chloroform, 1,2-dichloroethane, ace
  • the base examples include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, carbon dioxide lime, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, carbon dioxide lime, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • pyridine or the like can be used as a solvent.
  • the reaction can be carried out at a temperature ranging from 180 ° C. to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • Base equivalent As the base, the base can be used in the range of 0.5 to 50 equivalents, and preferably in the range
  • (4a) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, for (49) and (53), respectively.
  • (4b) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, to (49) and (53), respectively.
  • any solvent may be used as long as it is inert to the reaction.
  • Lower alcohols such as methanol, ethanol, etc., ethers such as diethyl ether, tetrahydrofuran, and dimethoxetane, aromatic hydrocarbons such as benzene, xylene, and toluene, dichloromethane, chloroform, 1,2-dichloroethane, etc.
  • Halogenated hydrocarbons esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N, Amides such as N'-dimethylimidazolidinone; aliphatic carbons such as pentane, hexane, and cyclohexane Examples include hydrogens, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • Examples of the base include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, and potassium carbonate.
  • Inorganic bases such as sodium carbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, sodium hydride and the like are used.
  • Examples of the alkylating agent include alkyl octylides such as methyl iodide and methyl bromide, sulfonic acid esters such as dimethyl sulfuric acid and trifluoromethyl sulfonic acid methyl ester, and trimethyloxodimethyltetrafluoate.
  • Examples include trialkyloxodimethyl salts such as boroborate salts, and more preferably, dimethyl sulfate or methyl iodide. It can also be synthesized using a dehydrating agent in alcohol. Examples of the dehydrating agent include concentrated sulfuric acid, acetyldiazoxycarboxylate, trifluoromethanesulfonic anhydride, dicyclohexylcarposimid, phosphorus pentachloride or phosphorus oxychloride. Etc. are used. The reaction can also be carried out by azeotropic dehydration using a solvent such as toluene, benzene, or xylene. The reaction temperature should be between 80 ° C and the boiling point of the solvent. It is preferably in the range of 0 ° C. to the boiling point of the solvent. The reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours. The equivalent of the base is (1-7a) or (1-13a) with respect to 0.01
  • the equivalent of the alkylating agent is (l-7a) or (1-1-3a), 0.0
  • the equivalent of the dehydrating agent is (1-7a) or (1-3a) with respect to 0.0
  • the compound of the present invention represented by Z ( In addition to the methods described in Production method 1) and (Production method 2), the compounds of the present invention (1-1) obtained by (Production method 1) and (Production method 3) can be used to prepare (1-26), (1 The heteroiminophenylacetic acid compound represented by (la) corresponding to (13b) and (11-17b) can also be produced by the following method using a starting material.
  • L 15 is a good leaving group, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkoxy group having 1 to 4 carbon atoms.
  • L 16 is a good leaving group, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, an alkylsulfonyloxy having 1 to 4 carbon atoms, benzenesulfonyloxy, toluenesulfonyloxy and the like.
  • L 17 represents an alkyl having 1 to 6 carbon atoms or an inorganic salt such as sodium and potassium.
  • the compound (la) of the present invention is reacted with a formic acid halide compound, a formic acid ester compound or a formic acid amide compound represented by the formula (54) in a solvent in the presence of a base and, in some cases, a catalyst.
  • a formic acid halide compound a formic acid ester compound or a formic acid amide compound represented by the formula (54)
  • a solvent in the presence of a base and, in some cases, a catalyst.
  • a catalyst in some cases, a catalyst.
  • (lb) is reacted with an alkyl halide or an alkyl sulfate represented by the formula (55) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst.
  • an alkyl halide or an alkyl sulfate represented by the formula (55) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst.
  • (lc) can also be directly synthesized without isolating (lb) by using an excess of base.
  • the solvent only needs to be inert to the reaction, and examples thereof include ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, aromatic hydrocarbons such as benzene, xylene, and toluene, dichloromethane, and chloroform.
  • Halogenated hydrocarbons such as 1,2-dichlorobenzene, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetate nitrile and propionitrile, dimethyl
  • amides such as formamide, dimethylacetamide, and N-methylpyrrolidone
  • aliphatic hydrocarbons such as pentane, hexane, and cyclohexane
  • dimethyl sulfoxide or water or a mixed solvent thereof.
  • tetrahydrofuran, benzene, xylene, toluene, and dichloromethane preferably, tetrahydrofuran, benzene, xylene, toluene, and dichloromethane.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, and potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • An inorganic base is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction temperature should be between 80 ° C and the boiling point of the solvent. The range of 0 ° C. to the boiling point of the solvent is preferred.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (la), and preferably in the range of 1 to 20 equivalents.
  • As the equivalent of the substrate, (54) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (1a).
  • the compound of the present invention (la) is reacted with a nitrite compound or a nitrite represented by the formula (56) in a solvent in the presence of a base and, in some cases, a catalyst to give the compound of the present invention (la).
  • (Id) may be reacted with an alkyl halide or an alkyl sulfate represented by the formula (55) in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst. Can be converted to the compound (le) of the present invention.
  • (le) can be directly synthesized without isolating (Id) by using an excess of base.
  • any solvent may be used as long as it is inert to the reaction.
  • ethers such as getyl ether, tetrahydrofuran, and dimethoxetane
  • aromatic hydrocarbons such as benzene, xylene, and toluene
  • dichloromethane chloroform
  • Halogenated hydrocarbons such as dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, and dimethylacetamide And amides such as N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, from 0 ° C to the boiling point of the solvent. Is preferable.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (la), and preferably in the range of 1 to 20 equivalents.
  • As the equivalent of the substrate, (56) can be used in the range of 0.5 to 50 equivalents to (la), and the range of 1 to 20 equivalents is preferable.
  • the compound of the present invention (1) can be prepared in the same manner as in the above synthesis method using the aniline compound (4c) as a starting material instead of (4) in (Production method 1) and (Production method 2).
  • the heterocyclic iminophenyl compound (If) corresponding to (1) to (1-26) it can also be produced by the following method.
  • L 18 is a good leaving group such as a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and an alkyl group having 1 to 4 carbon atoms. It represents sulfonyloxy, haloalkylsulfonyloxy having 1 to 4 carbon atoms, benzenesulfonyloxy, toluenesulfonyloxy, etc.
  • the compound can be synthesized by reacting (If) with a zinc acrylate complex (57) according to the method described in (1998) or according to the method.
  • G a represents one O—, one N (R 4 ) —, one N (OR 4 ) one, one S— or one CH 2 —N (R 4 ) —.
  • the compound of the present invention (1i) can be prepared by reacting the heterocyclic iminophenyl compound represented by the formula (1h) or the like in a solvent in the presence of a base and, in some cases, a catalyst with the compound (58) in the presence of a base. It can be produced by reacting.
  • the solvent may be any solvent as long as it is inert to the reaction, for example, ethers such as getyl ether, tetrahydrofuran, and dimethyloxetane, aromatic hydrocarbons such as benzene, xylene, and toluene, dichloromethane, and chloroform.
  • Halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, Amides such as dimethylacetamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water; or a mixed solvent thereof, and the like are preferable.
  • Tetrahydrofuran, benzene, xylene, toluene, dichloromethane examples include black form, 1,2-dichloroethane, acetonitrile, dimethylformamide and the like.
  • Examples of the base include organic bases such as triethylamine, tributylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and sodium hydride. And the like.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (111), and preferably in the range of 1 to 20 equivalents.
  • As the equivalent of the substrate, (58) can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (l h).
  • the compound (1j) of the present invention is reacted with an octaacetic acid compound represented by the formula (59) in a solvent, in the presence of a base, and in some cases, in the presence of a catalyst, with a heterocyclic iminophenyl compound (lh). Can be manufactured. As a solvent, it is inert to the reaction.
  • ethers such as getyl ether, tetrahydrofuran, and dimethoxyethane
  • aromatic hydrocarbons such as benzene, xylene, and toluene
  • halogenated carbons such as dichloromethane, chloroform, and 1,2-dichloroethane
  • Hydrogens esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone.
  • aliphatic hydrocarbons such as pentane, hexane, and cyclohexane; dimethyl sulfoxide or water; or a mixed solvent thereof.
  • Preferred are tetrahydrofuran, benzene, xylene, toluene, dichloromethane, and methyl chloride. Holm, 1,2-dichloroeta , Acetonitrile, dimethylformamide and the like.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents, preferably 1 to 20 equivalents, relative to (lh). Also, the equivalent of the substrate
  • (59) can be used in a range of 0.5 to 50 equivalents, preferably 1 to 20 equivalents, based on (1h).
  • reaction of obtaining the compound of the present invention (11) from the compound of the present invention (1j) via the compound of the present invention (lk) and the compound of the present invention (In) from the compound of the present invention (1j) via the compound of the present invention (lm) The reaction for obtaining (1) can be carried out in the same manner as the method for obtaining (lc) and (1e) from (la) shown in (Production method 4).
  • the heteroiminobenzene compound (lo) obtained from the aniline compound (4d) having a nitro group as a starting material instead of G in (4) in (Production method 1) and (Production method 2) It can also be manufactured by the method shown below
  • the heterocyclic iminonitrobenzene compound (lo) can be prepared by reducing the nitro group in a solvent, if necessary, in the presence of a base, and optionally in the presence of a catalyst, if necessary. ), And then reacted with a carbonyl compound (58) in a solvent, if necessary, in the presence of a base, and optionally a catalyst, to obtain the compound (1q) of the present invention.
  • (1Q) is obtained by converting the alkyl represented by the formula (60) into a ride or an alkyl sulfate, etc., in a solvent, if necessary, in the presence of a base, if necessary, in the presence of a catalyst. Conversion to the compound of the present invention (1r)
  • the compound (lr) of the present invention can also be obtained by first reacting (lp) with (60) and then reacting it with a carbonyl compound (58).
  • the solvent may be any solvent as long as it is inert to the reaction, for example, alcohols such as methanol and ethanol, organic acids such as acetic acid, formic acid and propionic acid, and getyl.
  • Ethers such as ether, tetrahydrofuran, and dimethoxetane; aromatic hydrocarbons such as benzene, xylene, and toluene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, and ethyl acetate; Esters, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, pentane, and hexene Aliphatic hydrocarbons such as sun, cyclohexane, dimethyl sulfoxide or water, Rui include a mixture of these solvents, preferably, tetrahydrofuran, benzene, xylene, toluene, dichloromethane, black hole Holm, 1, 2-dichloroethane
  • Examples of the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylpyridine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and the like.
  • An inorganic base such as hydrogenated sodium is used.
  • Examples of the reducing agent include aluminum hydrides such as lithium aluminum hydride and diisobutylaluminum hydride; borohydrides such as sodium borohydride and potassium borohydride; and metals such as iron, zinc, and copper. And hydrogen gas.
  • Examples of the catalyst include copper chloride, palladium chloride, palladium / activated carbon, platinum / activated carbon, and the like.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, based on (lo).
  • the equivalent of the reducing agent can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, based on (1 o).
  • any solvent may be used as long as it is inert to the reaction.
  • ethers such as diethyl ether, tetrahydrofuran, and dimethoxetane
  • aromatic hydrocarbons such as benzene, xylene, and toluene
  • dichloromethane Halogenated hydrocarbons such as form and 1,2-dichloroethane
  • esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide
  • amides such as dimethylacetamide and N-methylpyrrolidone
  • aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • Is tetrahydrofuran, benzene, xylene, toluene, dichloro Examples include methyl, chloroform, 1,2-dichloroethane, acetonitrile, dimethylformamide and the like.
  • Examples of the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylbiperidine, and 4-dimethylaminopyridine, and potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents with respect to (lp) or (Is), and the range of 1 to 20 equivalents is preferable.
  • As for the equivalent of the substrate, (58) can be used in a range of 0.5 to 50 equivalents with respect to (1p) or (1S), and in a range of 1 to 20 equivalents. Is preferred.
  • any solvent may be used as long as it is inert to the reaction.
  • Ethers such as tetrahydrofuran and dimethoxetane, aromatic hydrocarbons such as benzene, xylene, and toluene; halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane; esters such as ethyl acetate; Ketones such as setone and methyl ethyl ketone, nitriles such as acetonitrile and propionitrile, dimethylformamide, dimethylacetamide, N-methylbiethyl Examples include amides such as mouth ridone, aliphatic hydrocarbons such as pentane, hexane, and cyclohexane, dimethyl sulfoxide or water, or a mixed solvent thereof.
  • tetrahydrofuran and dimethoxetane aromatic hydrocarbons such as benzene, x
  • the base examples include organic bases such as triethylamine, tributylamine, pyridine, N-methylpiperidine, and 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogencarbonate, sodium hydroxide, potassium hydroxide, and hydrogenation.
  • An inorganic base such as sodium is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction temperature can be in the range of 180 ° C to the boiling point of the solvent, preferably in the range of 0 to the boiling point of the solvent.
  • the reaction time may be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the base can be used in the range of 0.05 to 150 equivalents to (lq) or (lp), and preferably in the range of 1 to 20 equivalents.
  • the equivalent of the substrate can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (1q) or (lp).
  • the compound represented by the formula (1t) by reacting the compound represented by the formula (1t) with an amine compound (61) as necessary in a solvent, optionally in the presence of a base, and in some cases in the presence of a catalyst, (lu) and You can do it.
  • (Lu) is converted to (lv) by hydrolyzing (1t) in a solvent, if necessary, in the presence of a catalyst, if necessary, in the presence of an acid or a base, if necessary.
  • the compound can also be obtained by dehydration-condensation with an amine compound (61) in a solvent, in some cases, in the presence of a base, and in some cases, in the presence of a catalyst.
  • (lv) may be converted into a nodule in a solvent, if necessary, in the presence of a catalyst, to give an acid halide compound (lx), and then, if necessary, in a solvent, if necessary, in the presence of a base.
  • (lu) can also be obtained by reacting with an amine compound (61) in the presence of a catalyst.
  • any solvent may be used as long as it is inert to the reaction.
  • lower alcohols such as methanol and ethanol
  • Aromatic hydrocarbons such as benzene, xylene, toluene, etc., dichloromethane, chloroform, halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, acetone, methyl ethyl ketone, etc.
  • Ketones, acetonitrile, propionitrile Amides such as dimethylformamide, dimethylacetamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; dimethyl sulfoxide or water;
  • a mixed solvent thereof may, for example, be mentioned, and preferably, a mixed solvent of methanol, ethanol or water, or a mixed solvent of methanol and water may be mentioned.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 ° C. to the boiling point of the solvent, preferably from 0 ° C.
  • reaction time may be from 5 minutes to 500 hours, preferably from 1 hour to 100 hours.
  • equivalent of the substrate (.61) can be used in the range of 0.5 to 1000 equivalents, and preferably 1 to 20 equivalents, with respect to (1t).
  • any solvent may be used as long as it is inert to the reaction.
  • examples thereof include lower alcohols such as methanol and ethanol, and alcohols such as getyl ether, tetrahydrofuran, and dimethoxetane.
  • Aromatic hydrocarbons such as ters, benzene, xylene, toluene, etc., halogenated hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, acetone, methylethyl ketone, etc.
  • Ketones such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide and N-methylvinylidone, and aliphatics such as pentane, hexane and cyclohexane Hydrocarbons, dimethyl sulfoxide or water, or a mixed solvent thereof;
  • methanol, ethanol, tetrahydrofuran, acetone, acetonitrile, dimethylformamide or water, or a mixed solvent thereof is used.
  • water can be used as a solvent.
  • inorganic bases such as potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and sodium hydride are used.
  • acid an inorganic acid such as hydrochloric acid or sulfuric acid or an organic acid such as acetic acid can be used.
  • catalyst for example, Tetra N-butylammonium bromide or the like is used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 200 hours, preferably from 1 hour to 50 hours.
  • water is 0.
  • the equivalents of the base and the acid can be used in the range of 0.5 to 10000 equivalents, and preferably in the range of 1 to 20 equivalents, based on (It).
  • the solvent may be inert to the reaction, for example, lower alcohols such as methanol and ethanol, ethers such as getyl ether, tetrahydrofuran, and dimethoxetane, and benzene.
  • Xylene aromatic hydrocarbons such as toluene, dichloromethane, chloroform, halogenated hydrocarbons such as 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, Nitrils such as acetonitrile and propionitrile, amides such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, dimethyl Sulfoxide or water, or a mixed solvent thereof, etc., is preferred.
  • aromatic hydrocarbons such as toluene, dichloromethane, chloroform
  • halogenated hydrocarbons such as 1,2-dichloroethane
  • esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone
  • Nitrils such as
  • the condensing agent include concentrated sulfuric acid, disuccinic hexylcarpoimide, 1,1'-carbonyldiimidazole, ezodicarboethylethyl triphenylphosphine, 1-ethyl-3- (3-dimethylaminopropyl) carbopimidide, etc. Is used.
  • the catalyst for example, tetra-N-butylammonium bromide, dimethylaminopyridine and the like are used.
  • the reaction can be carried out at a temperature ranging from 180 ° C to the boiling point of the solvent, preferably from 0 ° C to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 200 hours, preferably from 1 hour to 50 hours.
  • (61) can be used in the range of 0.5 to 10000 equivalents to (lv), and preferably in the range of 1 to 20 equivalents.
  • any solvent may be used as long as it is inert to the reaction.
  • ethers such as getyl ether, tetrahydrofuran, and dimethoxysilane, benzene, xylene, and toluene
  • Aromatic hydrocarbons such as dichloromethane, chloroform, 1,2-dichloroethane, etc., esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitrile Nitriles, dimethylformamide, Amides such as tilacetoamide and N-methylpyrrolidone; aliphatic hydrocarbons such as pentane, hexane and cyclohexane; and mixed solvents thereof, and the like, preferably, tetrahydrofuran, benzene, toluene, and chloroform
  • N, N-dimethylformamide-tetra-N-butylammonium bromide or the like is used as the catalyst.
  • halogenating agents include oxyphosphorus chloride, sulfuryl chloride, thionyl chloride, oxalic acid dichloride, chlorine gas, phosphorus pentachloride, phosphorus trichloride, bromine, N-bromosuccinic imid, and N-chlorosuccinic imid.
  • tetrabutylammonium tribromide, phosphorus tribromide, phosphorus oxybromide and the like are used as the catalyst.
  • the reaction can be carried out at a temperature ranging from ⁇ 80 X: to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the halogenating agent can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (lv).
  • the solvent may be any solvent as long as it is inert to the reaction. Examples thereof include ethers such as dimethyl ether, tetrahydrofuran, and dimethoxetane, benzene, xylene, and toluene.
  • Aromatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane, esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitrile and the like
  • esters such as ethyl acetate, ketones such as acetone and methyl ethyl ketone, acetonitrile, propionitrile and the like
  • Examples include nitriles, dimethylformamide, dimethylacetamide, amides such as N-methylpyrrolidone, aliphatic hydrocarbons such as pentane, hexane and cyclohexane, and mixed solvents thereof.
  • the base include organic bases such as triethylamine, triptylamine, pyridine, N-methylpyridine, 4-dimethylaminopyridine, potassium carbonate, sodium carbonate, sodium hydrogen carbonate, sodium hydroxide, potassium hydroxide, and hydrogen.
  • An inorganic base such as sodium fluoride is used.
  • the catalyst for example, tetra-N-butylammonium bromide or the like is used.
  • a solvent without using a base and a catalyst (Lu) can also be obtained by heating with The reaction can be carried out at a temperature ranging from 180 ° C. to the boiling point of the solvent, preferably from 0 to the boiling point of the solvent.
  • the reaction time can be from 5 minutes to 100 hours, preferably from 1 hour to 48 hours.
  • the equivalent of the substrate (61) can be used in a range of 0.5 to 50 equivalents, and preferably in a range of 1 to 20 equivalents, relative to (lx).
  • the equivalent of the base can be used in the range of 0.5 to 50 equivalents, and preferably in the range of 1 to 20 equivalents, relative to (lx).
  • the nitro compound represented by the formula (3) which is a starting material in (Production method 1), can be produced by a known method.
  • Nitroaniline compounds represented by Z are described in Organic Functional Group Preparations (Academic Preress) Vol. 2, No. 10 It can be produced from ortho-nitroaniline or ortho-octanitrobenzene by a known method described in Chapters 1 to 12 (1971).
  • - O- C H2C ( 0) Z
  • Nitrophenols and nitrothiophenol compounds can be prepared from orthophenol or orthothiophenol by known methods described in the literature.
  • a ⁇ s'A 2 a, A 2 d, A 2 f, A 2 g, A 2 h, 8 2 is one 0 ⁇ ! 2 —
  • B 2 is 1 CH ( CN) one,-CH (C ⁇ CH) one, one CH (OR 4 ) one, -N (OR 4 ) one, one N (R 4 ) one, one 0--, one S-, - ⁇ (OR 4 )
  • B 2 is 1 CH ( CN) one,-CH (C ⁇ CH) one, one CH (OR 4 ) one, -N (OR 4 ) one, one N (R 4 ) one, one 0--, one S-, - ⁇ (OR 4 )
  • B 2 is - CH (CN) one, - CH (C ⁇ CH) -, - CH (OR 4) -, - N (OR 4) CH
  • Compounds that are 2- , —N (R 4 ) CH 2 —, 1 O CH 2 — or 1 S CH 2 — can be similarly produced by appropriately changing the starting material, a halide or a cyano compound.
  • a compound wherein A 2 is pyridyl which may be substituted, A 2 e, A 2 j or A 2 k and B 2 is —CH (OR 4 ) — is described in International Application Publication WO97 / 128686. It can be manufactured by the method described in Japanese Patent Publication No.
  • a 2 is A 2 a, A 2 d, A 2 e, A 2 f, A 2 g, A 2 h, A 2 i, A 2 j, A 2 k or 1 B 2 is - N (OR 4) -, 1 N (R 4 ) 1, — ⁇ —, — S— compounds include, for example, — B 2 — H-substituted nitrobenzene compound and A 2 — L (where L is a good leaving group such as , A halogen atom, a methanesulfonyl group, etc.) or a nitrobenzene compound substituted by L (where L represents the same meaning as described above) and A 2 —B 2 —H Can be produced by the reaction with A 2 is A 2 1 compounds in International Application Publication WO 9 6/1 7 8 3 5 JP method, the compounds of A 2 is A 2 q International Application Publication WO 9 9/7 6 8 7 Patent Publication No. Each can be manufactured by the method described in the report.
  • G 1 2 or G 1 4-substituted for example the JP 1 1 one 3 3 5 3 6 1 JP Symbol mounting methods reference compounds G 1 3 is substituted, for example, Japanese Each of them can be produced with reference to the methods described in Japanese Unexamined Patent Application Publication No. Hei 11-222500, Japanese Unexamined Patent Application Publication No. 7-197950, and the like.
  • the compound of the present invention or an intermediate thereof produced in each step can be obtained from the reaction solution by a conventional method. However, if it becomes necessary to purify the compound, any purification method such as recrystallization or column chromatography can be used. It can be separated and purified by the method.
  • M e methyl group, Et: ethyl group, Pr: propyl group, Bu: butyl group, Pen: pentyl group, Hex: hexyl group, Ph: phenyl group, n: normal, i: Iso, s: secondary, t: evening, c: cyclo.
  • G1 to G30 represent the following:
  • G11 COOMe
  • G12 CONHMe

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Abstract

La présente invention concerne des composés hétérocyclo-iminophényle représentés par la formule générale (I) piézo-électrique certains de leurs sels admis pour l'agriculture. L'invention concerne également des pesticides, des fungicides et insecticides destinés à l'agriculture et l'horticulture, et contenant les composés ou les sels. Dans cette formule, A est hétérocycle éventuellement substitué. X est hydrogène ou analogue. Enfin G est -CH2COOMe, -N(Me)COOMe, ou analogue.
PCT/JP2002/006424 2001-06-26 2002-06-26 Composes heterocyclo-iminophenyle et fungicides et insecticides destines a l'agriculture et l'horticulture WO2003000659A1 (fr)

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US6818631B1 (en) 2003-08-15 2004-11-16 Nippon Soda Co. Ltd. Fungicidal pyrimidine derivatives
WO2009131170A1 (fr) * 2008-04-25 2009-10-29 大日本住友製薬株式会社 Compose cyclique a cinq elements
US8551980B2 (en) 2009-11-30 2013-10-08 Bayer Intellectual Property Gmbh Substituted triazolopyridines
US8748442B2 (en) 2010-06-30 2014-06-10 Ironwood Pharmaceuticals, Inc. sGC stimulators
CN103980223A (zh) * 2014-05-23 2014-08-13 贵州大学 2-取代基-5-取代苯胺基-1,3,4-噁二唑类衍生物及其合成方法和应用
US9061030B2 (en) 2010-11-09 2015-06-23 Ironwood Pharmaceuticals, Inc. sGC stimulators
US9139564B2 (en) 2011-12-27 2015-09-22 Ironwood Pharmaceuticals, Inc. 2-benzyl, 3-(pyrimidin-2-yl) substituted pyrazoles useful as sGC stimulators
WO2018054807A1 (fr) 2016-09-21 2018-03-29 Bayer Cropscience Aktiengesellschaft Procédé de préparation de 3-fluoroalkyl-5-pyrazolecarboxylates et d'acides 3-fluoroalkyl-5-pyrazolecarboxylique

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US6818631B1 (en) 2003-08-15 2004-11-16 Nippon Soda Co. Ltd. Fungicidal pyrimidine derivatives
WO2009131170A1 (fr) * 2008-04-25 2009-10-29 大日本住友製薬株式会社 Compose cyclique a cinq elements
US8551980B2 (en) 2009-11-30 2013-10-08 Bayer Intellectual Property Gmbh Substituted triazolopyridines
US8748442B2 (en) 2010-06-30 2014-06-10 Ironwood Pharmaceuticals, Inc. sGC stimulators
US10189809B2 (en) 2010-06-30 2019-01-29 Ironwood Pharmaceuticals, Inc. SGC stimulators
US9061030B2 (en) 2010-11-09 2015-06-23 Ironwood Pharmaceuticals, Inc. sGC stimulators
US9139564B2 (en) 2011-12-27 2015-09-22 Ironwood Pharmaceuticals, Inc. 2-benzyl, 3-(pyrimidin-2-yl) substituted pyrazoles useful as sGC stimulators
CN103980223A (zh) * 2014-05-23 2014-08-13 贵州大学 2-取代基-5-取代苯胺基-1,3,4-噁二唑类衍生物及其合成方法和应用
WO2018054807A1 (fr) 2016-09-21 2018-03-29 Bayer Cropscience Aktiengesellschaft Procédé de préparation de 3-fluoroalkyl-5-pyrazolecarboxylates et d'acides 3-fluoroalkyl-5-pyrazolecarboxylique
US10556867B2 (en) 2016-09-21 2020-02-11 Bayer Cropscience Aktiengesellschaft Process for preparing 3-fluoroalkyl-5-pyrazolecarboxylates and 3-fluoroalkyl-5-pyrazolecarboxylic acids

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