WO2004080984A1 - Insecticidal phthalamide derivatives - Google Patents

Insecticidal phthalamide derivatives Download PDF

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Publication number
WO2004080984A1
WO2004080984A1 PCT/EP2004/002024 EP2004002024W WO2004080984A1 WO 2004080984 A1 WO2004080984 A1 WO 2004080984A1 EP 2004002024 W EP2004002024 W EP 2004002024W WO 2004080984 A1 WO2004080984 A1 WO 2004080984A1
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Prior art keywords
alkyl
methyl
phenyl
dihydro
tetrazol
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PCT/EP2004/002024
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French (fr)
Inventor
Katsuaki Wada
Takuya Gomibuchi
Yasushi Yoneta
Yuichi Otsu
Katsuhiko Shibuya
Hanako Matsuo
Rüdiger Fischer
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Bayer Cropscience Ag
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Priority to MXPA05009725A priority Critical patent/MXPA05009725A/en
Priority to US10/549,080 priority patent/US20060223872A1/en
Priority to AU2004220444A priority patent/AU2004220444B2/en
Priority to JP2006504492A priority patent/JP4617295B2/en
Priority to BRPI0408354-7A priority patent/BRPI0408354A/en
Priority to EP04715900A priority patent/EP1606271A1/en
Publication of WO2004080984A1 publication Critical patent/WO2004080984A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
    • 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
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/44—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing at least one carboxylic group or a thio analogue, or a derivative thereof, and a nitrogen atom attached to the same carbon skeleton by a single or double bond, this nitrogen atom not being a member of a derivative or of a thio analogue of a carboxylic group, e.g. amino-carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D231/18—One oxygen or sulfur atom
    • C07D231/20—One oxygen atom attached in position 3 or 5
    • C07D231/22—One oxygen atom attached in position 3 or 5 with aryl radicals attached to ring nitrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member 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
    • C07D233/30—Oxygen or sulfur atoms
    • C07D233/32—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/64—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with substituted hydrocarbon radicals attached to ring carbon atoms, e.g. histidine
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/70—One oxygen atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D239/00—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings
    • C07D239/02—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings
    • C07D239/20—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D239/22—Heterocyclic compounds containing 1,3-diazine or hydrogenated 1,3-diazine rings not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D249/00—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms
    • C07D249/02—Heterocyclic compounds containing five-membered rings having three nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D249/08—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles
    • C07D249/10—1,2,4-Triazoles; Hydrogenated 1,2,4-triazoles 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
    • C07D249/12—Oxygen or sulfur atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D257/00—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms
    • C07D257/02—Heterocyclic compounds containing rings having four nitrogen atoms as the only ring hetero atoms not condensed with other rings
    • C07D257/04—Five-membered rings

Definitions

  • the present invention relates to novel phthalamide derivatives, to processes for their preparation and to their use as insecticides.
  • Certain phthalamide derivatives showing an action as insecticide are already known (cf. EP-A 0 919 542, WO 01/00575, JP-A 2001-64268, EP-A 1 006 107, JP-A 2003-40864, WO 01/21576 and WO 03/11028). Further, it is already known that certain phthalamide derivatives show an action as pharmaceutical (cf. EP-A 0 119 428).
  • X represents hydrogen, halogen, C ⁇ -C 6 -alkyl, C ⁇ -C 6 -haloalkyl, nitro, cyano, C ⁇ C 6 -alkyl ⁇ sulfonyloxy, C]-C 6 -haloalkylsulfonyloxy, phenylsulfonyloxy, Ci-C ⁇ -alkylthio- - -alkyl, Ci-C ⁇ -alkylsulfinyl-C C ⁇ -alkyl, Ci-C ⁇ -alkylsulfonyl- -Ce-alkyl, C ⁇ -C 6 -alkylsulfonylamino, bis(C ⁇ -C 6 -alkylsulfonyl)amino or C C 6 -alkylcarbonyloxy, n represents 1, 2, 3 or 4,
  • Y represents hydrogen, halogen, C)-C 6 -alkyl, -Cg-haloalkyl, Ci-Ce-alkoxy, -C 6 -haloalkoxy,
  • R 1 represents C ⁇ -C 8 -alkyl, -Cs-alkyl which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, C ⁇ -C 6 -alkylaminosulfonyl, N,N-di(C C 6 - alkyl)aminosulfonyl, C C 6 -alkylsulfonylamino, N-C ⁇ -C 6 -alkylsulfonyl-N-C ⁇ -C 6 -alkylamino, C ⁇ -C 6 -alkyl-carbonylamino, halo-C ⁇ -C 6 -alkyl, N-Gx-C ⁇ -alkyl-carbonyl-N-Ci-Ce-alkylamino, C ⁇ -C 6 -alkyl-thiocarbonylamino, N-C C ⁇ -alkylthiocarbonyl-N-Ci-C ⁇ -alkylamino
  • R 2 represents hydrogen or C ⁇ -C 6 -alkyl
  • R 3 represents hydrogen or C ⁇ -C 6 -alkyl
  • a 1 represents straight chain or branched chain Ci-Q-alkylene, C ⁇ -C 8 -haloalkylene, C 2 -C 3 -alke- nylene, C 2 -C 8 -haloalkenylene, C 2 -C 8 -alkynylene, C 2 -C 8 -haloalkynylene, C ⁇ -C 8 -alkylene- amino, C ⁇ -C 8 -alkylene(C C 6 -alkylamino), C r C 8 -alkyleneoxy or C ⁇ -C 8 -alkylenethio, r represents 0 or 1,
  • a 2 represents straight chain or branched chain C ⁇ -C 3 -alkylene, C ⁇ -C 8 -haloalkylene, C 2 -C 8 -alke- nylene, C 2 -C 8 -haloalkenylene, C 2 -Cs-alkynylene or C 2 -C 8 -haloalkynylene, s represents 0 or 1,
  • Q represents a 5- or 6-membered heterocyclic group containing 1 to 4 hetero atoms selected from 0 to 4 nitrogen atom, 0 to 1 oxygen atom, and 0 to 1 sulphur atom, however not containing an oxygen atom and a sulphur " atom at the same time, and said heterocyclic group
  • ⁇ C _— O may have one to three ⁇ C _— O , one to three ⁇ C _— S , one ⁇ S _— O or one ⁇ S ⁇ .o
  • heterocyclic group may be optionally substituted with at least one or more substituents selected from the below-mentioned group of substituents W 1 wherein said substituents may be identical or different,
  • W 1 represents halogen, C C 6 -alkyl, Ci-Q-alkoxy, d-Q-alkylthio, C C 6 -alkylsulfinyl, C C 6 - alkylsulfonyl, C ⁇ -C 6 -haloalkyl, C C 6 -haloalkoxy, C]-C 6 -haloalkylthio, C ⁇ -C 6 -haloalkylsulfi- nyl, C C 6 -haloalkylsulfonyl, C 3 -C 6 -cycloalkyl, Cj-C ⁇ -alkylthio-Ci-C ⁇ -alkyl, C C 6 -alkylsul- fmyl-C ⁇ -C 6 -alkyl, C ⁇ -C 6 -alkylsulfonyl-C,-C 6 -alkyl,
  • E represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group is optionally mono- or poly-substituted by substituents selected from the group W 2 wherein said substituents may be identical or different,
  • W 2 represents halogen, nitro, C C 6 -alkyl, d-C 6 -alkoxy, C r C 6 -alkylthio, C C 6 -alkylsulf ⁇ nyl, C C 6 -alkylsulfonyl, C ⁇ -C 6 -haloalkyl, C C 6 -haloalkoxy, C ⁇ -C 6 -haloalkylthio, C ⁇ -C 6 -haloalkyl- sulfmyl, C ⁇ -C 6 -haloalkylsulfonyl, C 3 -C 6 -cycloalkyl, C ⁇ -C 6 -alkylthio-C ⁇ -C 6 -alkyl, C C 6 -al- kylsulfinyl-C C 6 -alkyl or d-C ⁇ -alkylsulfonyl-d-C ⁇ -alkyl, or represents C 3 -C 5 -alkylene
  • the compounds of the formula (I) can be present as geometrical and/or optical isomers, regioisomers and/or configurational isomers or isomer mixtures thereof of varying composition.
  • What is claimed by the invention are both the pure isomers and the isomer mixtures.
  • the compounds of the formula (I) of the present invention can be obtained, for example, by the following preparation processes (a), (b), (c), (d), (e) and (f):
  • R 3 , Y, m, A 1 , r, Q, A 2 , s and E have the same definition as aforementioned, in the presence of inert solvents.
  • R 1 and R 2 have the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
  • R 3 , Y, m, A 1 , r, Q, A 2 , s and E have the same definition as aforementioned, in the presence of inert solvents.
  • R 1 and R 2 have the same definition as aforementioned, in the presence of inert solvents .
  • R 1 and R 2 have the same definition as aforementioned, in the presence of inert solvents.
  • R lf represents C ⁇ -C 6 -alkylthio-C ⁇ -C 6 -alkyl
  • X, n, R 2 , R 3 , Y, m, A 1 , r, Q, A 2 , s and E have the same definition as aforementioned, with an oxidizing agent in the presence of inert solvents.
  • the phthalamide derivatives of the aforementioned formula (I) show strong insecticidal action.
  • the formula (I) provides a general definition of the phthalamide derivatives according to the in- vention.
  • X preferably represents hydrogen, halogen, C ⁇ -C 4 -alkyl, C ⁇ -C -haloalkyl, nitro, cyano, C C 4 - alkylsulfonyloxy, C C 4 -haloalkylsulfonyloxy, phenylsulfonyloxy, C ⁇ -C 4 -alkylthio-C C - alkyl, Ci -alkylsuljBmyl-Ci- -alkyl, C C 4 -alkylsulfonyl-d-C 4 -alkyl, C r C 4 -alkylsulfonyl- amino, bis(C C 4 -alkylsulfonyl)amino or C C 4 -alkylcarbonyloxy.
  • X particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, trifluoromethyl, difluoromethyl, dichloro- fluoromethyl, trichloromethyl, nitro, cyano, methylsulfonyloxy, ethylsulfonyloxy, trifluoro- methylsulfonyloxy, phenylsulfonyloxy, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethyl, ethyl- sulfinylethyl, methylsulfonylmethyl, methylsulfonyleth
  • X very particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, tert-butyl, trifluoromethyl, nitro, cyano, methylsulfonyloxy, ethylsulfonyloxy, trifluoro- methylsulfonyloxy, phenylsulfonyloxy, methylsulfonylamino, di(methylsulfonyl)arnino or methylcarbonyloxy.
  • n preferably represents 1, 2 or 4. n particularly preferably represents 1. n furthermore, particularly preferably represents 2. n furthermore, particularly preferably represents 4.
  • Y preferably represents hydrogen, halogen, d-Q-alkyl, C C 4 -haloalkyl, C ⁇ -C 4 -alkoxy, C ⁇ -C - haloalkoxy, C ⁇ -C 4 -alkylthio, C C 4 -haloalkylthio or cyano.
  • Y particularly preferably represents hydrogen, fluorine, chlorine, bromine, metliyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, trifluoromethyl, difluoromethyl, dichlorofluoromethyl, trichloromethyl, methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert-butoxy, trifluoromethoxy, methylthio, ethylthio, n- or iso-propylthio, n-, sec-, iso- or tert-butylthio, trifluoromethylthio or cyano.
  • Y very particularly preferably represents hydrogen, chlorine, methyl, trifluoromethyl, methoxy or trifluoromethoxy.
  • n preferably represents 1 or 2. m particularly preferably represents 1. m furthermore, particularly preferably represents 2.
  • R 1 preferably represents d-Q-alkyl, d-d-alkyl which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, C C 4 -alkylaminosulfonyl, N,N- di(C 1 -C 4 -alkyl)aminosulfonyl, d-d-alkylsulfonylamino, N-C r C -alkylsulfonyl-N-C ⁇ -C 4 -al- kylamino, C ⁇ -C 4 -alkyl-carbonylamino, halo-C ⁇ -C 4 -alkyl, N-C ⁇ -C 4 -alkyl-carbonyl-N-C ⁇ -C 4 - alkylamino, C ⁇ -C 4 -alkyl-thiocarbonylamino, N-d-C 4 -alkyltMocarbonyl-N-d-C 4
  • R 1 very particularly preferably represents methyl, ethyl, n- or iso-propyl, n- or sec-butyl, n- pentyl, 1-methylbutyl, 1-ethylpropyl, 1,3-dimethylbutyl; methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, each of which is mono- or poly-substituted by substituents selected from the group consisting of cyano, methylaminosulfonyl, ethylaminosulfonyl, N,N-di-
  • R 2 preferably represents hydrogen or d-C 4 -alkyl.
  • R 2 particularly preferably represents hydrogen, methyl or ethyl.
  • R 2 very particularly preferably represents hydrogen or ethyl.
  • R 3 preferably represents hydrogen or C ⁇ -C 4 -alkyl.
  • R 3 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl.
  • R 3 very particularly preferably represents hydrogen, methyl, ethyl or iso-propyl.
  • a 1 preferably represents straight chain or branched chain d-C 6 -alkylene ; C r C 6 -haloalkylene, C 2 -C 6 -alkenylene, C 2 -C 6 -haloalkenylene, C 2 -C 6 -alkynylene, C 2 -C 6 -haloalkynylene, C ⁇ -C 6 -al- kylene-amino, C r C 6 -alkylene(C ⁇ -C 4 -alkylamino), d-C 6 -alkyleneoxy or C ⁇ -C 6 -alkylenethio.
  • a 1 particularly preferably represents -CH 2 -, -(CH 2 ) 2 -, -(CH 2 ) 3 -, -CH(CH 3 )-, -OCH 2 -, -CH 2 0.-, -0(CH 2 ) 2 -, -(CH 2 ) 2 0-, -SCH 2 -, -CH 2 S-, -S(CH 2 ) 2 - or -(CH 2 ) 2 S-.
  • a 1 very particularly preferably represents -CH 2 -, -(CH 2 ) 2 -, -CH(CH 3 )-, -OCH 2 -, -0(CH 2 ) 2 - or -CH 2 S-.
  • r preferably represents 0. r furthermore preferably represents 1.
  • a 2 preferably represents straight chain or branched chain d-C 6 -alkylene, C ⁇ -C 6 -haloalkylene, d-Q-alkenylene, C 2 -C 6 -haloalkenylene, d-C ⁇ -alkynylene or C 2 -C 6 -haloalkynylene.
  • s preferably represents 0. s furthermore preferably represents 1.
  • pyridinylene preferably represents pyridinylene, pyridazinylene, pyrimidinylene, pyrazinylene, each of which is optionally mono- or poly-substituted by substituents selected from group W 1 wherein said substituents may be identical or different, or further represents the below- mentioned groups;
  • Q particularly preferably represents Q15, Q17, Q22, Q23, Q29, Q34, Q35, Q45, Q48, Q50, Q55, Q56, Q58, Q59, Q60, Q61, Q62, Q63, Q64, Q66 and Q69.
  • Q very particularly preferably represents Q15.
  • Q furthermore very particularly preferably represents Q 17.
  • Q furthermore very particularly preferably represents Q22.
  • Q furthermore very particularly preferably represents Q23.
  • Q furthermore very particularly preferably represents Q29.
  • Q furthermore very particularly preferably represents Q34.
  • Q furthermore very particularly preferably represents Q35.
  • Q furthermore very particularly preferably represents Q45.
  • Q furthermore very particularly preferably represents Q48.
  • Q furthermore very particularly preferably represents Q50.
  • Q furthermore very particularly preferably represents Q55.
  • Q furthermore very particularly preferably represents Q56.
  • Q furthermore very particularly preferably represents Q58.
  • Q furthermore very particularly preferably represents Q59.
  • Q furthermore very particularly preferably represents Q60.
  • Q furthermore very particularly preferably represents Q61.
  • Q furthermore very particularly preferably represents Q62.
  • Q furthermore very particularly preferably represents Q63.
  • Q furthermore very particularly preferably represents Q64.
  • Q furthermore very particularly preferably represents 066.
  • Q furthermore very particularly preferably represents Q69.
  • W 1 preferably represents halogen, C ⁇ -C 4 -al yl, d-Q-alkoxy, Ci-Q-alkylthio, C ⁇ -C - alkylsulfinyl, C ⁇ -C 4 -alkylsulfonyl, Ci-Q-haloalkyl, C ⁇ -C 4 -haloalkoxy, C ⁇ -C 4 -haloalkylthio, Ci-Q-haloalkylsulfinyl, d-Q-haloalkylsulfonyl, C 3 -C 6 -cycloalkyl, d-C 4 -alkylthio-C ⁇ -C - alkyl, C ⁇ -C -alkylsulfinyl-C ⁇ -C 4 -alkyl, C ⁇ -C 4 -alkylsulfonyl-C ⁇ -C -alkyl.
  • W 1 particularly preferably represents methyl, ethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl.
  • W 1 very particularly preferably represents methyl.
  • E preferably represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group is optionally mono- or poly-substituted by substituents selected from the group W 2 wherein said substituents may be identical or different.
  • E particularly preferably represents phenyl, biphenyl, 3 -pyridyl, 2-thienyl, 2-furyl or 2-pyrrolyl, wherein said group is optionally mono- to terra-substituted by substituents selected from the group W 2 wherein said substituents may be identical or different.
  • E very particularly preferably represents phenyl, biphenyl, 3 -pyridyl or 2-thienyl, wherein said group is optionally mono- to terra-substituted by substituents selected from the group W 2 wherein said substituents may be identical or different.
  • W 2 preferably represents halogen, nitro, d-C 4 -alkyl, C C 4 -alkoxy, Ci-Q-alkylthio, C r C 4 - alkylsulfinyl, d-C 4 -alkylsulfonyl, C ⁇ -C 4 -haloalkyl, d-Q-haloalkoxy, d-C 4 -haloalkylthio, d-d-haloalkylsulfinyl, C r C 4 -haloalkylsulfonyl, C 3 -C 6 -cycloalkyl, d-C 4 -alkylthio-d-C 4 - alkyl, Ci-Q-alkylsulfinyl-Crd-alkyl or C 1 -C 4 -alkylsulfonyl-C 1 -C 4 -alkyl, or represents C 3 - C 5 -alkylene,
  • W 2 particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or isopropyl, n-, sec-, iso- or tert-butyl, methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert- butoxy, trifluoromethoxy, difluoromethoxy, methylthio, ethylthio, n- or iso-propylthio, n-, sec-, iso- or tert-butylthio, trifluoromethyl, difluoromethyl, dichlorofluoromethyl, trichloro- methyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or represents -OCF 2 0-,
  • W 2 very particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, isopropyl, methoxy, trifluoromethoxy, difluoromethoxy, methylthio, trifluoromethylthio, or represents -OCF 2 0-, -0(CF 2 ) 2 0-, -OCHFCF 2 0-, -OCF 2 CHFO-, in case W 2 are two adjacent substituents.
  • W 3 represents hydrogen or has the same definition as the aforementioned W 1 , W 3 preferably represents hydrogen, methyl, trifluoromethyl or methylthio.
  • p 0, 1 or 2. p preferably represents 0. p furthermore preferably represents 1.
  • q 0, 1, 2 or 3. q preferably represents 0. q furthermore preferably represents 1.
  • radical definitions or illustrations listed above apply both to the end products and, correspondingly, to the starting materials and intermediates. These radical definitions can be combined with one another as desired, i.e. including combinations between the respective preferred ranges.
  • carbon radicals such as alkyl
  • alkyl are in each case straight-chain or branched as far as this is possible - including in combination with hetero atoms such as alkoxy.
  • the aforementioned preparation process (a) can be illustrated by the following reaction scheme in case, for example, that 3-(l,l-dimethyl-2- memylthioethylimino)-4-iodo-3H-isobenzofuran-l-one and l-(4-amino-3-methylbenzyl)- 4-(4-trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one are used as starting materials.
  • the aforementioned preparation process (b) can be illustrated by the following reaction scheme in case, for example, that 2- ⁇ 2-methyl-4-[5-oxo-4-(4-trifluoromethylphenyl)-4,5-dihydrotetrazol-l-yl- methyl]phenyl ⁇ isoindole-l,3-dione and sec-butylamine are used as starting materials.
  • the aforementioned preparation process (c) can be illustrated by the following reaction scheme in case, for example, that N-(l-methyl-propyl)phthalamic acid and l-(4-amino-3-methylbenzyl)-4-(4- trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one are used as starting materials.
  • the aforementioned preparation process (d) can be illustrated by the following reaction scheme in case, for example, that l-[4-(3-oxo-3H-isobenzofuran-l-ylideneamino)-3-memyl-benzyl]-4-(4-tri- fluoromethyl-phenyl)-l,4-dihydrotetrazol-5-one and sec-butylamine are used as starting materials.
  • the aforementioned preparation process (e) can be illustrated by the following reaction scheme in case, for example, that N- ⁇ 2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-yl- methyl]-phenyl ⁇ -phthalamic acid and sec-butylamine are used as starting materials.
  • the aforementioned preparation process (f) can be illustrated by the following reaction scheme in case, for example, that N 2 -(l,l-dimethyl-2-methylthioethyl)-3-iodo-N 1 -[2-methyl-4-(5-oxo-4-(4-tri- fluoromethylphenyl)-4,5-dihydro-tetrazol-l-ylmethyl)-phenyl]-phthalamide and m-chloroperbenzoic acid are used as starting materials.
  • the compounds of the formula (II), starting material in the above-mentioned preparation process (a), are per se known compounds and can be easily prepared according to the process described in, for example, EP-A 0 919 542, EP-A 1 006 107.
  • the compounds of the formula (EI), starting material in the above-mentioned preparation process (a), include novel compounds not mentioned in the existing literature as a part.
  • Y, m, A 1 , r, Q, A 2 , s and E have the same definitions as aforementioned with hydrogen in the presence of a catalytic reduction catalyst, for example, palladium carbon, Raney nickel, platinum oxide.
  • a catalytic reduction catalyst for example, palladium carbon, Raney nickel, platinum oxide.
  • Compounds of the formula (IH), in which R 3 corresponds alkyl can be obtained by formylating the amino group of the anilines, further alkylating and then de-formylating.
  • compounds of the formula (IE), in which R 3 corresponds alkyl can also be obtained by preparing a Schiff base complex by a reaction of the anilines obtained by the reduction of compounds of the formula (IX) and a ketone or an aldehyde and then by catalytically reducing it.
  • the compounds of the formula (TV), starting materials in the above-mentioned preparation process (b), are novel ones and can be easily obtained according to the process described in JP-A 61- 246161, for example, by reacting a compound represented by the formula'
  • the reaction can be conducted in an adequate diluent.
  • aliphatic, alicyclic arid aromatic hydrocarbons may be optionally chlorinated
  • ethers for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); esters, for example, ethyl acetate, amyl acetate; acid amides, for example, pentane, hexane, cyclohex
  • the reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally room temperature to about 200°C, preferably room temperature to 150°C.
  • reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting equimolar amount or a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (X) in a diluent, for example, acetic acid.
  • a diluent for example, acetic acid.
  • 3-nitrophthalic anhydride 3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4,5,6-tetrafluorophthalic anhydride, 3,4,5,6-tetrachlorophthalic anhydride, 3-methanesulfonyloxyphthalic anhydride.
  • 3-methanesulfonyloxyphthalic anhydride can be easily obtained from 3-hydroxvphthalic anhydride and methanesulfonyl chloride according to the process described in Tetrahedron Lett., 1988, 29, 5595-5598.
  • the catalytic hydrogen reduction can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, tetrahydrofuran (THF); alcohols, for example, methanol, etha- nol, isopropanol, butanol, ethylene glycol, and as catalytic reduction catalyst there can be mentioned palladium carbon, Raney nickel, platinum oxide.
  • ethers for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, tetrahydrofuran (THF)
  • alcohols for example, methanol, etha- nol, isopropanol, butanol, ethylene glycol
  • catalytic reduction catalyst there can be mentioned
  • Said reaction can be operated under normal pressure to elevated pressure.
  • an objective compound of the formula (IE), in wliich R 3 represents hydrogen can be obtained by hydrogenation of 1 mole of the nitro compound in a diluent, for example, ethanol in the presence ofO.1-10 % (w/w) palladium carbon.
  • a diluent for example, ethanol in the presence ofO.1-10 % (w/w) palladium carbon.
  • the compounds of the formula (IE), in wliich R 3 represents hydrogen, can also be obtained by a reaction with a metal etc. instead of a catalytic hydrogen reduction.
  • a process using a metal etc. there can be mentioned, for example, a process of treating iron powder in acetic acid, a process of reacting zinc dust under the neutral condition (Organic Syntheses Collective Vol. II, p. 447), a process of reacting stannic chloride under an acidic condition (Organic Syntheses Collective Vol. E, p. 254), a process of reacting titanium trichloride under the neutral condition, etc.
  • R 3 represents a hydrogen atom
  • R 3 represents a hydrogen atom
  • the compounds of the above-mentioned formula (XI) are compounds well known in the field of organic chemistry (cf. Chem. Ahstr. 1963, 58, 3444e; Bull. Soc. Chim. Fr. 1934, 539-545; J Chem. Res. Miniprint, 1987, 8, 2133-2139; J. Chem. Soc. B 1967, 1154-1158; J. Chem. Soc. 1961, 221-222; J. Amer. Chem. Soc. 1989, 111, 5880-5886).
  • 4-nitrobenzyl chloride (available on the market) 4-bromobenzyl chloride, (available on the market) 2-chloro-4-nitrobenzyl chloride, 2-methyl-4-nitrobenzyl chloride, 2-methoxy-4-nitrobenzyl chloride,
  • nitro-substituted benzoic acids and their esters, starting materials for the compounds of the formula (XT) are known from the literature (cf., for example, Chem. Ber. 1919, 52, 1083; Bull. Soc.
  • the process to prepare the compounds of the above-mentioned formula (IX) can be conducted in an adequate diluent.
  • aliphatic, alicyclic and aromatic hydrocarbons may be optionally chlorinated
  • ethers for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (ME3K);
  • the reaction can be conducted in the presence of an acid binder and as such an acid binder there can be mentioned, as inorganic base, hydrides, hydroxides, carbonates, bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide; as organic base, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-teframethylethylenediamine (TMEDA), N,N-dimethylaml Le, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]oc
  • the reaction can also be conducted by a process using a phase-transfer catalyst.
  • a phase-transfer catalyst examples of the diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM).
  • DME dimethoxyethane
  • THF diethylene glycol dimethyl ether
  • phase-transfer catalyst there can be mentioned, quaternary ions, for example, tetramethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabu- tylammonium bissulfate, tetrabutylammonium iodide, trioctylmethylammonium chloride, benzyl- triethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltri- ethylammonium chloride; crown ethers, for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6; cryptands, for example, [2.2.2]-cryptate, [2.1.1]-cryptate, [2.2.1]-cryptate, [2.2.B]- cryptate, [20202S]-
  • the reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about 0°C to about 200°C, preferably room temperature to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of a compound of the formula (XE) to 1 mole of the compounds of the formula (XT) in a diluent, for example, DMF, in the presence of potassium carbonate.
  • the compounds of the formula (V), starting materials in the preparation process (b), are either well- known compounds in the field of organic chemistry or can be synthesized according to the process described in DE-A 2045 905, WO 01/23350 etc.
  • N-isopropyl-phthalamic acid 3-fluoro-N-isopropyl-phthalamic acid
  • R 1 and R 2 have the same definition as aforementioned.
  • phthalic anhydride 3 -fluorophthalic anhydride, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 3-iodophthalic anhydride, 3-methylphthalic anhydride, 3-nitrophthalic anhydride, 3,6-di- fluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4,5,6- tetrafluorophthalic anhydride, 3,4,5,6-tetrachlprophthalic anhydride, 3-methanesulfonyloxyphthalic anhydride.
  • ethylamine n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butyl- amine, t-amylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, 2-(methylthio)-ethyl- amine, 2-(ethylthio)-ethylamine, l-methyl-2-(methylthio)-ethylamine, l,l-dimethyl-2-(methylthio)- ethylamine.
  • the reaction for synthesizing the compounds of the formula (VI) can be conducted according to the process described in J Org. Chem. 1981, 46, 175 etc.
  • Such a reaction can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl iso
  • the preparation process (e) can be conducted in the presence of a base and as such a base there can be mentioned tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 10 1,1 ,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and 1,8-diazabi- cyclo[5.4.0]undec-7-ene (DBU), etc.
  • tertiary amines dialkylaminoanilines and pyridines
  • TEDA 1,1 ,4,4-tetramethylethylenediamine
  • DMAP dimethylaminopyridine
  • DABCO 1,8-diazabi- cyclo[5.4.0]undec-7-ene
  • the reaction can be conducted in a substantially wide range of temperature. It can be conducted at the 15 temperatures in a range of generally about -70°C to about 100°C, preferably about 50°C to about 80°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole ' 20 amount to 4 mole amount of the compounds of the formula (XTV) to 1 mole of the compounds of the formula (XIII) in a diluent, for example, acetonitrile.
  • the compounds of the formula (VII), starting materials in the preparation process (d), are novel compounds and can be easily obtained, for example, by reacting a compound represented by the 25 formula (VEI-a)
  • VTE-a The compounds of the above-mentioned formula (VTE-a) are also novel compounds and can be easily obtained by reacting phthalic anhydrides of the aforementioned formula (X) and the compounds of the aforementioned formula (IE), in which R 3 is a hydrogen atom.
  • the reaction can be conducted in the presence of a base and as such a base there can be mentioned tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethyl- ethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylami- nopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7- ene (DBU).
  • TMEDA 1,1,4,4-tetramethyl- ethylenediamine
  • DMAP 4-dimethylami- nopyridine
  • DABCO l,4-diazabicyclo[2.2.2]octane
  • DBU l,8-diazabicyclo[5.4.0]undec-7- ene
  • the reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -70°C to about 100°C, preferably about -50°C to about 80°C.
  • reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to 4 mole amount of the compounds of the formula (EI), in which R 3 is a hydrogen atom, to 1 mole of the compounds of the formula (X) in a diluent, for example, acetonitrile.
  • a diluent for example, acetonitrile
  • the compounds of the formula (VIE), starting materials in the preparation process (e), are novel compounds and can be easily obtained, as described in the aforementioned preparation process (d), generally by reacting phthalic anhydrides of the aforementioned formula (X) with the compounds of the aforementioned formula (IE).
  • reaction is the same as already described in the aforementioned preparation process (d).
  • n, R 3 , m, A 1 , r, Q, A 2 , s and E have the same definition as aforementioned
  • X 1 and Y 1 each has a definition of the aforementioned X and Y but excluding bromo and iodo, is reacted with a metal reagent, for example, butyl lithium, and then reacted with carbon dioxide to obtain the compounds of the corresponding formula (VIE) (however, X and Y do not represent bromo or iodo).
  • the compounds of the above-mentioned formula (XV) are novel compounds and can be easily obtained generally by reacting a benzoic acid halide represented by the formula
  • R Y, m, A 1 , r, Q, A 2 , s and E have the same definition as aforementioned.
  • XVT The compounds of the above-mentioned formula (XVT) are well-known compounds in the field of organic chemistry and there can be mentioned specifically, benzoyl chloride, 3-fluorobenzoyl chloride, 3-chlorobenzoyl chloride, 3-methylbenzoyl chloride, 3-nitrobenzoyl chloride.
  • the reaction to prepare the compounds of the above-mentioned formula (XV) can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF),- diethylene glycol dimethyl ether (DGM); esters, for example, ethyl
  • the reaction can be conducted in the presence of an acid binder and as such an acid binder there can be mentioned, as inorganic base, hydroxides, carbonates, bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassiurii hydroxide, calcium hydroxide; as organic base, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
  • the reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20 to about 150°C, preferably about 0°C to about 100°C.
  • reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (XVT) in a diluent, for example, 1,2-dichloroethane, in the presence of triethylamine.
  • a diluent for example, 1,2-dichloroethane
  • the compounds of the formula (If), starting materials in the preparation process (f), are the compounds included in the aforementioned formula (I) of the present invention.
  • the definition of R lf in the formula (If) compounds of the formula (I) corresponding to C ⁇ -C 6 -alkylsulfinyl-C ⁇ -C 6 -alkyl or d-d-alkylsulfonyl-Ci-d-alkyl can be obtained.
  • the compounds of the formula (If) can be prepared by the aforementioned preparation processes (a), (b), (c), (d) and/or (e).
  • N I - ⁇ 4-[4-(3,5-bis-trifluoromethyl-phenyl)-5-oxo-4,5-dihydro-triazol-l-ylmethyl]-2-methyl-phenyl ⁇ - N 2 -(l , 1 -dimethyl-2-methylsulfanyl-ethyl)- 3 -iodo-phthalamide, etc .
  • the reaction of the aforementioned preparation process (a) can be conducted by using adequate diluents, singly or mixed, and as examples of the diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); nitriles, for example,
  • the preparation process (a) can be conducted in the presence of an acid catalyst and as examples of such an acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid, sulfuric acid, organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenes ⁇ lfonic acid.
  • mineral acids for example, hydrochloric acid, sulfuric acid, organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenes ⁇ lfonic acid.
  • the preparation process (a) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20°C to about 100°C, preferably about 0°C to about 100°C.
  • reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (TT) in a diluent, for example, 1,2-dichlor ⁇ ethane, in the presence of 0.01-0.1 mole amount of p-toluenesulfonic acid.
  • a diluent for example, 1,2-dichlor ⁇ ethane
  • the preparation process (b) can be conducted in the presence of a base such as tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc.
  • a base such as tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP
  • the preparation process (b) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20°C to about 150°C, preferably room temperature to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to 25 mole amount of the compounds of the formula (V) to 1 mole of the compounds of the formula (TV).
  • the reaction of the aforementioned preparation process (f) can be conducted in an adequate diluent and as examples of the diluents used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; alcohols, for example, methanol, ethanol, isopropanol, butanol, acids: formic acid, acetic acid.
  • aliphatic, alicyclic and aromatic hydrocarbons may be optionally chlorinated
  • alcohols for example, methanol,
  • oxidizing agent for example, metachloroperbenzoic acid, peracetic acid, potassium metaperiodate, potassium hydrogen persulfate (oxone), hydrogen peroxide.
  • the preparation process (f) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -50°C to about 150°C, preferably about - 10°C to about 100°C.
  • reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
  • the aimed compounds can be obtained, for example, by reacting 1 mole amount to 5 mole amount of an oxidizing agent to 1 mole of the compounds of the formula (If) in a diluent, for example, dichloromethane.
  • a diluent for example, dichloromethane.
  • the reaction of the preparation process (f) can be conducted according to the process described in, for example, Jikken Kagaku Kohza (Lectures of experimental chemistry), compiled by the Chemical Society of Japan, 4 th ed., Vol. 24, page 350 (1992) published by Maruzen or ibid., page 365.
  • the compounds of the formula (I) of the present invention show strong insecticidal action. They can, therefore, be used, as insecticidal agents. And the active compounds of the formula (I) of the present invention exhibit exact controlling effect against harrnful insects without phytotoxicity against cultured plants.
  • the compounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests, etc. and applied for their extermination.
  • coleoptera pests for example, Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis,
  • Lepidoptera pests for example, Lymantria dispar, Malacosoma neustria,- Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella;
  • Hemiptera pests for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki,
  • Homoptera pests for example, Reticulitermes speratus, Coptotermes formosanus;
  • Diptera pests for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens,
  • Anopheles slnensis Culex tritaeniorhynchus.
  • mites there can be mentioned, for example, Tetranychus telarius, Tetranychus urticae,
  • nematodes there can be mentioned, for example, Meloidogyne incognita
  • novel compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes.
  • animal-parasitic pests there can be mentioned the following pests:
  • Gastrophilus spp. As insects there can be mentioned, for example, Gastrophilus spp., Stornoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis.
  • insects substances having insecticidal action against pests, which include all of them, are in some cases called as insecticides.
  • the active compounds of the present invention can be made into customary formulation forms, when they are used as insecticides.
  • formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foaming agents, pastes, tablets, granules, aerosols, active compound-impregnated natural and synthetic substances, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc.
  • formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
  • extenders namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
  • organic solvents can be used also as auxiliary solvents.
  • liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc.
  • aromatic hydrocarbons for example, xylene, toluene, alkylnaphthalene etc.
  • chlorinated aromatic or chlorinated aliphatic hydrocarbons for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.
  • aliphatic hydrocarbons for example, cyclohexane etc.
  • paraffins for example, mineral oil fractions etc.
  • alcohols for example, butanol, glycols and their ethers, esters, etc.
  • ketones for ' example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.
  • strongly polar solvents for example, dimethylformamide, dimethyl sulfoxide, etc.
  • Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons.
  • aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons.
  • solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).
  • crushed and fractionated rocks for example, calcite, marble, pumice, sepiolite, dolomite, etc.
  • synthetic granules of inorganic and organic meals for example, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.
  • nonionic and anionic emulsifiers for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, etc.)], albximin hydrolysis products, etc.
  • Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.
  • Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates).
  • tac bombs there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
  • Colorants can also be used.
  • inorganic pigments for example, iron oxide, titanium oxide, Prussian Blue, etc.
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs
  • nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • Said formulations can contain the aforementioned active components of the amount in the range of generally 0.1 -95 % by weight, preferably 0.5 -90 % by weight.
  • the active compounds of the formula (I) of the present invention can exist also as a mixed agent with ' other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators or herbicides in the form of their commercially useful formulations or in the application forms prepared from such formulations.
  • insecticides there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microbes, etc.
  • the active compounds of the formula (T) of the present invention can exist also as a mixed agent with a synergist and such formulations and application forms can be mentioned as commercially useful.
  • Said synergist itself must not be active, but is a compound that enhances the action of the active compound.
  • the content of the active compounds of the formula (I) of the present invention in a commercially useful application form can be varied in a wide range.
  • the concentration of the active compounds of the formula (I) of the present invention at the time of application can be, for example, in the range of 0.0000001-100 % by weight, preferably in the range of 0.00001-1 % by weight.
  • the compounds of the formula (I) of the present invention can be used by usual methods suitable to the application forms.
  • the active compounds of the present invention have a good stability against alkali on a calcific substance and further show an excellent residual effectiveness in wood and soil.
  • Phthalic anhydride (1.0 g) and l-(4-amino-3-methylbenzyl)-4-(4-trifluoromethylphenyl)-l,4-dihydro- tetrazol-5-one (2.4 g) were refluxed in 60ml of acetic acid for 3 hours.
  • Leaves of sweet potato were soaked in the test agent diluted to a prescribed concentration with water, dried in the air and put in a dish of 9 cm diameter. 10 larvae of Spodoptera litura at the third instar were placed on the leaves and kept in a room at the constant temperature of 25°C. After 2 and 4 days further leaves of sweet potato were added and after 7 days the number of dead larvae was counted and the rate of death was calculated.
  • test results As specific examples the compounds of the compound no. 2-12, 2-17, 2-50, 2-54, 2-140, 2-141, 2- 154, 2-172, 2-173, 2-234, 2-248, 2-253, 2-256, 2-310, 2-333, 2-337, 4-8, 4-15 and 4-16 showed 100% of rate of death at 20 ppm concentration of effective component.

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Abstract

Novel insecticidal phthalamide derivatives of the formula (I), in which is a 5- or 6- membered heterocyclic group, a plurality of processes for preparing these compounds and their use for controlling pests.

Description

Insecticidal Phthalamide Derivatives
The present invention relates to novel phthalamide derivatives, to processes for their preparation and to their use as insecticides.
Certain phthalamide derivatives showing an action as insecticide are already known (cf. EP-A 0 919 542, WO 01/00575, JP-A 2001-64268, EP-A 1 006 107, JP-A 2003-40864, WO 01/21576 and WO 03/11028). Further, it is already known that certain phthalamide derivatives show an action as pharmaceutical (cf. EP-A 0 119 428).
The conventional phthalamide derivatives, however, are not fully satisfactory in terms of effects as insecticide.
There have now been found novel phthalamide derivatives of the following formula (I)
Figure imgf000002_0001
wherein
X represents hydrogen, halogen, Cι-C6-alkyl, Cι-C6-haloalkyl, nitro, cyano, Cι~C6-alkyl~ sulfonyloxy, C]-C6-haloalkylsulfonyloxy, phenylsulfonyloxy, Ci-Cό-alkylthio- - -alkyl, Ci-Cβ-alkylsulfinyl-C Cβ-alkyl, Ci-Cβ-alkylsulfonyl- -Ce-alkyl, Cι-C6-alkylsulfonylamino, bis(Cι-C6-alkylsulfonyl)amino or C C6-alkylcarbonyloxy, n represents 1, 2, 3 or 4,
Y represents hydrogen, halogen, C)-C6-alkyl, -Cg-haloalkyl, Ci-Ce-alkoxy, -C6-haloalkoxy,
C C6-alkylthio, Cι-C6-haloalkylthio or cyano, m represents 1, 2, 3 or 4,
R1 represents Cι-C8-alkyl, -Cs-alkyl which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, Cι-C6-alkylaminosulfonyl, N,N-di(C C6- alkyl)aminosulfonyl, C C6-alkylsulfonylamino, N-Cι-C6-alkylsulfonyl-N-Cι-C6-alkylamino, Cι-C6-alkyl-carbonylamino, halo-Cι-C6-alkyl, N-Gx-Cβ-alkyl-carbonyl-N-Ci-Ce-alkylamino, Cι-C6-alkyl-thiocarbonylamino, N-C Cβ-alkylthiocarbonyl-N-Ci-Cβ-alkylamino, C C6-alk- oxyimino-Ci-Cβ-alkyl, Cι-C6-alkyl-aminocarbonyl, N,N-di(Cι-Cβ-alkyl)-aminocarbonyl, Cj- C6-alkyl-aminothiocarbonyl, N,N-di(Cι-C6-alkyl)-ammothiocarbonyl, C C6-alkoxy-carbo- nylamino, Ci-Cβ-alkoxy-carbonyl-C Cβ-alkylamino, Cι-C6-alkylamino-carbonyloxy, N,N- di(Cι-C6-alkyl)amino-ca bonyloxy, Cι-C6-alkoxy-thiocarbonylamino, CrC6-alkoxy-thiocar- bonyl-Cι-C6-alkylamino, d-Ce-alkylamino-thiocarbonyloxy, N,N-di(d-C6-alkyl)-amino- thiocarbonyloxy, ' Cι-C6-alkylthio-carbonylamino, d-d-alkylthio-carbonyl-d-Q-alkyl- amino, d-d-alkylammo-carbonylthio, N,N-di(d-C6-alkyl)ammo-carbonylthio, Cι-C6-alkyl- thio-tMocarbonylamino, Cι-C6-alkyl io-thiocarbonyl-Cι-C6-alkylamino, Cι-C6-alkylamino- thiocarbonylthio, N,N-di(Cι-C6-alkyl)amino-miocarbonylthio, C3-C6-cycloalkyl, C C6- alkoxy-d-Cβ-alkyl, d-C6-alkylthio-d-C6-alkyl, Ci-Cβ-alkylsulfmyl-d-Ce-alkyl and CrC6- alkylsulfonyl-Cι-C6-alkyl, or represents C3-C8-cycloalkyl which may be substituted by substituents selected from the group consisting of C]-C4-alkyl, C C4-alkylthio or C]-C2- alkylthio-d-C2-alkyl,
R2 represents hydrogen or Cι-C6-alkyl,
R3 represents hydrogen or Cι-C6-alkyl,
A1 represents straight chain or branched chain Ci-Q-alkylene, Cι-C8-haloalkylene, C2-C3-alke- nylene, C2-C8-haloalkenylene, C2-C8-alkynylene, C2-C8-haloalkynylene, Cι-C8-alkylene- amino, Cι-C8-alkylene(C C6-alkylamino), CrC8-alkyleneoxy or Cι-C8-alkylenethio, r represents 0 or 1,
A2 represents straight chain or branched chain Cι-C3-alkylene, Cι-C8-haloalkylene, C2-C8-alke- nylene, C2-C8-haloalkenylene, C2-Cs-alkynylene or C2-C8-haloalkynylene, s represents 0 or 1, Q represents a 5- or 6-membered heterocyclic group containing 1 to 4 hetero atoms selected from 0 to 4 nitrogen atom, 0 to 1 oxygen atom, and 0 to 1 sulphur atom, however not containing an oxygen atom and a sulphur" atom at the same time, and said heterocyclic group
may have one to three \ C _— O , one to three \ C _— S , one \ S _— O or one \ S^.o
as ring constituent, and said heterocyclic group may be optionally substituted with at least one or more substituents selected from the below-mentioned group of substituents W1 wherein said substituents may be identical or different,
W1 represents halogen, C C6-alkyl, Ci-Q-alkoxy, d-Q-alkylthio, C C6-alkylsulfinyl, C C6- alkylsulfonyl, Cι-C6-haloalkyl, C C6-haloalkoxy, C]-C6-haloalkylthio, Cι-C6-haloalkylsulfi- nyl, C C6-haloalkylsulfonyl, C3-C6-cycloalkyl, Cj-Cβ-alkylthio-Ci-Cβ-alkyl, C C6-alkylsul- fmyl-Cι-C6-alkyl, Cι-C6-alkylsulfonyl-C,-C6-alkyl,
E represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group is optionally mono- or poly-substituted by substituents selected from the group W2 wherein said substituents may be identical or different,
W2 represents halogen, nitro, C C6-alkyl, d-C6-alkoxy, CrC6-alkylthio, C C6-alkylsulfϊnyl, C C6-alkylsulfonyl, Cι-C6-haloalkyl, C C6-haloalkoxy, Cι-C6-haloalkylthio, Cι-C6-haloalkyl- sulfmyl, Cι-C6-haloalkylsulfonyl, C3-C6-cycloalkyl, Cι-C6-alkylthio-Cι-C6-alkyl, C C6-al- kylsulfinyl-C C6-alkyl or d-Cβ-alkylsulfonyl-d-Cβ-alkyl, or represents C3-C5-alkylene, C3- C5-haloalkylene, oxy-C2-C4-alkylene, oxy-C2-C -haloalkylene, C2-C4-alkyleneoxy, C2-C4- haloalkyleneoxy, Cι-C3-alkylenedioxy or Cι-C3-haloalkylenedioxy, in case that W2 are two adjacent substituents.
Depending, if appropriate, on the type and number of substituents, the compounds of the formula (I) can be present as geometrical and/or optical isomers, regioisomers and/or configurational isomers or isomer mixtures thereof of varying composition. What is claimed by the invention are both the pure isomers and the isomer mixtures.
The compounds of the formula (I) of the present invention can be obtained, for example, by the following preparation processes (a), (b), (c), (d), (e) and (f):
Preparation process (a): in case that R2 in the formula (I) represents hydrogen. A process of reacting compounds of the formula (II)
Figure imgf000004_0001
wherein R , X and n have the same definition as aforementioned, with compounds of the formula (IU)
Figure imgf000004_0002
wherein R3, Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned, in the presence of inert solvents.
Preparation process (b): in case that R3 in the formula (I) represents hydrogen atom. A process of reacting compounds of the formula (TV)
Figure imgf000004_0003
wherein X, n, Ϋ, m, A 1 , ~ r, , s and E have the same definition as aforementioned, with compounds of the formula (V)
R1
(V)
H"Λ R2 wherein R1 and R2 have the same definition as aforementioned, in the presence of inert solvents, and if appropriate, in the presence of a base.
Preparation process (c):
A process of reacting a compound represented by the formula (VT)
Figure imgf000005_0001
wherein X, n, R1 and R2 have the same definition as aforementioned, with the compounds of the- formula (EI),
Figure imgf000005_0002
wherein R3, Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned, in the presence of inert solvents.
Preparation process (d): in case that R3 in the formula (I) represents hydrogen atom. A process of reacting compounds of the formula (VII)
Figure imgf000005_0003
wherein X, n, Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned, with the compounds of the formula (V),
R
H-r{ (V)
R2 wherein R1 and R2 have the same definition as aforementioned, in the presence of inert solvents .
Preparation process (e):
A process of reacting a compounds of the formula (VIII)
Figure imgf000006_0001
wherein X, n, R3, Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned, with the compounds of the formula (V),
Figure imgf000006_0002
wherein R1 and R2 have the same definition as aforementioned, in the presence of inert solvents.
Preparation process (f): in case that R1 in the formula (I) represents Cι-C6-alkylsulfinyl-Cι-C6-alkyl or d-Q-alkylsulfonyl-d-d-alkyl. A process of reacting compounds of the formula (If)
Figure imgf000006_0003
wherein Rlf represents Cι-C6-alkylthio-Cι-C6-alkyl, and
X, n, R2, R3, Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned, with an oxidizing agent in the presence of inert solvents.
According to the present invention, the phthalamide derivatives of the aforementioned formula (I) show strong insecticidal action.
The formula (I) provides a general definition of the phthalamide derivatives according to the in- vention.
Preferred substituents or ranges of radicals listed in the formulae mentioned above and below are illustrated below:
X preferably represents hydrogen, halogen, Cι-C4-alkyl, Cι-C -haloalkyl, nitro, cyano, C C4- alkylsulfonyloxy, C C4-haloalkylsulfonyloxy, phenylsulfonyloxy, Cι-C4-alkylthio-C C - alkyl, Ci -alkylsuljBmyl-Ci- -alkyl, C C4-alkylsulfonyl-d-C4-alkyl, CrC4-alkylsulfonyl- amino, bis(C C4-alkylsulfonyl)amino or C C4-alkylcarbonyloxy.
X particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, trifluoromethyl, difluoromethyl, dichloro- fluoromethyl, trichloromethyl, nitro, cyano, methylsulfonyloxy, ethylsulfonyloxy, trifluoro- methylsulfonyloxy, phenylsulfonyloxy, methylthiomethyl, methylthioethyl, ethylthiomethyl, ethylthioethyl, methylsulfinylmethyl, methylsulfinylethyl, ethylsulfinylmethyl, ethyl- sulfinylethyl, methylsulfonylmethyl, methylsulfonylethyl, ethylsulfonylmethyl, ethylsulfo- nylethyl, methylsulfonylamino, ethylsulfonylamino, di(methylsulfonyl)amino, di(ethylsulfo- nyl)amino, methylcarbonyloxy or ethylcarbonyloxy.
X very particularly preferably represents hydrogen, fluorine, chlorine, bromine, iodine, methyl, tert-butyl, trifluoromethyl, nitro, cyano, methylsulfonyloxy, ethylsulfonyloxy, trifluoro- methylsulfonyloxy, phenylsulfonyloxy, methylsulfonylamino, di(methylsulfonyl)arnino or methylcarbonyloxy.
n preferably represents 1, 2 or 4. n particularly preferably represents 1. n furthermore, particularly preferably represents 2. n furthermore, particularly preferably represents 4.
Y preferably represents hydrogen, halogen, d-Q-alkyl, C C4-haloalkyl, Cι-C4-alkoxy, Cι-C - haloalkoxy, Cι-C4-alkylthio, C C4-haloalkylthio or cyano.
Y particularly preferably represents hydrogen, fluorine, chlorine, bromine, metliyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, trifluoromethyl, difluoromethyl, dichlorofluoromethyl, trichloromethyl, methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert-butoxy, trifluoromethoxy, methylthio, ethylthio, n- or iso-propylthio, n-, sec-, iso- or tert-butylthio, trifluoromethylthio or cyano.
Y very particularly preferably represents hydrogen, chlorine, methyl, trifluoromethyl, methoxy or trifluoromethoxy.
m preferably represents 1 or 2. m particularly preferably represents 1. m furthermore, particularly preferably represents 2.
R1 preferably represents d-Q-alkyl, d-d-alkyl which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, C C4-alkylaminosulfonyl, N,N- di(C1-C4-alkyl)aminosulfonyl, d-d-alkylsulfonylamino, N-CrC -alkylsulfonyl-N-Cι-C4-al- kylamino, Cι-C4-alkyl-carbonylamino, halo-Cι-C4-alkyl, N-Cι-C4-alkyl-carbonyl-N-Cι-C4- alkylamino, Cι-C4-alkyl-thiocarbonylamino, N-d-C4-alkyltMocarbonyl-N-d-C4-alkyl- amino, Cι-C -alkoxyimino-C1-C4-alkyl, Cι-C -alkyl-aminocarbonyl, N,N-di(C1-C4-alkyl)- aminocarbonyl, CrC4-alkyl-aminothiocarbonyl, N,N-di(Cι-C -alkyl)-aminothiocarbonyl, C C4-alkoxy-carbonylamino, C1-C4-alkoxy-carbonyl-Cι-C4-alkylamino, CrC4-alkylamino-car- bonyloxy, N,N-di(C1-C4-alkyl)amino-carbonyloxy, Cι-C4-alkoxy-thiocarbonylamino, C C4- alkoxy-thiocarbonyl-Cι-C4-alkylamino, Cι-C4-alkylamino-thiocarbonyloxy, N,N-di(CrC4- alkyl)amino-thiocarbonyloxy, C]-C -alkylthio-carbonylamino, Cι-C4-alkylthio-carbonyl-Cι- C4-alkylamino, Cι-C4-alkylamino-carbonylthio, N,N-di(Cι-C4-alkyl)amino-carbonylthio, C C4-alkylthio-thiocarbonylamino, d-Q-alkylthio-thiocarbonyl-d^-alkylamino, C C -al- kylamino-thiocarbonylthio, N,N-di(Cι-C4-alkyl)amino-thiocarbonylthio, C3-C6-cycloalkyl, C,-C4-alkoxy-d-C4-alkyl, d-C4-alkylthio-C C4-alkyl, d-C4-alkylsulfmyl-C,-C4-alkyl and Cι-C -alkylsulfonyl-Cι-C4-alkyl, or represents C3-C6-cycloalkyl which may be substituted by d-C2-alkyl, d-d-alkylthio or d-C2-alkylthio-d-C2-alkyl. particularly preferably represents methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, n- pentyl, 1-methylbutyl, 1-ethylpropyl, n-hexyl, 1,3-dimethylbutyl; methyl, ethyl, n- or isopropyl, n-, sec-, iso- or tert-butyl, each of which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, methylaminosulfonyl, ethylaminosulfonyl, N,N-di(me&yl)aminosulfonyl, N,N-di(ethyl)aminosulfonyl, methylsulfonylamino, ethylsul- fonylamino, N-methylsulfonyl-N-methylamino, N-ethylsulfonyl-N-methylamino, N-methyl- sulfonyl-N-ethylamino, N-ethylsulfonyl-N-ethylamino, methyl-carbonylamino, ethyl-carbo- nylamino, trifluoromethyl, pentafluoroethyl, N-methyl-carbonyl-N-methylamino, methyl- thiocarbonylamino, ethyl-thiocarbonylamino, N-methylthiocarbonyl-N-methylamino, meth- oxyimino-methyl, methoxyimino-ethyl, ethoxyimino-methyl, ethoxyimino-ethyl, methyl- aminocarbonyl, ethyl-aminocarbonyl, N,_ -di(methyl)-aminocarbonyl, N,N-di(ethyl)-amino- carbonyl, methyl-aminothiocarbonyl, ethyl-aminothiocarbonyl, N,N-di(methyl)-aminothio- carbonyl, N,N-di(ethyl)-aminothiocarbonyl, methoxy-carbonylamino, ethoxy-carbonylamino, methoxy-carbonyl-methylamino, ethoxy-carbonyl-methylamino, methoxy-carbonyl-ethyl- amino, ethoxy-carbonyl-ethylamino, methylamino-carbonyloxy, ethylamino-carbonyloxy, N,N-di(methyl)amino-carbonyloxy, N,N-di(ethyl)amino-carbonyloxy, methoxy-thiocarbo- nylamino, ethoxy-thiocarbonylamino, methoxy-thiocarbonyl-methylamino, methoxy-thiocar- bonyl-ethylamino, ethoxy-thiocarbonyl-methylamino, ethoxy-thiocarbonyl-ethylamino, me- thylamino-thiocarbonyloxy, ethylamino-thiocarbonyloxy, N,N-di(methyl)amino-thiocarbo- nyloxy, N,N-di(ethyl)amino-thiocarbonyloxy, methylthio-carbonylamino, ethylthio-carbonyl- amino, methylthio-carbonyl-methylamino, ethylthio-carbonyl-methylamino, ethylthio-car- bonyl-ethylamino, ethylthio-carbonyl-ethylamino, methylamino-carbonylthio, ethylamino- carbonylthio, N,N-di(methyl)amino-carbonylthio, N,N-di(ethyl)amino-carbonylthio, methyl- thio-thiocarbonylainino, ethylthio-thiocarbonylamino, memylthio-tMocarbonylrmethylamino, ethylthio-thiocarbonyl-methylamino, methyllMo-thiocarbonyl-ethylamino, ethylthio-thiocar- bonyl-ethylamino, methylamino-thiocarbonylthio, ethylamino-thiocarbonylthio, N,N-di(me- thyl)amino-thiocarbonylthio, N,N-di(methyl)amino-thiocarbonylthio, cyclopropyl, cyclopen- tyl, cyclohexyl, methoxy-methyl, ethoxy-methyl, methoxy-ethyl, ethoxy-ethyl, methylthio- methyl, ethylthio-methyl, methylfhio-ethyl, ethylthio-ethyl, methylsulfinyl-methyl, ethylsulfi- nyl-methyl, methylsulfinyl-ethyl, ethylsulfinyl-ethyl, methylsulfonyl-methyl, ethylsulfonyl- methyl, methylsulfonyl-ethyl, and ethylsulfonyl-ethyl; or represents cyclopropyl, cyclopentyl, cyclohexyl, each of which may be substituted by substituents selected from the group consisting of methyl, ethyl, methylthio, ethylthio, methylthiomethyl, ethylthiomethyl, methylthioetbyl and ethylthioethyl.
R1 very particularly preferably represents methyl, ethyl, n- or iso-propyl, n- or sec-butyl, n- pentyl, 1-methylbutyl, 1-ethylpropyl, 1,3-dimethylbutyl; methyl, ethyl, n- or iso-propyl, n-, sec-, iso- or tert-butyl, each of which is mono- or poly-substituted by substituents selected from the group consisting of cyano, methylaminosulfonyl, ethylaminosulfonyl, N,N-di-
(methyl)aminosulfonyl, N,N-di(ethyl)aminosulfonyl, N-methylsulfonyl-N-methylamino, me- thyl-carbonylamino, trifluoromethyl, pentafluoroethyl, methoxyimino-methyl, methoxy- imino-ethyl, ethoxyimino-methyl, ethoxyimino-ethyl, methyl-aminocarbonyl, efhyl-amino- carbonyl, N,N-di(methyl)-aminocarbonyl, N,N-di(ethyl)-aminocarbonyl, methyl-aminothio- carbonyl, ethyl-aminothiocarbonyl, N,N-di(methyl)-aminothiocarbonyl, N,N-di(ethyl)-ami- nothiocarbonyl, methoxy-carbonylamino, methylamino-carbonyloxy, ethylamino-carbonyl- oxy, N,N-di(methyl)amino-carbonyloxy, N,N-di(ethyl)amino-carbonyloxy, methylamino- thiocarbonyloxy, N,N-di(methyl)amino-thiocarbonyloxy, methylamino-carbonylthio, ethyl- amino-carbonylthio, methylamino-thiocarbonylthio, ethylamino-tliiocarbonylthio, cyclohe- xyl, methoxy-methyl, ethoxy-methyl, methylthio-methyl, methylsulfinyl-methyl and methylsulfonyl-methyl; or cyclopropyl, cyclopentyl, cyclohexyl, each of which may be substituted by substituents selected from the group consisting of methyl, methylthio and methylthiomethyl.
R2 preferably represents hydrogen or d-C4-alkyl.
R2 particularly preferably represents hydrogen, methyl or ethyl. R2 very particularly preferably represents hydrogen or ethyl.
R3 preferably represents hydrogen or Cι-C4-alkyl. R3 particularly preferably represents hydrogen, methyl, ethyl, n- or iso-propyl. R3 very particularly preferably represents hydrogen, methyl, ethyl or iso-propyl. A1 preferably represents straight chain or branched chain d-C6-alkylene; CrC6-haloalkylene, C2-C6-alkenylene, C2-C6-haloalkenylene, C2-C6-alkynylene, C2-C6-haloalkynylene, Cι-C6-al- kylene-amino, CrC6-alkylene(Cι-C4-alkylamino), d-C6-alkyleneoxy or Cι-C6-alkylenethio.
A1 particularly preferably represents -CH2-, -(CH2)2-, -(CH2)3-, -CH(CH3)-, -OCH2-, -CH20.-, -0(CH2)2-, -(CH2)20-, -SCH2-, -CH2S-, -S(CH2)2- or -(CH2)2S-.
A1 very particularly preferably represents -CH2-, -(CH2)2-, -CH(CH3)-, -OCH2-, -0(CH2)2- or -CH2S-.
r preferably represents 0. r furthermore preferably represents 1.
A2 preferably represents straight chain or branched chain d-C6-alkylene, Cι-C6-haloalkylene, d-Q-alkenylene, C2-C6-haloalkenylene, d-Cβ-alkynylene or C2-C6-haloalkynylene. A2 particularly preferably represents -CH2-, -(CH2)2-, -(CH2)3-, -CH(CH3)-, -CH2-CH=CH-.
s preferably represents 0. s furthermore preferably represents 1.
preferably represents pyridinylene, pyridazinylene, pyrimidinylene, pyrazinylene, each of which is optionally mono- or poly-substituted by substituents selected from group W1 wherein said substituents may be identical or different, or further represents the below- mentioned groups;
Figure imgf000010_0001
Figure imgf000011_0001
Q35 Q36 Q37 Q38 Q39 Q40
Figure imgf000011_0002
Q41 Q42 Q43 Q44
Figure imgf000011_0003
Q45 Q46 Q47
Figure imgf000012_0001
Q48 Q49 Q50 Q51 Q52
Figure imgf000012_0003
Figure imgf000012_0002
Figure imgf000012_0004
Q66 Q67 Q68 Q69 Q70
(wherein the bond marked with * connects with A1 and the bond marked with # connects with A2, or the bond marked with # connects with A1 and the bond marked with * connects with A2) Q particularly preferably represents Q15, Q17, Q22, Q23, Q29, Q34, Q35, Q45, Q48, Q50, Q55, Q56, Q58, Q59, Q60, Q61, Q62, Q63, Q64, Q66 and Q69.
Q very particularly preferably represents Q15.
Q furthermore very particularly preferably represents Q 17.
Q furthermore very particularly preferably represents Q22.
Q furthermore very particularly preferably represents Q23. Q furthermore very particularly preferably represents Q29.
Q furthermore very particularly preferably represents Q34.
Q furthermore very particularly preferably represents Q35.
Q furthermore very particularly preferably represents Q45.
Q furthermore very particularly preferably represents Q48. Q furthermore very particularly preferably represents Q50. Q furthermore very particularly preferably represents Q55.
Q furthermore very particularly preferably represents Q56.
Q furthermore very particularly preferably represents Q58.
Q furthermore very particularly preferably represents Q59. Q furthermore very particularly preferably represents Q60.
Q furthermore very particularly preferably represents Q61.
Q furthermore very particularly preferably represents Q62.
Q furthermore very particularly preferably represents Q63.
Q furthermore very particularly preferably represents Q64. Q furthermore very particularly preferably represents 066.
Q furthermore very particularly preferably represents Q69.
W1 preferably represents halogen, Cι-C4-al yl, d-Q-alkoxy, Ci-Q-alkylthio, Cι-C - alkylsulfinyl, Cι-C4-alkylsulfonyl, Ci-Q-haloalkyl, Cι-C4-haloalkoxy, Cι-C4-haloalkylthio, Ci-Q-haloalkylsulfinyl, d-Q-haloalkylsulfonyl, C3-C6-cycloalkyl, d-C4-alkylthio-Cι-C - alkyl, Cι-C -alkylsulfinyl-Cι-C4-alkyl, Cι-C4-alkylsulfonyl-Cι-C -alkyl.
W1 particularly preferably represents methyl, ethyl, methoxy, methylthio, methylsulfinyl or methylsulfonyl.
W1 very particularly preferably represents methyl.
E preferably represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group is optionally mono- or poly-substituted by substituents selected from the group W2 wherein said substituents may be identical or different.
E particularly preferably represents phenyl, biphenyl, 3 -pyridyl, 2-thienyl, 2-furyl or 2-pyrrolyl, wherein said group is optionally mono- to terra-substituted by substituents selected from the group W2 wherein said substituents may be identical or different.
E very particularly preferably represents phenyl, biphenyl, 3 -pyridyl or 2-thienyl, wherein said group is optionally mono- to terra-substituted by substituents selected from the group W2 wherein said substituents may be identical or different.
W2 preferably represents halogen, nitro, d-C4-alkyl, C C4-alkoxy, Ci-Q-alkylthio, CrC4- alkylsulfinyl, d-C4-alkylsulfonyl, Cι-C4-haloalkyl, d-Q-haloalkoxy, d-C4-haloalkylthio, d-d-haloalkylsulfinyl, CrC4-haloalkylsulfonyl, C3-C6-cycloalkyl, d-C4-alkylthio-d-C4- alkyl, Ci-Q-alkylsulfinyl-Crd-alkyl or C1-C4-alkylsulfonyl-C1-C4-alkyl, or represents C3- C5-alkylene, C3-C5-haloalkylene, oxy-C2-C4-alkylene, oxy-C2-C4-haloal ylene, C2-C4-alky- leneoxy, C2-C4-haloalkyleneoxy, d-C3-alkylenedioxy or Cι-C3-haloalkylenedioxy, in case W2 are two adjacent substituents. W2 particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, n- or isopropyl, n-, sec-, iso- or tert-butyl, methoxy, ethoxy, n- or iso-propoxy, n-, sec-, iso- or tert- butoxy, trifluoromethoxy, difluoromethoxy, methylthio, ethylthio, n- or iso-propylthio, n-, sec-, iso- or tert-butylthio, trifluoromethyl, difluoromethyl, dichlorofluoromethyl, trichloro- methyl, trifluoromethoxy, difluoromethoxy, trifluoromethylthio, or represents -OCF20-,
-0(CF2)20-, -OCHFCF20-, -OCF2CHFO-, in case W2 are two adjacent substituents.
W2 very particularly preferably represents fluorine, chlorine, bromine, nitro, methyl, ethyl, isopropyl, methoxy, trifluoromethoxy, difluoromethoxy, methylthio, trifluoromethylthio, or represents -OCF20-, -0(CF2)20-, -OCHFCF20-, -OCF2CHFO-, in case W2 are two adjacent substituents.
W3 represents hydrogen or has the same definition as the aforementioned W1, W3 preferably represents hydrogen, methyl, trifluoromethyl or methylthio.
p represents 0, 1 or 2. p preferably represents 0. p furthermore preferably represents 1.
q represents 0, 1, 2 or 3. q preferably represents 0. q furthermore preferably represents 1.
Compounds of formula (I), in which r is 0 and s is 0 are preferred.
Compounds of formula (I), in which r is 1 and s is 1 are preferred. , Compounds of formula (I), in which r is 1 and s is 0 are particularly preferred.
Compounds of formula (I), in which R2 and R3 are both hydrogen are preferred.
Compounds of formula (I), in which n is 1 and X is located in 3-position are preferred.
Compounds of formula (I), in which X is iodine are preferred.
Compounds of formula (I), in which Y is methyl are preferred. Compounds of formula (I), in which A1 is -CH2- are preferred.
Compounds of formula (I), in which E is mono- to tetra-substituted phenyl, where the substituents are selected from the group W2, are preferred.
Compounds of formula (I), in which Q is Q66 are preferred.
The general or preferred radical definitions or illustrations listed above apply both to the end products and, correspondingly, to the starting materials and intermediates. These radical definitions can be combined with one another as desired, i.e. including combinations between the respective preferred ranges.
Preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being preferred.
Particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being particularly preferred.
Very particular preference according to the invention is given to the compounds of the formula (I) which contain a combination of the meanings listed above as being very particularly preferred.
In the radical definitions given above and below, carbon radicals, such as alkyl, are in each case straight-chain or branched as far as this is possible - including in combination with hetero atoms such as alkoxy.
The aforementioned preparation process (a) can be illustrated by the following reaction scheme in case, for example, that 3-(l,l-dimethyl-2- memylthioethylimino)-4-iodo-3H-isobenzofuran-l-one and l-(4-amino-3-methylbenzyl)- 4-(4-trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one are used as starting materials.
Figure imgf000015_0001
The aforementioned preparation process (b) can be illustrated by the following reaction scheme in case, for example, that 2-{2-methyl-4-[5-oxo-4-(4-trifluoromethylphenyl)-4,5-dihydrotetrazol-l-yl- methyl]phenyl}isoindole-l,3-dione and sec-butylamine are used as starting materials.
Figure imgf000016_0001
The aforementioned preparation process (c) can be illustrated by the following reaction scheme in case, for example, that N-(l-methyl-propyl)phthalamic acid and l-(4-amino-3-methylbenzyl)-4-(4- trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one are used as starting materials.
Figure imgf000016_0002
The aforementioned preparation process (d) can be illustrated by the following reaction scheme in case, for example, that l-[4-(3-oxo-3H-isobenzofuran-l-ylideneamino)-3-memyl-benzyl]-4-(4-tri- fluoromethyl-phenyl)-l,4-dihydrotetrazol-5-one and sec-butylamine are used as starting materials.
Figure imgf000016_0003
The aforementioned preparation process (e) can be illustrated by the following reaction scheme in case, for example, that N-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-yl- methyl]-phenyl}-phthalamic acid and sec-butylamine are used as starting materials.
Figure imgf000017_0001
The aforementioned preparation process (f) can be illustrated by the following reaction scheme in case, for example, that N2-(l,l-dimethyl-2-methylthioethyl)-3-iodo-N1-[2-methyl-4-(5-oxo-4-(4-tri- fluoromethylphenyl)-4,5-dihydro-tetrazol-l-ylmethyl)-phenyl]-phthalamide and m-chloroperbenzoic acid are used as starting materials.
Figure imgf000017_0002
The compounds of the formula (II), starting material in the above-mentioned preparation process (a), are per se known compounds and can be easily prepared according to the process described in, for example, EP-A 0 919 542, EP-A 1 006 107.
As specific examples of the compounds of the formula (II) used as starting material in the preparation process (a) there can be mentioned the following: 3 -isopropylimino-3H-isobenzofuran- 1 -one, 4-fluoro-3 -isopropylimino-3H-isobenzofuran- 1 -one, 4-chloro-3-isopropylimmo-3H-isobeιιzofuran-l-one, 4-bromo-3-isopropylimmo-3H-isobeιιzofuran-l-one, 4-iodo-3 -isopropylimino-3H-isobenzofuran- 1 -one, 3-isopropylimino-4-nitro-3H-isobeιιzofuran-l-one, 3-isopropylimino-5-nitro-3H-isobenzofuran-l-one, 3-(l-methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-l-one, 4-fluoro-3 -(1 -methyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran- 1 -one, 4-chloro-3-(l-mefrιyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran-l-one, 4-bromo-3 -(1 -methyl-2-methylsulfanyl-etfrylim o)-3H-isobenzofuran- 1 -one, 4-iodo-3 -(1 -methyl-2-methylsulfanyl-ethylimino)-3H-isobeιιzofuran- 1 -one, 3 -( 1 -methyl-2-methylsulfanyl-ethylimino)-4-nitro-3H-isobenzofuran- 1 -one, 3-(l , 1 -dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran- 1 -one, 3-(l,l-dimethyl-2-methylsulfanyl-ethylimmo)-4-fluoro-3H-isobenzofuran-l-one, 4-chloro-3-(l,l-dimethyl-2-memylsulfanyl-ethylimmo)-3H-isobenzofuran-l-one, 4-bromo-3 -(1,1 -dimethyl-2-memylsulfanyl-ethylimino)-3H-isobenzofuran- 1 -one, 3-(l,l-dimethyl-2-methylsulfanyl-ethylimmo)-4-iodo-3H-isobenzofuran-l-one, 3 -(1 , 1 -dimethyl-2-memylsulfanyl-ethylimino)-4-mfro-3H-isobenzo_f_uran- 1 -one, 3 -( 1 , 1 -dimethyl-2-methylsulfanyl-ethylimino)-4-methyl-3H-isobenzofuran- 1 -one, 3-( 1 , 1 -dimethyl-2-methylsulfanyl-ethylimino)-5 -methyl-3H-isobenzofuran- 1 -one, 4,7-dichloro-3-( 1 , 1 -dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran- 1 -one, 5,6-dichloro-3 -( 1 , 1 -dimethyl-2-methylsulfanyl-ethylimino)-3H-isobenzofuran- 1 -one, 4,5,6,7-tefrachloro-3-(l,l-dimethyl-2-methylsulfanyl-ethylimmo)-3H-isoberιzo___uran- 1-one, 3 -isopropylimino- 1 -oxo- 1 ,3 -dihydro-isobenzofuran-4-yl methanesulfonate, 3-(l-methyl-2-methylsulfanyl-ethylimmo-l-oxo-l,3-dihydro-isobenzofuran-4-yl methanesulfonate, 3-( 1 , 1 -dimethyl-2-methylsulfanyl-ethylimino- 1 -oxo- 1 ,3 -dihydro-isobenzofuran-4-yl methanesulfonate.
The compounds of the formula (EI), starting material in the above-mentioned preparation process (a), include novel compounds not mentioned in the existing literature as a part.
Their corresponding anilines can be obtained, for example, by a catalytic hydrogen reduction, a well- known process in the field of organic chemistry, by reducing compounds of the formula
Figure imgf000018_0001
wherein Y, m, A1, r, Q, A2, s and E have the same definitions as aforementioned with hydrogen in the presence of a catalytic reduction catalyst, for example, palladium carbon, Raney nickel, platinum oxide.
Compounds of the formula (IH), in which R3 corresponds alkyl, can be obtained by formylating the amino group of the anilines, further alkylating and then de-formylating. Moreover, compounds of the formula (IE), in which R3 corresponds alkyl, can also be obtained by preparing a Schiff base complex by a reaction of the anilines obtained by the reduction of compounds of the formula (IX) and a ketone or an aldehyde and then by catalytically reducing it.
The compounds of the above-mentioned formula (IX) are, as will be described later in detail, novel compounds.
As specific examples of the compounds of the formula (III) there can be mentioned, for example, 1 -(4-amino-3-methyl ■benzyl)- lH-pyrazole, l-(4-amino-3 -methyl ■benzyl)-3-methyl-lH-pyrazole, 1 -(4-amino-3 -methyl ■benzyl)-4-mefhyl- lH-pyrazole, 1 -(4-amino-3 -methyl ■benzyl)-4,5-dichloro-lH-imidazole, 1 -(4-amino-3-methyl ■benzyl)-lH-l,2,3-triazole, 1 -(4-amino-3 -methyl ■benzyl)-lH-l,2,4-triazole, l-(4-amino-3 -methyl ■benzyl)- lH-tetrazole, 1 -(4-amino-3 -methyl ■benzyl)-5-methyl-lH-tetrazole, 1 -(4-amino-3 -methyl •benzyl)-5-(2-chloro-phenyl)-lH-tetrazole, 1 -(4-amino-3-methyL •benzyl)-5-(3-trifluoromethyl-phenyl)-lH-tetrazole3 1 -(4-amino-3-methyl- ■benzyl)-5- 4-trifluoromethyl-phenyl)-lH-tetrazole, l-(4-amino-3-methyI ■benzyl)-5- 3,5 -bis-trifluoromethyl-phenyl)- 1 H-tetrazole, 1 -(4-amino-3 -methyl -benzyl)-5-(3-trifluoromethoxy-phenyl)-lH-tetrazole3 1 -(4-amino-3 -methyl benzyl)-3 4-trifluoromethyl-phenyl)-imidazolydin-2-one, 1 -(4-amino-3 -methyl benzyl)-3-ι 4-trifluoromethyl-phenyl)- 1 ,3 -dihydro-imidazol-2-one, 1 -(4-amino-3 -methyl •benzyl)-3 4-trifluoromethyl-phenyl)-imidazolydin-2,4-dione, l-(4-amino-3 -methyl ■benzyl)-3-ι 4-trifluoromethyl-phenyl)-imidazolydin-2,4,5-trione, 1 -(4-amino-3 -methyl ■benzyl)-3 4-triflUoromethyl-phenyl)- lH-pyrazole, . 4-(4-amino-3 -methyl •benzyl)-2-ι 2-fluoro-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-amino-3 -methyl ■benzyl)-2-ι 2-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl •benzyl)-2-ι 2-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl ■benzyl)-2-ι 3-fluoro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl ■benzyl)-2 3-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl ■benzyl)-2-ι 3-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(4-fluoro-phenyl)-4-(4-amino-3 -methyl-benzyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-ammo-3-methyl-benzyl)-2-(4-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-me1lιyl-benzyl)-2-(4-trifluoromemyl-phenyl)-2,4-dmydro-l,2,4-1riazol-3-one, 4-(4-amino-3-metIιyl-ben2_yl)-2-(3,4-bis-1rifl 4-(4-amino-3-methyl-benzyl)-2-(3,5-bis-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-ammo-3-methyl-berιzyl)-5-trifluorome1^ triazol-3-one,
2-(4-amino-3-methyl-berιzyl)-4-(2-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(4-amino-3-me1lιyl-ben2_yl)-4-(4-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(4-amino-3-methyl-benzyl)-5-methyl-4-(4-trifluoromethyi-phenyl)-2,4-d ydro-l,2,4-triazol-3-one, 2-(4-amino-3-methyl-ben2yl)-4-(2-chloro-phenyl)-5-me1iιylsulfanyl-2,4-dihydro-l,2,4-triazol-3-one, 2-(4-ammo-3-methyl-benzyl)-5-methylsulfanyl-4-(4-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4- triazol-3-one, 1 -(4-amino-3 -methyl-benzyl)-4-methyl- 1 ,4-dihydro-tetrazol-5 -one, 1 -(4-amino-3 -methyl-benzyl)-4-ethyl- 1 ,4-dihydro-tetrazol-5 -one, l-(4-ammo-3-methyl-benzyl)-4-propyl-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-beιιzyl)-4-isobutyl-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-memyl-benzyl)-4-(2,2,2-trifluoro-ethyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4,4,4-trifluoro-butyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,3,3-trichloro-2-methyl-propyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-cyclopropyl-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-cyclohexyl- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-phenyl-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(2-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -(4-amino-benzyl)-4-(2-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -[ 1 -(4-amino-3 -methyl-phenyl)-ethyl] -4-(2-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2-mefhyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-methoxy-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(2-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(2-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(3 -fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3-methyl-benzyl)-4-(3-chloro-phenyl)-l,4-dihydro-tetτazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3-methyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-benzyl)-4-(3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3-difluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(4-fluoro-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(4-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(4-bromo-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, 1 -(4-amino-3-methyl-benzyl)-4-(4-methyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-isopropyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-ben2yl)-4-(4-1rifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-2-chloro-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, _ l-(4-amino-3-chloro-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(4-difluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3-methyl-berιzyl)-4-(4-1rifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-trifluoromethylsulfanyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(4 ' -trifluoromethyl-biphenyl-4-yl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3 5'-bis-trifluoromethyl-biphenyl-4-yl)-l,4-dihyάro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-bromo-2-fluoro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-fluoro-3-frifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-metiιyl-benyyl)-4-(3-bromo-4-trifluoromethoxy-phenyl)-l54-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3-chloro-4-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-fluoro-3-trifluoromemyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-fluoro-5-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-chloro-3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one3 l-(4-ammo-3-methyl-benzyl)-4-(3,4-dichloro-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(3 ,4-bis-trifluoromethyl-phenyl)- 1 ,4-dihydro -tetrazol-5 -one, l-(4-amino-3-methyl-benzyl)-4-(3-fluoro-5-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-dichloro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3,5-dimethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-2-chloro-beιτzyl)-4-(3,5-bis-tτifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-chloro-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4~amino-2-methoxy-benzyl)-4-(3 ,5 -bis-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methoxy-benzyl)-4-(3,5-bis-1rifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3,5-dimethyl-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-[l-(4-am o-3-memyl-phenyl)-e yl]-4-(3,5-bis-1rifluoromemyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(3 -chloro-2-methoxy-5 -methyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3-methyl-benzyl)-4-(2,2-difluoro-berιzo[l,3]dioxol-5-yl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-(2,2,3 ,3 -tetrafluoro-2,3 -dihydro-benzo[ 1 ,4] dioxin-6-yl)- 1 ,4-dihydro- tetrazol-5-one, l-(4-ammo-3-methyl-beri2yl)-4-(2,2,3-trifluoro-2,3-dihydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro- tetrazol-5-one, l-(4-ammo-3-methyl-berιzyl)-4-(2,3,3-trifluoro-2,3-dihydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro- tetrazol-5-one, l-(4-amino-3-methyl-berιzyl)-4-(2,2,3,3,7-pentafluoro-2,3-dihy(_lro-benzo[l,4]dioxin-6-yl)-l,4- dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-dichloro-2,6-diethyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-benzyl- 1 ,4-dihydro-tetrazol-5-one, - l-(4-amino-3-methyl-benzyl)-4-(4-fluoro-benzyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4-(4-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, 1 -(4-amino-3 -methyl-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3-methyl-benzyl)-4-[l-(2-fluoro-phenyl)ethyl]-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4-[l -(2-chloro-phenyl)ethyl]- 1 ,4-dihydro-tetrazol-5-one, l-(4-am o-3-methyl-ben_zyl)-4-[l-(2-trifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3-methyl-benzyl)-4- 1 -[ l-(3-fluoro-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-[l-(3-chloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-[l-(3-trifluoromethyl-phenyl)-etiiyl]-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-[l-(4-fluoro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-[l-(4-chloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-beri2yl)-4-[l-(4-frifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-[l-(2,4-difluoro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-[l-(2,4-dichloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, 1 -(4-amino-3 -methyl-benzyl)-4- [ 1 -(3 ,4-difluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5-one.
The compounds of the formula (TV), starting materials in the above-mentioned preparation process (b), are novel ones and can be easily obtained according to the process described in JP-A 61- 246161, for example, by reacting a compound represented by the formula'
Figure imgf000022_0001
wherein X and n have the same definition as aforementioned, with the compounds of the aforementioned formula (IE)
Figure imgf000023_0001
in which R represents a hydrogen atom and Y, m, A1, r, Q, A2, s and E have the same definitions as aforementioned.
The reaction can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic arid aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, di- chlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); esters, for example, ethyl acetate, amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA); acids, for example, acetic acid.
The reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally room temperature to about 200°C, preferably room temperature to 150°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the reaction, the aimed compounds can be obtained, for example, by reacting equimolar amount or a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (X) in a diluent, for example, acetic acid.
Many of the compounds of the above-mentioned formula (X) are known (available on the market) compounds and as their specific examples there can be mentioned, phthalic anhydride,
3-fluorophthalic anhydride, 3-chlorophthalic anhydride,
3-bromophthalic anhydride,
3-iodophthalic anhydride,
3-methylphthalic anhydride,
3-nitrophthalic anhydride, 3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4,5,6-tetrafluorophthalic anhydride, 3,4,5,6-tetrachlorophthalic anhydride, 3-methanesulfonyloxyphthalic anhydride.
Among the above-mentioned examples, 3-methanesulfonyloxyphthalic anhydride can be easily obtained from 3-hydroxvphthalic anhydride and methanesulfonyl chloride according to the process described in Tetrahedron Lett., 1988, 29, 5595-5598.
Similarly the compounds of the aforementioned formula (EE), in which R3 represents a hydrogen atom, starting materials for the compounds of the formula (IV), can be easily obtained, as described in the aforementioned preparation process (a), by a catalytic hydrogen reduction of the compounds represented by the aforementioned formula (IX) having a nitro group in place of an amino group, corresponding to the amino group (R3 = H) in the formula (IE).
The catalytic hydrogen reduction can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, tetrahydrofuran (THF); alcohols, for example, methanol, etha- nol, isopropanol, butanol, ethylene glycol, and as catalytic reduction catalyst there can be mentioned palladium carbon, Raney nickel, platinum oxide.
It can be conducted at the temperatures generally between about 0 to about 100°C, preferably room temperature to about 80°C.
Said reaction can be operated under normal pressure to elevated pressure.
For example, an objective compound of the formula (IE), in wliich R3 represents hydrogen, can be obtained by hydrogenation of 1 mole of the nitro compound in a diluent, for example, ethanol in the presence ofO.1-10 % (w/w) palladium carbon.
Moreover, the compounds of the formula (IE), in wliich R3 represents hydrogen, can also be obtained by a reaction with a metal etc. instead of a catalytic hydrogen reduction.
As a process using a metal etc. there can be mentioned, for example, a process of treating iron powder in acetic acid, a process of reacting zinc dust under the neutral condition (Organic Syntheses Collective Vol. II, p. 447), a process of reacting stannic chloride under an acidic condition (Organic Syntheses Collective Vol. E, p. 254), a process of reacting titanium trichloride under the neutral condition, etc.
As specific examples of the compounds of the formula (IE), in which R3 represents a hydrogen atom, there can be mentioned, for example, l-(4-amino-3-methyl-benzyl)-lH-pyrazole,
1 -(4-amino-3 -methyl-benzyl)-3 -methyl- lH-pyrazole, l-(4-amino-3-methyl-benzyl)-4-methyl-lH-pyrazole,
1 -(4-amino-3-methyl-benzyl)-4,5-dichloro- lH-imidazole, l-(4-amino-3-methyl-benzyl)-lH-l,2,3-triazole, 1 -(4-amino-3-methyl-benzyl)- IH- 1 ,2,4-triazole, l-(4-amino-3-methyl-benzyl)-lH-tetrazole, 1 -(4-amino-3-methyl-benzyl)-5-methyl- lH-tetrazole, 1 -(4-amino-3 -methyl-benzyl)-5-(2-chloro-phenyl)- 1 H-tetrazole, l-(4-amino-3-methyl-benzyl)-5-(3-trifluoromethyl-phenyl)-lH-tetrazole, l-(4-amino-3-methyl-benzyl)-5-(4-trifluoromethyl-phenyl)-lH-tetrazole, l-(4-amino-3-methyl-benzyl)-5-(3,5-bis-trifluoromethyl-phenyl)-lH-tetrazole, l-(4-amino-3-methyl-benzyl)-5-(3-trifluoromethoxy-phenyl)-lH-tetrazole, l-(4-aιnino-3-me11ιyl-benzyl)-3-(4-trifluoromethyl-phenyl)-imidazolydin-2-one, l-(4-amino-3-methyl-benzyl)-3-(4-trifluoromethyl-phenyl)-l,3-dihydro-imidazol-2- one, l-(4-amino-3-methyl-benzyl)-3-(4-trifluoromethyl-phenyl)-imidazolydin-2,4-dione, l-(4-ammo-3-meti yl-benzyl)-3-(4-1rifluorometiιyl-phenyl)-imidazolydin-2,4,5-trione3 l-(4-amiιιo-3-methyl-benzyl)-3-(4-trifluoromethyl-phenyl)-lH-pyrazole, 4-(4-amino-3 -methyl-benzyl)-2-(2-fluoro-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-amino-3 -methyl-benzyl)-2-(2-chloro-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one,
4-(4-amtno-3 -methyl-benzyl)-2-(2-trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-amino-3 -methyl-benzyl)-2-(3 -fluoro-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-ammo-3-methyl-benzyl)-2-(3-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3 -methyl-benzyl)-2-(3 -trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 2-(4-fluoro-phenyl)-4-(4-amino-3-methyl-beιιzyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl-benzyl)-2-(4-chloro-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3 -methyl-benzyl)-2-(4-trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 4-(4-ammo-3-methyl-benzyl)-2-(3,4-bis-trifluoromethyl-phenyl)-2,4-dmydro-l,2,4-triazol-3-one, 4-(4-amino-3-methyl-benzyl)-2-(3,5-bis-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(4-amino-3 -methyl-benzyl)-5 -trifluoromethyl-2-(4-trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4- triazol-3-one, 2-(4-amino-3 -methyl-benzyl)-4-(2-chloro-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 2-(4-amino-3-memyl-benzyl)-4-(4-trifluoromethyl-ρhenyl)-2,4-dihy(iro-l,2,4-1ri
2-(4-ammo-3-memyl-benzyl)-5-methyl-4-(4-trifluoromethyl-phenyl)-2,4-dmydro-l,2,4-triazol-3-one,
2-(4-amino-3 -methyl-benzyl)-4-(2-chloro-phenyl)-5 -methylsulfanyl-2,4-dihydro- 1 ,2,4-triazol-3 -one,
2-(4-ammo-3-me yl-ben2yl)-5-methιylsulfanyl-4-(4-trifluoromethyl-phenyi)-2,4-dihydro-l,2,^ triazol-3-one, l-(4-amino-3-methyl-benzyl)-4-methyl-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-ethyl- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-amino-3 -methyl-benzyl)-4-propyl- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3-methyl-benzyl)-4-isobutyl-l,4-dihydiO-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2,2,2-trifluoro-ethyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-ammo-3-memyl-beιιzyl)-4-(4,4,4-trifluoro-butyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-beιιzyl)-4-(3,3,3-trichloro-2-methyl-propyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-cyclopropyl- 1 ,4-dihydro-tetrazol-5-one, '
1 -(4-amino-3 -methyl-benzyl)-4-cyclohexyl- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-amino-3 -methyl-benzyl)-4-phenyl- 1 ,4-dihydro-tetrazol-5 -one, _, l-(4-amino-3-methyl-benzyl)-4-(2-fluoro-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-benzyl)-4-(2-cl loro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-aminp-3-methyl-benzyl)-4-(2-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-[l-(4-amino-3-methyl-phenyl)-ethyl]-4-(2-chloro-phenyl)-l,4-dihydro-tetrazol-5- one, l-(4-ammo-3-methyl-benzyl)-4-(2-methyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-methoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-trifluorometh3'l-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5- one,
1 -(4-amino-3-methyl-benzyl)-4-(3-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(3-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(3-methyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-ammo-benzyl)-4-(3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(3 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-amino-3 -methyl-benzyl)-4-(3 -difluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 - one,
1 -(4-amino-3 -methyl-benzyl)-4-(3 -trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 - one,
1 -(4-amino-3-methyl-benzyl)-4-(4-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(4-cMoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(4-bromo-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-methyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3 -methyl-benzyl)-4-(4-isopropyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-benzyl)-4-(4-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-2-chloro-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-c oro-benzyl)-4-(4-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(4-difluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(4-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5- one,
1 -(4-amino-3-methyl-benzyl)-4-(4-trifluoromethylsulfanyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(4'-trifluoromethyl-biphenyl-4-yl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3 5'-bis-trifluoromethyl-biphenyl-4-yl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(4-bromo-2-fluoro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-fluoro-3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(3 -bromo-4-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-amino-3-methyl-benzyl)-4-(3 -chloro-4-trifluoromethoxy-phenyl)- 1 ,4-dihydro- tetrazol-5 -one, l-(4-ammo-3-methyl-berιzyl)-4-(4-fluoro-3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2-fluoro-5-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(4-chloro-3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,4-dichloro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amιino-3-methyl-ben_zyl)-4-(3,4-bis-frifluoromethyl-phenyl)-l,4-dmydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3-fluoro-5-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-dichloro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3,5-dimethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-2-cUoro-ber_zyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-ammo-3-chloro-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-bis-1rifluoromethyl-phen3 )-l,4-dihydro-tetrazol-5-one, l-(4-amino-2-methoxy-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methoxy-benzyl)-4-(3 ,5 -bis-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino-3,5-dimethyl-benzyl)-4-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -[ 1 -(4-amino-3 -methyl-phenyl)-ethyl]-4-(3 ,5-bis-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3-cWoro-2-methoxy-5-methyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2,2-difluoro-benzo[l,3]dioxol-5-yl)-l,4-dihydro-tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2,2,3,3-tetrafluoro-2,3-dihydro-benzo[l ,4]dioxin-6-yl)- 1 ,4-dihydro- tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2,2,3-trifluoro-2,3-dihydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro- tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(2,3,3-trifluoro-2,3-dihydro-benzo[l ,4]dioxin-6-yl)- 1 ,4-dihydro- tetrazol-5-one,
1 -(4-amino-3-methyl-benzyl)-4-(2,2,3 ,3 ,7-pentafluoro-2,3-dihydro-benzo[ 1 ,4]dioxin-6-yl)- 1 ,4- dihydro-tetrazol-5-one, l-(4-ammo-3-methyl-benzyl)-4-(3,5-dichloro-2,6-diethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino- 3 -methyl-benzyl)' -4-benzyl- 1 ,4-dihydrortetrazol-5 -one, l-(4-amino- 3 -methyl-benzyl)' ■4-(4-fluoro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino- 3-methyl-benzyl} ■4-(4-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino- ■3-methyl-benzyl} •4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino- ■3-methyl-benzyl)' ■4-[l-(2-fluoro-phenyl)ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-amino- ■3-methyl-benzyl)' ■4-[l -(2-chloro-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino- ■3 -methyl-benzyl)' ■4-[ 1 -(2-trifluoromethyl-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5- ■one, l-(4-amino- •3 -methyl-benzyl)' •4- 1 - [ 1 -(3 -fluoro-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5 - one, l-(4-amino- 3-methyl-benzyl} •4-[l-(3-chloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(4-amino- 3-methyl-benzyl)' •4-[ 1 -(3 -trifluoromethyl-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5 • one, l-(4-amino- 3-methyl-benzyl)' ■4- [ 1 -(4-fluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino- 3-methyl-benzyl) ■4-[ 1 -(4-chloro-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5-one, l-(4-amino- ■3-methyl-benzyl)' •4- [ 1 -(4-trifluoromethyl-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5- one, l-(4-amino- •3-methyl-benzyl)1 ■4-[ 1 -(2,4-difluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5 -one, l-(4-amino- ■3-methyl-benzyl) ■4-[ 1 -(2,4-dichloro-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5-one, l-(4-aminb- ■3-methyl-benzyl)' •4-[l-(3,4-difluoro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one.
The compounds of the above-mentioned formula (IX) are novel compounds and can be obtained, for example, by reacting compounds of the formula
Figure imgf000028_0001
wherein Y, m, A1 and r have the same definition as aforementioned and M represents chloro, bromo or methylsulfonyloxy, and compounds of the formula
H-Q -H4: (XII) wherein Q, A , s and E have the same definition as aforementioned.
The compounds of the above-mentioned formula (XI) are compounds well known in the field of organic chemistry (cf. Chem. Ahstr. 1963, 58, 3444e; Bull. Soc. Chim. Fr. 1934, 539-545; J Chem. Res. Miniprint, 1987, 8, 2133-2139; J. Chem. Soc. B 1967, 1154-1158; J. Chem. Soc. 1961, 221-222; J. Amer. Chem. Soc. 1989, 111, 5880-5886). Specifically there can be mentioned as examples 4-nitrobenzyl chloride, (available on the market) 4-bromobenzyl chloride, (available on the market) 2-chloro-4-nitrobenzyl chloride, 2-methyl-4-nitrobenzyl chloride, 2-methoxy-4-nitrobenzyl chloride,
3-chloro-4-nitrobenzyl chloride,
3-methyl-4-nitrobenzyl chloride,
3-methoxy-4-nitrobenzyl chloride, 4-nitrobenzyl methanesulfonate,
2-chloro-4-nitrobenzyl methanesulfonate,
2-methyl-4-nitrobenzyl methanesulfonate,
2-methoxy-4-nitrobenzyl methanesulfonate,
3 -chloro-4-nitrobenzyl methanesulfonate, 3-methyl-4-nitrobenzyl methanesulfonate,
3-methoxy-4-nitrobenzyl methanesulfonate,
1 -(3-chloro-4-nitro-phenyl)-ethyl methanesulfonate,
1 -(3 -methyl-4-nitro-phenyl)-ethyl methanesulfonate, l-(3-methoxy-4-nitro-phenyl)-ethyl methanesulfonate.
The nitro-substituted benzoic acids and their esters, starting materials for the compounds of the formula (XT) are known from the literature (cf., for example, Chem. Ber. 1919, 52, 1083; Bull. Soc.
Chim. Fr. 1962, 2255-2261; Tetrahedron 1985, 115-118; Chem. Pharm. Bull, 1993, 41, 894-906).
The compounds of the above-mentioned formula (XE) include known compounds and as their specific examples there can be mentioned,
IH-pyrrole,
3-methyl-lH-pyrrole,
2,5-dimethyl-lH-pyrrole, lH-pyrazole,
3-methyl-lH-pyrazole,
4-methyl- lH-pyrazole,
4-chloro- lH-pyrazole,
3 ,5 -dimethyl- lH-pyrazole, lH-imidazole,
4-methyl- lH-imidazole,
4,5-dichloro-lH-imidazole, lH-[l,2,3]-triazole, lH-[l,2,4]-triazole, lH-tetrazole,
5-metyl- lH-tetrazole,
5-phenyl-lH-tetrazole, 5-(2-chloro-phenyl)-lH-tetrazole,
5-(4-chloro-phenyl)- lH-tetrazole,
5-(3-τrifluoromethyl-phenyl)-lH-tetrazole,
5-(4-trifluoromethyl-phenyl)-lH-tetrazole, 5-(3 ,5-bis-trifluoromethyl-phenyl)- lH-tetrazole,
5-(3-trifluoromethoxy-phenyl)-lH-tetrazole, succinimide, l-(4-trifluoromethyl-phenyl)-imidazolidin-2-one l-(4-trifluoromethyl-phenyl)-l,3-dihydro-imidazol-2-one, 3-(4-trifluoromethyl-phenyl)-imidazolidin-2,4-dione
2-(2-chloro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-o e,
2-(2-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
2-(3-fluoro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
2-(3-chloro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one, 2-(3 -trifluoromethyl-phenyl)-2,4-dihydro-[ 1 ,2,4]triazol-3 -one,
2-(4-fluoro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
2-(4-chloro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
2-(4-trifluoromethyl-phenyl)-2,4-dihydro- [ 1 ,2,4] triazol-3 -one,
2-(3,4-bis-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one, 2-(3,5-bis-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
5-trifluoromethyl-2-(4-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
4-(2-chloro-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
4-(4-trifluoromethyl-phenyl)-2,4-dihydro- [ 1 ,2,4]triazol-3 -one,
5-methyl-4-(4-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one, 4-(2-chloro-phenyl)-5-methylsulfanyl-2,4-dihydro-[l,2,4]triazol-3-one,
5-me1hylsulfanyl-4-(4-trifluoromethyl-phenyl)-2,4-dihydro-[l,2,4]triazol-3-one,
1 -methyl- 1 ,4-dihydiO-tetrazol-5-one,
1 -ethyl- 1 ,4-dihydro-tetrazol-5-one, l-propyl-l,4-dihydro-tetrazol-5-one, 1 -isobutyl- 1 ,4-dihydro-tetrazol-5-one, l-(2,2,2-trifluoro-ethyl)-l,4-dihydro-tetrazol-5-one,
1 -(4,4,4-trifluoro-butyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ,3 ,3 -trichloro-2-methyl-propyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -cyclopropyl- 1 ,4-dihydro-tetrazol-5-one, 1 -cyclohexyl- 1 ,4-dihydro-tetrazol-5-one,
1 -phenyl- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -(2-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(2-methyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(2-methoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-fluoro-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-chloro-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 -methyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 -difluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-chloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-bromo-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-methyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-isopropyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-difluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-trifluoromethylsulfanyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4 ' -trifluoromethyl-biphenyl-4-yl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ' ,5 '-bis-trifluoromethyl-biphenyl-4-yl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-bromo-2-fluoro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-fluoro-3 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 -bromo-4-trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-chloro-4-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(4-fluoro-3-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-fluoro-5 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-chloro-3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 ,4-dichloro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 ,4-dichloro-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3,4-bis-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 -fluoro-5 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3 ,5-dichloro-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ,5-dimethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ,5 -bis-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(3-chloro-2-methoxy-5-methyl-phenyl)-l,4-dihydro-tetrazol-5-one, 1 -(2,2-difluorθτbenzo [ 1 ,3]dioxol-5-yl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(2,2,3 ,3 -tetrafluoro-2,3 -dihydro-benzo[ 1 ,4] dioxin-6-yl)- 1 ,4-dihydro-tetrazol-5-one, l-(2,2,3-1rifluoro-2,3-ώhydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro-tetrazol-5-one, l-(2,3,3-trifluoro-2,3-ώhydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro-tetrazol-5-one, 1 -(2,2,3,3 ,7-pentafluoro-2,3-dihydro-benzo[ 1 ,4]dioxin-6-yl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ,5 -dichloro-2,6-diethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -thiophen-2-yl- 1 ,4-dihydro-tetrazol-5 -one,
1 -benzyl- 1 ,4-dihydro-tetrazol-5-one, l-(4-fluoro-benzyl)-l,4-dihydro-tetrazol-5-one, 1 -(4-chloro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-trifluoromethyl-benzyl)- 1 ,4-dihydro-tetrazol-5-one,
1 - [ 1 -(2-fluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5-one,
1 -[ 1 -(2-chloro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5-one,
1 - [ 1 -(2-trifluoromethyl-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5 -one, 1 -[ 1 -(3-fluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5 -one, l-[l-(3-chloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-[ 1 -(3-trifluoromethyl-phenyl)-ethyl]- 1 ,4-dihydro-tetrazol-5-one,
1 - [ 1 -(4-fluoro-phenyl)-ethyl] - 1 ,4-dihydro-tetrazol-5-one, l-[l-(4-chloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-[l-(4-trifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-[l-(2,4-difluoro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-[l-(2,4-dichloro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one,
1 - [ 1 -(3 ,4-difluoro-phenyl)-erhyl]- 1 ,4-dihydro-tetrazol-5 -one.
Furthermore, there can be provided from the processes described in the literature, for example, l-(4- trifluoromethylphenyl)imidazolidin-2,4,5-trione from 4-trifluoromethylphenylurea (cf. J. Chem. Soc. Perkin Trans. 2, 1977, 934, according to the process described in Chem. Ber. 1907, 40, 3131), there can be provided 3-(4-trifluoromethylphenyl)-lH-pyrazole from 4-trifluoromethylacetophenone, available on the market (cf. Synthesis 2001, 55-62), and further there can be provided 2-phenyl-2,4- dihydro-l,2,4-triazol-3-one and 2-(2-fluorophenyl)-2,4-dihydro-l,2,4-triazol-3-one (cf. J. Prakt. Chem. 1907, 75, 131), and furthermore, there can be provided l-mono-(or di-)(trifluoromethyl)- phenyl-l,4-dihydro-tetrazol-5-one by a reaction of mono-(or di-)(trifluoromethyl)phenyl isocyanate and known trimethylsilyl azide (cf. EP-A 0 146 279, Chem. Pharm. Bull, 1996, 44, 314-327).
The process to prepare the compounds of the above-mentioned formula (IX) can be conducted in an adequate diluent. As examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (ME3K); nitriles, for example, acetonitrile, propionitrile, acrylonitrile; esters, for example, ethyl acetate, amyl acetate; acid amides, for example, dimethylformamide (DMF), dimethylacetamide (DMA), N- methylpyrrolidone, l,3-dimethyl-2-imidazolidinone, hexamethyl phosphoric triamide (HMPA).
The reaction can be conducted in the presence of an acid binder and as such an acid binder there can be mentioned, as inorganic base, hydrides, hydroxides, carbonates, bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydride, lithium hydride, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide; inorganic alkali metal amides, for example, lithium amide, sodium amide, potassium amide; as organic base, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-teframethylethylenediamine (TMEDA), N,N-dimethylaml Le, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction can also be conducted by a process using a phase-transfer catalyst. As examples of the diluent used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM).
As examples of phase-transfer catalyst there can be mentioned, quaternary ions, for example, tetramethylammonium bromide, tetrapropylammonium bromide, tetrabutylammonium bromide, tetrabu- tylammonium bissulfate, tetrabutylammonium iodide, trioctylmethylammonium chloride, benzyl- triethylammonium bromide, butylpyridinium bromide, heptylpyridinium bromide, benzyltri- ethylammonium chloride; crown ethers, for example, dibenzo-18-crown-6, dicyclohexyl-18-crown-6, 18-crown-6; cryptands, for example, [2.2.2]-cryptate, [2.1.1]-cryptate, [2.2.1]-cryptate, [2.2.B]- cryptate, [20202S]-cryptate, [3.2.2]-cryptate.
The reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about 0°C to about 200°C, preferably room temperature to about 150°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure. In conducting the reaction, the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of a compound of the formula (XE) to 1 mole of the compounds of the formula (XT) in a diluent, for example, DMF, in the presence of potassium carbonate.
As specific examples of the compounds of the aforementioned formula (IX), obtained according to the above-mentioned process, there can be mentioned, for example, l-(4-nitro-benzyl)-lH-pyrrole, l-(3-methyl-4-nitro-benzyl)-lH-pyrazole, 3 -methyl- 1 -(3 -methyl-4-nitro-benzyl)- 1 H-pyrazole, 4-methyl- 1 -(3 -methyl-4-nitro-benzyl)- lH-pyrazole,
4,5 -dichloro- 1 -(3 -methyl-4-nitro-benzyl)- 1 H-imidazole, 1 -(3-methyl-4-nitro-benzyl)- IH- 1 ,2,3-triazole, 1 -(3-methyl-4-nitro-benzyl)- IH- 1 ,2,4-triazole, l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, 5-methyl- 1 -(3-methyl-4-nitro-benzyl)- lH-tetrazole,
5-(2-chloro-phenyl)-l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, 5-(3-trifluoromethyl-phenyl)-l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, 5-(4-trifluoromethyl-phenyl)-l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, 5-(3,5-bis-trifluoromethyl-phenyl)-l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, 5-(3-trifluoromethoxy-phenyl)-l-(3-methyl-4-nitro-benzyl)-lH-tetrazole, l-(3-methyl-4-nitro-benzyl)-3-(4-trifluoromethyl-phenyl)-imidazolidin-2-one, l-(3-methyl-4-nitro-benzyl)-3-(4-trifluoromethyl-phenyl)-l53-dihydro-imidazol-2-one, 1 -(3 -mβthyl-4-nitro-benzyl)-3 -(4-trifluoiOmethyl-phenyl)-imidazolidin-2,4-dione, l-(3-memyl-4-nitio-benzyl)-3-(4-trifluoromethyl-phenyl)-imidazolidin-2,4,5-trione, l-(3-methyl-4-nitro-benzyl)-3-(4-trifluoromethyl-phenyl)-lH-pyrazole,
2-(2-fluoro-phenyl)-4-(3-methyl-4-nitro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(2-chloro-phenyl)-4-(3-methyl-4-nitro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(3-methyl-4-nifro-beri2yl)-2-(2-1rifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(3 -fluoro-phenyl)-4-(3 -methyl-4-nitro-benzyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one, 2-(3-chloro-phenyl)-4-(3 -methyl-4-nitro-benzyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one,
4-(3-methyl-4-nifro-benzyl)-2-(3-trifluoromethyl-phenyl)-2,4-dmydro-l,2,4-triazol-3-one, 2-(4-fluoro-phenyl)-4-(3-methyl-4-nitro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(4-chloro-phenyl)-4-(3-methyl-4-nitro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(3-methyl-4-nifro-benzyl)-2-(4-trifluoromethyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(3,4-bis-trifluoromethyl-phenyl)-4-(3-methyl-4-nifro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 2-(3,5-bis-trifluoromethyl-phenyl)-4-(3-methyl-4-nifro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, 4-(3-methyl-4-nifro-benzyl)-5-trifluoromethyl-2-(4-trifluoromemyl-phenyl)-2,4-dihydro-l,2,4-triazol- 3-one, -(2-chloro-phenyl)-2-(3-methyl-4-nitro-benzyl)-2,4-dihydro-l,2,4-triazol-3-one, -(3 -metlιyl-4-nitro-benzyl)-4-(4-trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4-triazol-3 -one,
5-methyl-2-(3-methyl-4-nifro-beιιzyl)-4-(4-trifluorome1hyl-phenyl)-2,4-dihydro-l,2,4-triazol-3-one, -(2-chloro-phenyl)-2-(3-methyl-4-nifro-benzyl)-5-methylsulfanil-2,4-dihydro-l,2,4-triazol-3-one, -(3 -methyl-4-nifro-benzyl)-5-memylsulfanil-4-(4-trifluoromethyl-phenyl)-2,4-dihydro- 1 ,2,4-triazol-
3 -one,
1 -methyl-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -ethyl-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -propyl-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -isobutyl-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 -methyl-4-nitro-benzyl)-4-(2,2,2-trifluoro-ethyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 -methyl-4-nitro-benzyl)-4-(4,4,4-trifluoro-butyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 -methyl-4-nitro-benzyl)-4-(3 ,3 ,3 -trichloro-2-methyl-propyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -cyclopropyl-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one, l-cyclohexyl-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 -methyl-4-nitro-benzyl)-4-phenyl- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-fluoro-phenyl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(2-chloro-phenyl)-4-(4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(2-chloro-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(2-chloro-phenyl)-4-[l-(3-methyl-4-nitro-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nitro-benzyl)-4-(2-methyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nitro-benzyl)-4-(2-methoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-ni1ro-berιzyl)-4-(2-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nitio-benzyl)-4-(2-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-fluoro-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 -chloro-phenyl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(3 -methyl-4-nitro-benzyl)-4-(3 -methyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-nitro-benzyl)-4-(3 -trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(3-methyl-4-nifro-benzyl)-4-(3-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(3-difluoromethoxy-phenyl)-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3-methyl-4-nitro-benzyl)-4-(3 -trifluoromethoxy-phenyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-fluoro-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(4-chloro-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(4-bromo-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3-methyl-4-nitro-benzyl)-4-(4-methyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-isopropyl-phenyl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one, l-(4-nifro-benzyl)-4-(4-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(2-chloro-4-nitro-benzyl)-4-(4-trifluoromethyl-phenyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-cUoro-4-nitio-benzyl)-4-(4-trifluorome1iιyl-phenyl)-l,4-dihydrθ-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-(4-trifluorometiiyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(4-difluoromethoxy-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nitro-benzyl)-4-(4-trifluoromethoxy-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-(4-trifluoromethylsulfanil-phenyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 -methyl-4-nitro-benzyl)-4-(4 ' -trifluoromethyl-biphenyl-4-yl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(3 ' ,5 ' -bis-trifluoromethyl-biphenyl-4-yl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(4-bromo-2-fluoro-phenyl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(2-fluoro-3 -trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-bromo-4-1rifluoromethoxy-phenyl)-4-(3-methyl-4-nifro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 -chloro-4-trifluoromethoxy-phenyl)-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one,
1 -(4-fluoro-3-trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(2-fluoro-5-trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(4-chloro-3-trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3,4-dicUoro-phenyl)-4-(3-me1hyl-4-ndtro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3,4-bis-1rifluoromethyl-phenyl)-4-(3-methyl-4-nifro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-fluoro-5-trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 ,5-dichloro-phenyl)-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3,5-dimethoxy-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 ,5-bis-trifluoromethyl-phenyl)-4-(2-chloro-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3,5-bis-trifluoromethyl-phenyl)-4-(3-chloro-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3,5-bis-trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one,
1 -(3 ,5-bis-trifluoromethyl-phenyl)-4-(2-methoxy-4-mtro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3,5-bis-trifluoromethyl-phenyl)-4-(3-methoxy-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3,5-bis-trifluoromethyl-phenyl)-4-(3,5-dimethyl-4-nifro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3,5-bis-trifluoromethyl-phenyl)-4-[l-(3-methyl-4-nitro-phenyl)-ethyl]-l,4-dihydro-tetτazol-5-one, l-(3-chloro-2-methoxy-5-methyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(2,2-difluoro-benzo[l,3]dioxol-5-yl)-4-(3-methyl-4-mfro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-(2,2,3,3-tefrafluoro-2,3-dihydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro- tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-(2,2,3-trifluoro-2,3-dihydro-benzo[l,4]dioxin-6-yl)-l,4-dihydro- tetrazol-5-one,
1 -(3 -methyl-4-nitro-benzyl)-4-(2,3 ,3 -trifluoro-2,3-dihydro-benzo [ 1 ,4] dioxin-6-yl)- 1 ,4-dihydro- tetrazol-5-one,
1 -(3-methyl-4-nitro-benzyl)-4-(2,2,3 ,3 ,7-pentafluoro-2,3-dihydro-benzo[l ,4]dioxin-6-yl)- 1 ,4- dihydro-tetrazol-5-one, l-(3,5-dicMoro-2,6-die1lιyl-phenyl)-4-(3-methyl-4-nifro-benzyl)-l,4-dihyάι'o-tetrazol-5-one, 1 -benzyl-4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(4-fluoro-benzyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(4-chloro-benzyl)-4-(3-methyl-4-mfro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-(4-trifluoromethyl-benzyl)-l,4-dihydro-tetrazol-5-one, 1 -[1 -(2-fluoro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-[l-(2-chloro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-[l-(2-trifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, 1 - [ 1 -(3-fluoro-phenyl)-ethyl] -4-(3 -methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5 -one, l-[l-(3-chloro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-ben^l)-4-[l-(3-trifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, 1 -[ 1 -(4-fluoro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, 1 -[ 1 -(4-chloro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one, l-(3-methyl-4-nifro-benzyl)-4-[l-(4-trifluoromethyl-phenyl)-ethyl]-l,4-dihydro-tetrazol-5-one, l-[l-(2,4-difluoro-phenyl)-emyl]-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-όne, l-[l-(2,4-dichloro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, 1 -[1 -(3 ,4-difluoro-phenyl)-ethyl]-4-(3-methyl-4-nitro-benzyl)- 1 ,4-dihydro-tetrazol-5-one.
And as specific examples of the compounds of the formula (TV), starting materials in the preparation process (b), there can be mentioned, for example,
2- {2-methyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tetrazol- 1 -ylmethyl]-phenyl} -isoindol- 1,3- dione-,
4-fluoro-2-{2-methyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol-l,3-dione,
4-chloro-2- {2-methyl-4-[5 -oxo-4-(2-chloro-phenyl)-4,5 -dihydro-tetrazol- 1 -ylmethyl] -phenyl} - isoindol- 1 ,3-dione,
4-bromo-2-{2-methyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol- 1 ,3-dione, 4-iodo-2-{2-methyl-4-[5-oxo-4-(2-cMoro-phenyl)-4,5-dihydro-tefrazol-l-ylmethyl]-phenyl}-isoindol-
1,3-dione,
4,7-dichloro-2-{2-methyl-4-[5-oxo-4-(2-chioro-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol- 1 ,3 -dione,
5,6-dichloro-2-{2-me1_hyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tefrazol-l-ylmethyl]-phenyl}- isoindol- 1,3 -dione,
4-nitro-2-{2-methyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol- 1,3 -dione, 4-me yl-2-{2-methyl-4-[5-oxo-4-(2-chloro-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol-1 ,3-dione,
2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-α^ydro-tetrazol-l-ylmethyl]-phenyl}- isoindol-l,3-dione, 4-fluoro-2-{2-methyl-4-[5-oxo-4-(4-trifluoromemyl-phenyl)-4,5-dihy(lro-tefrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-chloro-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-bromo-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl}-isoindol-l,3-dione,
4-iodo-2-{2-methyl-4-[5-oxo-4-(4-trifluoromemyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol- 1 ,3-dione,
4,7-dicUoro-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione, 5,6-dichloro-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-nifro-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl}-isoindol-l,3-dione,
4-methyl-2-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1,3-dione,
2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-phenyl}- isoindol- 1 ,3-dione,
4-fluoro-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione, 4-chloro-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-bromo-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-iodo-2- {2-methyl-4-[5-oxo-4-(3 ,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol- 1 -ylmethyl]- phenyl}-isoindol-l,3-dione,
4,7-dichloro-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l- ylmethyl]-phenyl}-isoindol-l,3-dione,
5,6-dicMoro-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l- ylmethyl] -phenyl} -isoindol- 1 ,3-dione, 4-nifro-2-{2-ή ethyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3-dione,
4-metyl-2-{2-methyl-4-[5-oxo-4-(3,5-bis-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -isoindol- 1 ,3 -dione.
The compounds of the formula (V), starting materials in the preparation process (b), are either well- known compounds in the field of organic chemistry or can be synthesized according to the process described in DE-A 2045 905, WO 01/23350 etc. As their specific examples there can be mentioned ethylamine, diethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutyl- amine, t-butylamine, t-amylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, 3-methyl- cyclohexylamine, 2-(methylthio)-ethylamine, 2-(ethylthio)-ethylamine, l-methyl-2-(methylthio)- ethylamine, l,l-dimethyl-2-(methylthio)-ethylamine, etc.
Compounds of the formula (VI), starting materials in the preparation process (c), include known compounds or can be easily obtained according to the process described in EP-A 0 919 542, EP-A
1 006 107 etc. and as their specific examples there can be mentioned,
N-isopropyl-phthalamic acid, 3-fluoro-N-isopropyl-phthalamic acid,
3-chloro-N-isopropyl-phthalamic acid,
3 -bromo-N-isopropyl-phthalamic acid,
3 -iodo-N-isopropyl-phthalamic acid,
N-isopropyl-3-nitro-phthalamic acid, N-(l-methyl-2-methylsulfanil-ethyl)-phthalamic acid,
3 -fluoro-N-( 1 -methyl-2-methylsulfanil-ethyl)-phthalamic acid,
3 -chloro-N~( 1 -methyl-2-methylsulfanil-ethyl)-phthalamic acid,
3 -bromo-N-( 1 -methyl-2-methylsulfanil-ethyl)-phthalamic acid,
3 -iodo-N-( 1 -methyl-2-methylsulfanil-ethyl)-phthalamic acid, N-(l-methyl-2-methylsulfanil-ethyl)-3-nitro-phthalamic acid,
N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-phthalamic acid,
N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-3 -fluoro-phthalamic acid,
3 -chloro-N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-phthalamic acid,
3 -bromo-N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-phthalamic acid, N-(l,l-dimethyl-2-methylsulfanil-ethyl)-3-iodo-phthalamic acid,
N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-3 -nitro-phthalamic acid,
N-isopropyl-3 -methanesulf onyloxy-phthalamic acid,
N-(l-methyl-2-methylsulfanil-ethyl)-3-methanesulfonyloxy-phthalamic acid,
N-( 1 , 1 -dimethyl-2-methylsulfanil-ethyl)-3 -methanesulfonyloxy-phthalamic acid.
The compounds of the above-mentioned formula (VI) can be easily obtained generally by reacting phthalic anhydrides of the formula
Figure imgf000040_0001
wherein X and n have the same definition as aforementioned,
and amines of the formula
R1 H-l ( I )
R2 wherein R1 and R2 have the same definition as aforementioned.
, The above-mentioned compounds of the formula (XT T) and the compounds of the formula (XTV) are all well-known in the field of organic chemistry and specifically there can be mentioned the following as examples.
As examples of the compounds of the formula (XIE) there can be mentioned, phthalic anhydride, 3 -fluorophthalic anhydride, 3-chlorophthalic anhydride, 3-bromophthalic anhydride, 3-iodophthalic anhydride, 3-methylphthalic anhydride, 3-nitrophthalic anhydride, 3,6-di- fluorophthalic anhydride, 3,6-dichlorophthalic anhydride, 4,5-dichlorophthalic anhydride, 3,4,5,6- tetrafluorophthalic anhydride, 3,4,5,6-tetrachlprophthalic anhydride, 3-methanesulfonyloxyphthalic anhydride.
As examples of the compounds of the formula (XTV) there can be mentioned, ethylamine, n-propylamine, isopropylamine, n-butylamine, sec-butylamine, isobutylamine, t-butyl- amine, t-amylamine, cyclopropylamine, cyclopentylamine, cyclohexylamine, 2-(methylthio)-ethyl- amine, 2-(ethylthio)-ethylamine, l-methyl-2-(methylthio)-ethylamine, l,l-dimethyl-2-(methylthio)- ethylamine.
These amines can be easily obtained also by the process described in DE-A 2045 905, WO 01/23350.
The reaction for synthesizing the compounds of the formula (VI) can be conducted according to the process described in J Org. Chem. 1981, 46, 175 etc.
Such a reaction can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl 5 ketone (MIBK), etc.; nitriles, for example, acetonitrile, propionitrile, acrylonitrile; esters, for example, ethyl acetate, amyl acetate.
The preparation process (e) can be conducted in the presence of a base and as such a base there can be mentioned tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 10 1,1 ,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4- dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and 1,8-diazabi- cyclo[5.4.0]undec-7-ene (DBU), etc.
The reaction can be conducted in a substantially wide range of temperature. It can be conducted at the 15 temperatures in a range of generally about -70°C to about 100°C, preferably about 50°C to about 80°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the reaction, the aimed compounds can be obtained, for example, by reacting 1 mole ' 20 amount to 4 mole amount of the compounds of the formula (XTV) to 1 mole of the compounds of the formula (XIII) in a diluent, for example, acetonitrile.
The compounds of the formula (VII), starting materials in the preparation process (d), are novel compounds and can be easily obtained, for example, by reacting a compound represented by the 25 formula (VEI-a)
Figure imgf000041_0001
wherein X , n, A1, r, Q, A2, s and E have the same definition as aforementioned, in the presence of a condensing agent (cf. e.g. J. Med. Chem. 1967, 10, 982).
30 The compounds of the above-mentioned formula (VTE-a) are also novel compounds and can be easily obtained by reacting phthalic anhydrides of the aforementioned formula (X) and the compounds of the aforementioned formula (IE), in which R3 is a hydrogen atom. The above-mentioned reaction of a compound of the formula (VIE-a) and a compound of the formula (IE), in which R3 is a hydrogen atom, can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); ketones, for example, acetone, methyl ethyl ketone (MEK), methyl isopropyl ketone, methyl isobutyl ketone (MIBK); nitriles, for example, acetonitrile, propionitrile, acrylonitrile, etc.; esters, for example, ethyl acetate, amyl acetate.
The reaction can be conducted in the presence of a base and as such a base there can be mentioned tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethyl- ethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylami- nopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7- ene (DBU).
The reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -70°C to about 100°C, preferably about -50°C to about 80°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the reaction, the aimed compounds can be obtained, for example, by reacting 1 mole amount to 4 mole amount of the compounds of the formula (EI), in which R3 is a hydrogen atom, to 1 mole of the compounds of the formula (X) in a diluent, for example, acetonitrile.
As specific examples of the compounds of the above-mentioned formula (VTE-a), there can be mentioned, for example,
N-{4-[4-(2-chloro-phenyl)-5-oxo-4,5-dihydro-tetrazol-l-ylmethyl]-2-methyl-phenyl}-6-iodo- phthalamic acid,
6-iodo-N-{2-methyl-4-[5-oxo-4-(2-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]- phenyl} -phthalamic acid, N-{4-[4-(4-fluoro-phenyl)-5-oxo-4,5-dihydro-tetrazol-l-ylmethyl]-2-methyl-phenyl}-6-iodo- phthalamic acid, N-{4-[4-(4-chloro-phenyl)-5-oxo-4,5-dihydro-tetrazol-l-ylmethyl]-2-methyl-phenyl}-6-iodo- phthalamic acid,
6-iodo-N-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-ά hydro-tefrazol-l-ylmethyl]- phenyl} -phthalamic acid, etc.
And as specific examples of the compounds of the above-mentioned formula (VE), there can be mentioned, for example,
1 -(2-chϊoro-phenyl)-4-[4-(4-iodo-3-oxo-3H-isoberιz;ofuran- 1 -ylideneamino)-3 -methyl-benzyl] - 1 ,4- dihydro-tetrazol-5 -one, 1 -[4-(4-iodo-3-oxo-3H-isobenzofuran- 1 -ylideneamino)-3-methyl-benzyl]-4-(2-trifluoromethyl- phenyl)- 1 ,4-dihydro-tetrazol-5-one,
1 -(2-fluoro-phenyl)-4- [4-(4-iodo-3-oxo-3H-isobenzofuran- 1 -ylideneamino)-3 -methyl-benzyl] - 1 ,4- dihydro-tetrazol-5 -one, l-(4-chloro-phenyl)-4-[4-(4-iodo-3-oxo-3H-isobenzoftιran-l-ylideneammo)-3-methyl-benzyl]-l,4- dihydro-tetrazol-5-one, l-[4-(4-iodo-3-oxo-3H-isobenzofuran-l-ylideneamino)-3-methyl-benzyl]-4-(4-trifluoromethyl- phenyl)-l ,4-dihydro-tetrazol-5-one, etc.
The compounds of the formula (V), also starting materials in the preparation process (d), have been described in the aforementioned preparation process (b).
The compounds of the formula (VIE), starting materials in the preparation process (e), are novel compounds and can be easily obtained, as described in the aforementioned preparation process (d), generally by reacting phthalic anhydrides of the aforementioned formula (X) with the compounds of the aforementioned formula (IE).
The reaction is the same as already described in the aforementioned preparation process (d).
As specific examples of the compounds of the formula (VIE) there can be mentioned, N-{4-[4-(2-cWoro-phenyl)-5-oxo-4,5-dihydro-tefrazol-l-ylmethyl]-2-methyl-phenyl}-N-methyl-6- iodo-phthalamic acid,
6-iodo-N- {2-methyl-4-[5-oxo-4-(2-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol- 1-ylmethyl]- phenyl} -N-methyl-phthalamic acid,
N-{4-[4-(4-fluoro-phenyl)-5-oxo-4,5-dihydro-tefrazol-l-ylmethyl]-2-methyl-phenyl}-N-methyl-6- iodo-phthalamic acid,
N-{4-[4-(4-chloro-phenyl)-5-oxo-4,5-dihydro-tetrazol-l-ylmethyl]-2-methyl-phenyl}-N-methyl-6- iodo-phthalamic acid, 6-iodo-N-{2-metlιyl-4-[5-oxo-4-(4-trifluoromethyl-phenyl)-4,5-dihydro-tetrazol-l-ylmethyl]-N- methyl-phenyl} -phthalamic acid.
The compounds of the formula (V), also starting materials in the preparation process (e), are identical with those in the aforementioned preparation processes (b) and (d).
As another preparation process for the compounds of the aforementioned formula (VIE), the common starting materials in the preparation process (d) and preparation process (e), in which X and Y represent other groups than bromo or iodo, compounds of the formula
Figure imgf000044_0001
wherein n, R3, m, A1, r, Q, A2, s and E have the same definition as aforementioned, and X1 and Y1 each has a definition of the aforementioned X and Y but excluding bromo and iodo, is reacted with a metal reagent, for example, butyl lithium, and then reacted with carbon dioxide to obtain the compounds of the corresponding formula (VIE) (however, X and Y do not represent bromo or iodo).
The compounds of the above-mentioned formula (XV) are novel compounds and can be easily obtained generally by reacting a benzoic acid halide represented by the formula
Figure imgf000044_0002
wherein X1 and n have the same definition as aforementioned, and Hal represents a halogen atom, with the compoxmds of the aforementioned formula (TTT)
Figure imgf000044_0003
wherein R", Y, m, A1, r, Q, A2, s and E have the same definition as aforementioned.
The compounds of the above-mentioned formula (XVT) are well-known compounds in the field of organic chemistry and there can be mentioned specifically, benzoyl chloride, 3-fluorobenzoyl chloride, 3-chlorobenzoyl chloride, 3-methylbenzoyl chloride, 3-nitrobenzoyl chloride. The reaction to prepare the compounds of the above-mentioned formula (XV) can be conducted in an adequate diluent and as examples of the diluent used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF),- diethylene glycol dimethyl ether (DGM); esters, for example, ethyl acetate, amyl acetate.
The reaction can be conducted in the presence of an acid binder and as such an acid binder there can be mentioned, as inorganic base, hydroxides, carbonates, bicarbonates, etc. of alkali metals and alkaline earth metals, for example, sodium hydrogen carbonate, potassium hydrogen carbonate, sodium carbonate, potassium carbonate, lithium hydroxide, sodium hydroxide, potassiurii hydroxide, calcium hydroxide; as organic base, alcoholates, tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU).
The reaction can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20 to about 150°C, preferably about 0°C to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the reaction, the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (XVT) in a diluent, for example, 1,2-dichloroethane, in the presence of triethylamine.
The compounds of the formula (If), starting materials in the preparation process (f), are the compounds included in the aforementioned formula (I) of the present invention. By oxidizing Ci-Cβ- alkylthio-Crd-alkyl, the definition of Rlf in the formula (If), compounds of the formula (I) corresponding to Cι-C6-alkylsulfinyl-Cι-C6-alkyl or d-d-alkylsulfonyl-Ci-d-alkyl can be obtained.
The compounds of the formula (If) can be prepared by the aforementioned preparation processes (a), (b), (c), (d) and/or (e).
As specific examples of the compounds of the formula (If) there can be mentioned, for example, 3-iodo-N2-(l-me l-2-me lsulfanyl-ethyl)-N!-{2-methyl-4-[5-oxo-4-(3-trifluoromethyl-phenyl)- 4,5-dihydro-triazol-l-ylmethyl]-phenyl}-phthalamide,
N2-(l,l-dimethyl-2-methylsulfanyl-ethyl)-3-iodo-N1-{2-methyl-4-[5-oxo-4-(3-trifluoromethyl- phenyl)-4,5-dihydro-triazol- 1 -ylmethyl] -phenyl} -phthalamide, 3-iodo-N2-(l-methyl-2-memylsulfanyl-emyl)-Nl-{2-methyl-4-[5-oxo-4-(4-1rifluoromethyl-phenyl)- 4,5-dihydro-triazol-l-ylmethyl]-phenyl}-phthalamide,
N2-(l,l-dimethyl-2-methylsulfanyl-ethyl)-3-iodo-N1-{2-methyl-4-[5-oxo-4-(4-trifluoromethyl- phenyl)-4,5-dihydro-triazol-l-ylmethyl]-phenyl}-phthalamide,
N1 - {4- [4-(3 ,5 -bis-trifluoromethyl-phenyl)-5-oxo-4,5 -dihydro-triazol- 1 -ylmethyl] -2-methyl-phenyl} - 3-iodo-N2-(l-methyl-2-methylsulfanyl-ethyl)-phthalamide,
NI-{4-[4-(3,5-bis-trifluoromethyl-phenyl)-5-oxo-4,5-dihydro-triazol-l-ylmethyl]-2-methyl-phenyl}- N2-(l , 1 -dimethyl-2-methylsulfanyl-ethyl)- 3 -iodo-phthalamide, etc .
The reaction of the aforementioned preparation process (a) can be conducted by using adequate diluents, singly or mixed, and as examples of the diluents used in that case there can be mentioned water; aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, pentane, hexane, cyclohexane, petroleum ether, ligroine, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; ethers, for example, ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF), diethylene glycol dimethyl ether (DGM); nitriles, for example, . acetonitrile, propionitrile, acrylonitrile; esters, for example, ethyl acetate, amyl acetate.
The preparation process (a) can be conducted in the presence of an acid catalyst and as examples of such an acid catalyst there can be mentioned mineral acids, for example, hydrochloric acid, sulfuric acid, organic acids, for example, acetic acid, trifluoroacetic acid, propionic acid, methanesulfonic acid, benzenesulfonic acid, p-toluenesμlfonic acid.
The preparation process (a) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20°C to about 100°C, preferably about 0°C to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the preparation process (a), the aimed compounds can be obtained, for example, by reacting 1 mole amount to a little excess amount of the compounds of the formula (IE) to 1 mole of the compounds of the formula (TT) in a diluent, for example, 1,2-dichlorόethane, in the presence of 0.01-0.1 mole amount of p-toluenesulfonic acid.
The preparation process (b) can be conducted in the presence of a base such as tertiary amines, dialkylaminoanilines and pyridines, for example, triethylamine, 1,1,4,4-tetramethylethylenediamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimethylaminopyridine (DMAP), l,4-diazabicyclo[2.2.2]octane (DABCO) and l,8-diazabicyclo[5.4.0]undec-7-ene (DBU), etc. '
The preparation process (b) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -20°C to about 150°C, preferably room temperature to about 100°C. Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the preparation process (b), the aimed compounds can be obtained, for example, by reacting 1 mole amount to 25 mole amount of the compounds of the formula (V) to 1 mole of the compounds of the formula (TV).
The aforementioned preparation processes (c), (d) and (e) can be conducted under the similar conditions as for the above-mentioned preparation process (a).
The reaction of the aforementioned preparation process (f) can be conducted in an adequate diluent and as examples of the diluents used in that case there can be mentioned aliphatic, alicyclic and aromatic hydrocarbons (may be optionally chlorinated), for example, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene, dichlorobenzene; alcohols, for example, methanol, ethanol, isopropanol, butanol, acids: formic acid, acetic acid.
As oxidizing agent to be used there can be mentioned, for example, metachloroperbenzoic acid, peracetic acid, potassium metaperiodate, potassium hydrogen persulfate (oxone), hydrogen peroxide.
The preparation process (f) can be conducted in a substantially wide range of temperature. It can be conducted at the temperatures in a range of generally about -50°C to about 150°C, preferably about - 10°C to about 100°C.
Although said reaction is conducted desirably under normal pressure, it can be operated also under elevated pressure or under reduced pressure.
In conducting the preparation process (f), the aimed compounds can be obtained, for example, by reacting 1 mole amount to 5 mole amount of an oxidizing agent to 1 mole of the compounds of the formula (If) in a diluent, for example, dichloromethane. The reaction of the preparation process (f) can be conducted according to the process described in, for example, Jikken Kagaku Kohza (Lectures of experimental chemistry), compiled by the Chemical Society of Japan, 4th ed., Vol. 24, page 350 (1992) published by Maruzen or ibid., page 365.
The compounds of the formula (I) of the present invention show strong insecticidal action. They can, therefore, be used, as insecticidal agents. And the active compounds of the formula (I) of the present invention exhibit exact controlling effect against harrnful insects without phytotoxicity against cultured plants. The compounds of the present invention can be used for controlling a wide variety of pests, for example, harmful sucking insects, biting insects and other plant-parasitic pests, stored grain pests, hygienic pests, etc. and applied for their extermination.
As examples of such pests there can be mentioned the following pests:
As insects, there can be mentioned coleoptera pests, for example, Callosobruchus Chinensis, Sitophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis,
Anomala rufocuprea, Leptinotarsa decemlineata, Diabrotica spp., Manochamus alternatus,
Lissorhoptrus oryzophilus, Lyctus bruneus;
Lepidoptera pests, for example, Lymantria dispar, Malacosoma neustria,- Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo suppressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella maculipennis, Heliothis virescens, Phyllocnistis citrella;
Hemiptera pests, for example, Nephotettix cincticeps, Nilaparvata lugens, Pseudococcus comstocki,
Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Rhopalosiphum pseudobrassicas,
Stephanitis nashi, Nazara spp., Cimex lectularius, Trialeurodes vaporariorum, Psylla spp.; Orthoptera pests, for example, Blatella germanica, Periplaneta americana, Gryllotalpa africana,
Locusta migratoria migi'qtoriodes;
Homoptera pests, for example, Reticulitermes speratus, Coptotermes formosanus;
Diptera pests, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens,
Anopheles slnensis, Culex tritaeniorhynchus. Moreover, as mites there can be mentioned, for example, Tetranychus telarius, Tetranychus urticae,
Panonychus citri, Aculops pelekassi, Tarsonemus spp.
Furthermore, as nematodes there can be mentioned, for example, Meloidogyne incognita,
Bursaphelenchus lignicolus Mamiya et Kiyohara, Aphelenchoides basseyi, Heterodera glycines,
Pratylenchus spp.
In addition, in the field of veterinary medicine, the novel compounds of the present invention can be effectively used against various harmful animal-parasitic pests (endoparasites and ectoparasites), for example, insects and helminthes. As examples of such animal-parasitic pests there can be mentioned the following pests:
As insects there can be mentioned, for example, Gastrophilus spp., Stornoxys spp., Trichodectes spp., Rhodnius spp., Ctenocephalides canis.
As mites there can be mentioned, for example, Ornithodoros spp., Ixodes spp., Boophϊlus spp.
In the present invention substances having insecticidal action against pests, which include all of them, are in some cases called as insecticides.
The active compounds of the present invention can be made into customary formulation forms, when they are used as insecticides. As formulation forms there can be mentioned, for example, solutions, emulsions, wettable powders, water dispersible granules, suspensions, powders, foaming agents, pastes, tablets, granules, aerosols, active compound-impregnated natural and synthetic substances, microcapsules, seed coating agents, formulations used with burning equipment (as burning equipment, for example, fumigation and smoking cartridges, cans, coils, etc.), ULV [cold mist, warm mist], etc.
These formulations can be prepared according to per se known methods, for example, by mixing the active compounds with extenders, namely liquid diluents; liquefied gas diluents; solid diluents or carriers, and optionally by using surface-active agents, namely emulsifiers and/or dispersants and/or foam-forming agents.
In case that water is used as extender, for example, organic solvents can be used also as auxiliary solvents.
As liquid diluents or carriers there can be mentioned, for example, aromatic hydrocarbons (for example, xylene, toluene, alkylnaphthalene etc.), chlorinated aromatic or chlorinated aliphatic hydrocarbons (for example, chlorobenzenes, ethylene chlorides, methylene chloride, etc.), aliphatic hydrocarbons [for example, cyclohexane etc. or paraffins (for example, mineral oil fractions etc.)], alcohols (for example, butanol, glycols and their ethers, esters, etc.), ketones (for' example, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.), strongly polar solvents (for example, dimethylformamide, dimethyl sulfoxide, etc.), and water.
Liquefied gas diluents or carriers are substances that are gases at normal temperature and pressure and there can be mentioned, for example, aerosol propellants such as butane, propane, nitrogen gas, carbon dioxide, halogenated hydrocarbons. As solid diluents there can be mentioned, for example, ground natural minerals (for example, kaolin, clay, talc, chalk, quartz, attapulgite, montmorillonite, diatomaceous earth, etc.), ground synthetic minerals (for example, highly dispersed silicic acid, alumina, silicates, etc.).
As solid carriers for granules there can be mentioned, for example, crushed and fractionated rocks (for example, calcite, marble, pumice, sepiolite, dolomite, etc.) synthetic granules of inorganic and organic meals, particles of organic materials (for example, saw dust, coconut shells, maize cobs, tobacco stalks, etc.) etc.
As emulsifiers and/or foam-forming agents there can be mentioned, for example, nonionic and anionic emulsifiers [for example, polyoxyethylene fatty acid esters, polyoxyethylene fatty acid alcohol ethers (for example, alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates, etc.)], albximin hydrolysis products, etc.
Dispersants include, for example, lignin sulfite waste liquor and methyl cellulose.
Tackifiers can also be used in formulations (powders, granules, emulsifiable concentrates). As said tac fiers there can be mentioned, for example, carboxymethyl cellulose, natural and synthetic polymers (for example, gum Arabic, polyvinyl alcohol, polyvinyl acetate, etc.).
Colorants can also be used. As said colorants there can be mentioned, for example, inorganic pigments (for example, iron oxide, titanium oxide, Prussian Blue, etc,), organic dyestuffs such as alizarin dyestuffs, azo dyestuffs or metal phthalocyanine dyestuffs, and further traces nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
Said formulations can contain the aforementioned active components of the amount in the range of generally 0.1 -95 % by weight, preferably 0.5 -90 % by weight.
The active compounds of the formula (I) of the present invention can exist also as a mixed agent with ' other active compounds, for example, insecticides, poisonous baits, bactericides, miticides, nematicides, fungicides, growth regulators or herbicides in the form of their commercially useful formulations or in the application forms prepared from such formulations. Here, as the above- mentioned insecticides, there can be mentioned, for example, organophosphorous agents, carbamate agents, carboxylate type chemicals, chlorinated hydrocarbon type chemicals, insecticidal substances produced by microbes, etc. Fxirther, the active compounds of the formula (T) of the present invention can exist also as a mixed agent with a synergist and such formulations and application forms can be mentioned as commercially useful. Said synergist itself must not be active, but is a compound that enhances the action of the active compound.
The content of the active compounds of the formula (I) of the present invention in a commercially useful application form can be varied in a wide range.
The concentration of the active compounds of the formula (I) of the present invention at the time of application can be, for example, in the range of 0.0000001-100 % by weight, preferably in the range of 0.00001-1 % by weight.
The compounds of the formula (I) of the present invention can be used by usual methods suitable to the application forms.
In case of application against hygienic pests and stored grain pests the active compounds of the present invention have a good stability against alkali on a calcific substance and further show an excellent residual effectiveness in wood and soil.
Then the present invention will be described more specifically by examples. The present invention, however, should not be restricted only to them in any way.
Examples
Synthesis Example 1
Figure imgf000052_0001
3-(l,l-Dimethyl-2-memyltMoethylimino)-4-iodo-3H-isobenzofuran-l-0ne (0.94 g) and l-(4-amino- 3-methylbenzyl)-4-(4-trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one (0.87 g) were dissolved in dichloromethane (10 ml), to which p-toluenesulfonic acid monohydrate (0.01 g) was added, and the mixture was stirred at room temperature for 3 hours. After finishing the reaction, water was added to the mixture and the organic layer was separated and dried with anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure and the residue was purified by silica gel column chromatography to obtain N2-(l,l-dimethyl-2-methylthioethyl)-3-iodo-N1-[2-methyl-4-(5-oxo-4-(4- trifluoromethylphenyl)-4,5-dihydrotetrazol-l-ylmethyl)phenyl]phthalamide (0.6 g, mp. 83-87°C).
Synthesis Example 2
Figure imgf000052_0002
N1-{4-[4-(3,5-bis-trifluoromethylphenyl)-5-oxo-4,5-dihydrotefrazol-l-ylmethyl]-2-methyl-phenyl}- N2-(l,l-dimethyl-2-methylthioethyl)-3-iodo-phthalamide (0.5 g) was dissolved in dichloromethane, to which m-chloroperbenzoic acid (0.18 g) was added, and the mixture was stirred at room temperature for 5 hours. After finishing the reaction the mixture was washed successively with aqueous solution of sodium thiosulfate, saturated aqueous solution of sodium hydrogen carbonate and saturated aqueous solution of sodium chloride and dried with anhydrous magnesium sulfate. After the solvent was distilled off, the obtained residue was purified by silica gel column chromatography to obtain N1-{4-[4-(3,5-bis-trifluoromemylphenyl)-5-oxo-4,5-dihydrotetrazol-l-ylmethyl]-2-methyl- phenyl} -3 -iodo-N2-(2-methanesulfinyl-l,l-dimethylethyl)phthalamide (0.1 g, mp. 165-l71°C). Synthesis Example 3
Figure imgf000053_0001
N2-(l,l-Dimethyl-2-methyltmoe l)-3-iodo-NI-[2-me l-4-(5-oxo-4-(4-trifluoromet_hylphenyl)-4,5- dihydrotetrazol-l-ylmethyl)phenyl]phthalamide (0.4 g) was dissolved in dichloromethane, to which m-chloroperbenzoic acid (0.24 g) was added, and the mixture was stirred at room temperature for 5 hours. After finishing the reaction the mixture was washed successively with aqueous solution of sodium thiosulfate, saturated aqueous solution of sodium hydrogen carbonate and saturated aqueous solution of sodium chloride and dried -with anhydrous magnesium sulfate. After the solvent was distilled off, the obtained residue was purified by silica gel column chromatography to obtain 3-iodo- N2-(2-methanesulfonyl- 1 , 1 -dimethylethy^-N1 - {2-methyl-4- [5-oxo-4-(4-trifluoromethylphenyl)-4,5 - dihydrotetrazol-l-ylmethyl]phenyl}phthalamide (0.16 g, mp. 108-112°C).
Synthesis Example 4
Figure imgf000053_0002
2-{2-Metlιyl-4-[5-oxo-4-(4-trifluoromethylphenyl)-4,5-dihydrotefrazol-l-ylmethyl]phenyl}isoindol- 1,3-dione (0.25 g) was dissolved in sec-butylamine (5 ml) and the mixture was stirred at room temperature for 5 hours. After finishing the reaction, the solvent was distilled off under reduced pressure and the obtained residue was purified by silica gel column chromatography to obtain the objected N-sec-butyl-N-{2-methyl-4-[5-oxo-4-(4-trifluoromethylphenyl)-4,5-dihydrotetrazol-l- yl- methyl]phenyl}phthalamide (0.2 g, mp. 217-218°C).
Examples of the compounds of the formula (I) of the present invention obtained in the similar manner to the Synthesis Examples 1 to 4 and the compounds of the formula (I) obtained easily by the preparation processes (a) to (f) are shown in the Table 1 to Table 4, together with the compounds obtained in the above-mentioned Synthesis Examples 1 to 4. In all tables the abbreviations mean
Ph = phenyl, Me = methyl, Et = ethyl, n-Pr = n-propyl, i-Pr = iso-propyl.
Table l (r = 0, s = 0)
Figure imgf000054_0001
represents the following structures:
Figure imgf000054_0002
Q17-1 Q34-1 Q35-1 Q48-1
Figure imgf000054_0003
Q48-2 Q50 Q59-1 Q60-1
.(wherein the bond marked with * connects with A1 and the bond marked with # connects with A2)
Figure imgf000054_0004
Table 2 (1=1, s=0)
Figure imgf000055_0001
represents the following structures
Figure imgf000055_0002
Q15-1 Q15-2 Q22-1 Q23-1 Q29-1 041-1
Q45-1 Q48-1 Q54 Q55-1 Q56-1 Q56-2
Figure imgf000055_0004
Q64-1 Q64-2 Q64-3 Q64-4 Q64-5 Q64-6
Figure imgf000055_0005
Q66 Q69-1
(wherein the bond marked with * connects with A1 and the bond marked with # connects with.A2)
Figure imgf000055_0006
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
Figure imgf000061_0001
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0002
Figure imgf000066_0001
ppm): 1.4 (6H, s), 1.9 (3H, s), 2.3 (3H, s), 2.8 (2H, s), 5.7 (2H, s), 6.0 (IH, s), 7.0-8.3 (HH, m)
2) Η-NMR (CDC13, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.2 (3H, s), 2.9 (2H, s), 4.8 (2H, s), 6.3 (IH, d), 6.4 (IH, s), 6.6 (IH, d), 7.0-8.5 (11H, m)
3) Η-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.8 (2H, s), 3.9 (2H, s), 4.6 (2H, s), 6.1 (lH, s), 7.0-8.4 (HH, m)
4) 'H-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.2 (3H, s), 2.9 (2H, s), 4.8 (2H, s), 6.1 (IH, s), 7.1-8.4 (12H, m) 5) Η-NMR (CDC13, ppm): 1.6 (6H, s), 2.2 (3H, s), 2.6 (3H, s), 3.5 (2H, s), 4.9 (2H, s), 6.2 (IH, s), 7.1-8.2 (12H, m) 6) Η-NMR (CDC13, ppm): 1.6 (6H, s), 2.3 (3H, s), 2.6 (3H, s), 3.3 (3H, s), 3.6 (2H, s), 4.9 (2H, s), 6.8 (lH, s), 7.1-8.1 (12H, m)
7) Η-NMR (CDC13, ppm): -1.2 (6H, d), 2.3 (3H, s), 4.2 (IH, m), 5.1 (2H, s), 6.0 (IH, m), 7.2-8.6
(12H, m) 8) Η-NMR (CDCI3, ppm): 1.4 (6H, s), 2.1 (3H, s), 2.3 (3H, s), 3.0 (2H, s), 5.1 (2H, s), 6.1 (IH, s), 7.2-8.9 (12H, m)
9) 'H-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 5.1 (2H, s), 6.1 (IH, s), 7.2-8.3 (12H, m)
10) Η-NMR (CDCI3, ppm): 1.7 (6H, s), 2.3 (3H, s), 2.6 (3H, s), 3.5 (2H, s), 5.1 (2H, s), 6.2 (IH, s), 7.0-8.2 (12H, m)
11) Η-NMR (DMSO-d6, ppm): 1.0 (6H, d), 2.2 (3H, s), 4.0 (IH, m), 5.1 (2H, s), 7.0-8.2 (11H, m),
9.4 (IH, s)
12) Η-NMR (CDCI3, ppm): ' " 1.1 (6H, d), 4.1 (IH, m), 5.1 (2H, s), 5.9 (IH, d), 7.0-8.0 (11H, m),
8.9 (IH, s) 13) Η-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.9 (2H, s), 5.1 (2H, s), 6.1 (IH, s), 7.0-8.0
(llH, m), 8.9 (lH, s)
14) Η-NMR. (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.2 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 5.1 (2H, s), 6.0 (lH, s), 7.1-8.3 (llH, m)
15) Η-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 5.1 (2H, s), 6.1 (IH, s), 7.0-8.4 (llH, m)
16) Η-NMR (CDCI3, ppm): 1.1 (6H, d), 2.3 (3H, s), 4.1 (IH, m), 5.1 (2H, s), 5.9 (IH, m), 7.1-8.3
(HH, m)
17) Η-NMR
Figure imgf000067_0001
ppm): 1.2 (3H, d), 2.0 (3H, s), 2.3 (3H, s), 2.7 (2H, dd), 4.1 (IH, m), 5.1
(2H, s), 6.1 (IH, d), 7.1-8.3 (11H, m) 18) Η-NMR (CDC13, ppm): 1.6 (6H, s), 2.2 (3H, s), 2.6 (3H, s), 3.5 (2H, s), 5.1 (2H, s), 6.2 (IH, s), 7.1-8.1 (10H, m)
19) 'H-NMR (CDCI3, ppm): 1.4 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.8 (2H, s), 5.1 (2H, s), 6.1 (IH, s), 7.0-8.4 (9H, m)
20) 'H-NMR (CDCI3, ppm): 1.1 (6H, d), 2.3 (3H, s), 4.2 (IH, m), 5.1 (2H, s), 5.9 (IH, m), 7.2-8.3 (HH, m)
21) Η-NMR (CDCI3, ppm): 1.6 (6H, S), 2.2 (3H, s), 2.6 (3H, s), 3.2 (3H, s), 3.5 (2H, s), 5.1 (2H, s), 6.7 (IH, s), 7.2-8.0 (12H, m)
22) Η-NMR (CDCI3, ppm): 1.1 (6H, d), 3.2 (3H, s), 4.1 (IH, m), 5.1 (2H, s), 6.2 (IH, d), 7.3-7.9
(l lH, m), 8.9 (lH, s) 23) 'H-NMR (CDC13, ppm): 1.6 (6H, s), 2.3 (3H, s), 2.6 (3H, s), 3.2 (3H, s), 3.6 (2H, s), 5.1 (2H, s), 6.7 (lH, s), 7.2-8.1 (l lH, m) 24) Η-NMR (CDC13, ppm): 1.3 (6H, s), 2.0 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 3.3 (3H, s), 5.1 (2H, s), 6.6 (lH, s), 7.2-8.5 (llH, m)
25) Η-NMR (CDCI3, ppm): 1.4 (6H, s), 1.9 (3H, s), 2.3 (3H, s), 2.9 (2H, s), 3.2 (3H, s), 5.1 (2H, s), 6.3 (lH, s), 7.2-8.3 (HH, m) 26) Η-NMR (CDCI3, ppm): 1.6 (6H, s), 2.3 (3H, s), 2.6 (3H, s), 3.3 (3H, s), 3.7 (2H, s), 5.1 (2H, s), 6.8 (lH, s), 7.2-8.1 (HH, m) 27) Η-NMR (CDCI3, ppm): 1.6 (6H, s), 2.3 (3H, s), 2.6 (3H, s), 3.5 (2H, d), 5.0 (2H, s), 6.4 (IH, s), 7.1-8.2 (HH, m)
Table 3 (ι=0, s=l)
Figure imgf000068_0001
represents the following structures:
Figure imgf000068_0002
(wherein the bond marked with * connects with A1 and the bond marked with # connects with A2)
Figure imgf000068_0003
Table 4 (r=l, s=l)
Figure imgf000069_0001
represents the following structures:
Figure imgf000069_0002
Figure imgf000069_0003
* Η-NMR (CDC13, ppm): 1.6 (6H, s), 1.9 (3H, d), 2.3 (3H, s), 2.5 (3H, s), 3.5 (2H, s), 5.0 (2H, s), 5.5 (IH, q), 6.3 (IH, s), 7.0-8.1 (11H, m) Synthesis Example 5 (Starting Material Synthesis)
Figure imgf000070_0001
To an ethanol solution (100 mL) of l-(3-methyl-4-nitrobenzyl)-4-(4-trifluoromethylphenyl)-l,4- dihydrotetrazol-5-one (9.48g) 10% palladium carbon (0.25g) was added and the mixture was stirred under hydrogen atmosphere at room temperature for 6 hours. After finishing the reaction, palladium carbon was filtered off and the solvent was distilled off under reduced pressure to obtain 1 -(4-amino- 3-methyl-benzyl)-4-(4-trifluoromethyl-phenyl)-l,4-dihydrotetrazol-5-one (8.11 g, mp. 210-211°C).
Synthesis Example 6 (Starting Material Synthesis)
Figure imgf000070_0002
In a similar manner as Synthesis Example 5, by using l-(3-methyl-4-nitro-benzyl)-4-(3-triiluoro- methylphenyl)-l,4-dihydrotetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3-trifluoromethyl-phe- nyl)-l,4-dihydrotetrazol-5-one was obtained (mp. 89-94°C).
Synthesis Example 7 (Starting Material Synthesis)
Figure imgf000070_0003
In a similar manner as Synthesis Example 5, by using l-(3,5-bis-trifluoromethyl-phenyl)-4-(3-me- thyl-4-nitro-benzyl)-l,4-dihydro-tetrazol-5-one, l-(4-amino-3-methyl-benzyl)-4-(3,5-bis-trifluoro- methyl-phenyl)- l,4-dihydro-tetrazol-5 -one was obtained (mp. 129-130°C).
Synthesis Example 8 (Starting Material Synthesis)
Figure imgf000070_0004
3-Methyl-4-nitrobenzyl chloride (1.6 g), l-(4-trifluoromethylphenyl)-l,4-dihydrotetrazol-5-one (2.0 g) and potassium carbonate (1.4 g) were stirred in DMF (50 ml) at room temperature for 5 hours. After finishing the reaction, water (100 ml) was added and the mixture was extracted with ethyl acetate. The organic layer was washed with a saturated aqueous solution of sodium chloride (100 ml) and dried with magnesium sulfate. After the solvent was distilled off, the obtained residue was purified by silica gel column chromatography to obtain l-(3-methyl-4-nitrobenzyl)-4-(4-tri- fluoromethylphenyl)-l,4-dihydrotetrazol-5-one [2.6 g, Η-NMR (CDC13, ppm) ; 2.6 (3H, s), 5.3 (2H, s), 7.4-8.3 (7H, m)].
Synthesis Example 9 (Starting Material Synthesis)
Figure imgf000071_0001
In a similar manner as Synthesis Example 8, by using 1 -(3 -trifluoromethyl-phenyl)- 1,4-dihydro-tetra- zol-5 -one, 1 -(3 -methyl-4-nitro-benzyl)-4-(3-trifluoromethyl-phenyl)- 1 ,4-dihydrotetrazol-5 -one was obtained [Η-NMR (CDC13, ppm) ; 2.6 (3H, s), 5.2 (2H, s), 7.3-8.2 (7H, m)].
Synthesis : Example 10 (Starting Material Synthesis)
Figure imgf000071_0002
In a similar manner as Synthesis Example 8, by using l-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro- tetrazol-5-one in place of l-(4-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one, l-(3,5-bis- trifluoromethyl-phenyl)-4-(3-methyl-4-nitro-benzyl)-l,4-dihydro-tetazol-5-one was obtained [Η- NMR (CDC13, ppm) ; 2.6 (3H, s), 5.2 (2H, s), 7.2-8.0 (4H, m), 8.5 (2H, bs)].
Synthesis Example 11 (Starting Material Synthesis)
Figure imgf000071_0003
3,5-Bis(trifluoromethyl) phenyl isocyanate (10.20 g) and trimethylsilyl azide (9.36 g) were stirred at 120-130°C for 10 hours. After the reaction mixture was brought to the room temperature, excess of trimethylsilyl azide was distilled off under reduced pressure and the obtained crude crystals were washed with petroleum ether to obtain l-(3,5-bis-trifluoromethyl-phenyl)-l,4-dihydro-tetrazol-5-one (11.05g, mp. 145-147°C). Synthesis Example 12 (Starting Material Synthesis)
Figure imgf000072_0001
Phthalic anhydride (1.0 g) and l-(4-amino-3-methylbenzyl)-4-(4-trifluoromethylphenyl)-l,4-dihydro- tetrazol-5-one (2.4 g) were refluxed in 60ml of acetic acid for 3 hours. After finishing the reaction the solvent was distilled off under reduced pressure to obtain the objected 2-{2-methyl-4-[5-oxo-4-(4- trifluoromethylphenyl)-4,5-dihydrotetrazol-l-ylmethyl]phenyl}isoindol-l,3-dione [3.0g, Η NMR (DMSO-d6, ppm) ; 2.1 (3H, s), 5.2 (2H, s), 7.3-8.2 (11H, m)].
Synthesis Example 13 (Starting Material Synthesis)
Figure imgf000072_0002
l-(3-Methyl-4-nitrobenzyl)-3-(4-trifluoromethylphenyl)urea (1.0 g) was dissolved in 20 ml of dichloromethane, to which 5 ml of dichloromethane solution of oxalyl chloride (0.49 g) was added at room temperature, and the mixture was stirred for 8 hours. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column' chromatography to obtain the objected l-(3-me yl-4-nitroben_zyl)-3-(4-trifluoromethylphenyl)imidazolidin-2,4,5-trione [l.lg, Η NMR (CDC13, ppm) ; 2.6 (3H, s), 4.9 (2H, s), 7.3-8.0 (7H, m)].
Synthesis Example 14 (Starting Material Synthesis)
Figure imgf000072_0003
Methanol solution (5 ml) of 3-methyl-4-nitrobenzaldehyde (0.9 g) was added to a methanol suspension (5 ml) of glycine ethyl ester acetate (1.1 g) and sodium cyanotrihydroborate (0.53 g) at 0°C. After stirring the mixture at room temperature for 10 hours, 2N hydrochloric acid (10 ml) and ethyl acetate (10 ml) were added thereto. After removing the organic layer, IN aqueous solution of sodium hydroxide .(30 ml) was added to the aqueous layer and extracted with ethyl acetate. After washing the organic layer with a saturated aqueous solution of sodium chloride (20 ml), it was dried with anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain the objected ethyl (3-methyl-4- nitrobenzylamino)acetate [0.9 g, Η NMR (CDC13, ppm) ; 1.2 (3H, t), 2.6 (3H, s), 3.4 (2H, s), 3.9 (2H, s), 4.2 (2H, q), 4.8 (2H, s), 7.2-8.1 (3H, m)]. Synthesis ; Example 15 (Starting Material Synthesis)
Figure imgf000073_0001
4-(trifluoromethyl)phenylisocyanate (0.83 g) was added to a diethyl ether solution (50 ml) of ethyl (3- methyl-4-nitrobenzylamino)acetate (0.9 g) and the mixture was stirred vigorously at room temperature for 7 hours. By filtering the crystals a crude product ethyl [l-(3-methyl-4-nitrobenzyl)-3-(4- trifluoromethylphenyl)ureido] acetate (0.8 g) was obtained and used in the next reaction without purification.
Synthesis Example 16 (Starting Material Synthesis)
Figure imgf000073_0002
Acetic acid solution (10 ml) of ethyl [l-(3-memyl-4-nitrobenzyl)-3-(4-trifluoromethylphenyl)- ureido]acetate (0.5 g) and concentrated hydrochloric acid (3 ml) was refluxed for 5 hours. After adding water (50 ml) the mixture was extracted with ethyl acetate. After washing the organic layer with water and a saturated aqueous solution of sodium chloride, it was dried with anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain the objected l-(3-methyl-4-nitrobenzyl)- 3-(4-trifluoromethylphenyl)imidazolidin-2,4-dione [0.3 g, Η NMR (CDC13, ppm) ; 2.7 (3H, s), 4.0 (2H, s), 4.8 (2H, s), 7.2-8.2 (7H, m)].
Synthesis Example 17 (Starting Material Synthesis)
Figure imgf000073_0003
4-Chloromethyl-2-methyl-l -nitrobenzene (1.9 g), aminoacetaldehyde dimethyl acetal (6.3 g) and potassium carbonate (6.2 g) were mixed in acetonitrile (200 ml) and the mixture was refluxed for 20 hours. After adding water the mixture was extracted with ethyl acetate. After washing the organic layer with a saturated aqueous solution of sodium chloride, it was dried with anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain the objected (2,2-dimethoxyethyl)-3-(methyl-4- nitrobenzyl)amine [2.5g, Η NMR (CDC13, ppm) ; 2.6 (3H, s), 2.8 (2H, d), 3.5 (6H, s), 3.9 (2H, s), 4.6 (lH, m), 7.2-8.1 (4H, m)].
Synthesis Example 18 (Starting Material Synthesis)
Figure imgf000074_0001
(2,2-Dimethoxye yl)-3-(methyl-4-nitrobenz_yl)an ine (1.2 g) was dissolved in ether (50 ml), to which 4-(trifluoromethyl)phenyl- isocyanate (1.3 g) was added at room temperature, and the mixture was stirred vigorously for 7 hours. After finishing the reaction, water was added to the mixture and it was extracted with ethyl acetate. After drying the organic layer with anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain a crude product l-(2,2-dimethoxyethyl)-l- (3-methyl-4-nitrobenzyl)-3-(4-(trifluoromethylphenyl)urea (1.8 g), which was used in the next reaction without purification.
Synthesis Example 19 (Starting Material Synthesis)
Figure imgf000074_0002
l-(2,2-Dimethoxyethyl)-l-(3-methyl-4-nitrobenzyl)-3-(4-(trifluoromethylphenyl)urea (1.8 g) was dissolved in THF (5 ml), to which 50 % aqueous solution of trifluoroacetic acid (20 ml), and the mixture was stirred at room temperature. After finishing the reaction and adding water, the mixture was extracted with ethyl acetate. After washing the organic layer with water and a saturated aqueous solution of sodium chloride, it was dried with anhydrous magnesium sulfate. After the solvent was distilled off under reduced pressure, the obtained residue was purified by silica gel column chromatography to obtain the objected l-(3-methyl-4-nitrobenzyl)-3-(4-(trifluoromethylphenyl)-l,3- dihydroimidazol-2-one [1.2 g, Η NMR (CDC13, ppm) ; 2.6 (3H, s), 4.9 (2H, s), 6.4 (IH, d), 6.7 (IH, d), 7.2-8.1 (7H, m)]. Biological Test Example 1: Test against larva of Spodoptera litura
Preparation of test agent:
Solvent: Dimethylformamide 3 parts by weight Emulsifier: Polyoxyethylene alkyl phenyl ether 1 part by weight
In order to make an appropriate formulation of an active compound, 1 part by weight of the active compound was mixed with the above-mentioned amount of solvent containing the above-mentioned amount of emulsifier and the mixture was diluted with water to a prescribed concentration.
Test method:
Leaves of sweet potato were soaked in the test agent diluted to a prescribed concentration with water, dried in the air and put in a dish of 9 cm diameter. 10 larvae of Spodoptera litura at the third instar were placed on the leaves and kept in a room at the constant temperature of 25°C. After 2 and 4 days further leaves of sweet potato were added and after 7 days the number of dead larvae was counted and the rate of death was calculated.
In this test the results of 2 dishes at 1 section were averaged.
Test results:
As specific examples the compounds of the compound no. 2-7, 2-35, 2-67, 2-71, 2-72, 2-96, 2-140, 2-
141, 2-142, 2-147, 2-173, 2-176, 2-181, 2-182, 2-270, 2-283, 2-293, 2-323, 2-333 and 2-337 showed 100% of rate of death at 20 ppm concentration of effective component.
Biological Test Example 2: Test against larva of Cnaphalocrocis nedinalis Guenee
Test method:
Rice seedlings (cultivar: Tamanishiki) of 4-5 leaf stage, planted in a vinyl pot (9 cm diameter) were sprayed with the diluted aqueous solution of the prescribed concentration of the active compound prepared in the same manner as in the above mentioned Biological Test Example 1. After drying, top 1/3 part of the leaves of the plants was cut and put into a Petri-dish (9 cm diameter), in which a piece of filter paper (9 cm diameter) was laid and moistened. Five larvae of Cnaphalocrocis rnedinalis at the second instar were released in the Petri-dish and the dish was placed in a room at the constant temperature of 25°C. After 2 and 4 days, another 1/3 part of the plant leaves was cut and added to the dish. After seven days, the number of dead larvae was counted and the rate of death was calculated. In this test the results of 2 dishes at 1 treatment were averaged. Test results: As specific examples the compounds of the compound no. 2-12, 2-17, 2-50, 2-54, 2-140, 2-141, 2- 154, 2-172, 2-173, 2-234, 2-248, 2-253, 2-256, 2-310, 2-333, 2-337, 4-8, 4-15 and 4-16 showed 100% of rate of death at 20 ppm concentration of effective component.
Formulation Example 1 (Granule)
To a mixture of 10 parts of the compound of the present invention (No. 2-7), 30 parts of bentonite (montmorillonite), 58 parts of talc and 2 parts of ligninsulfonate salt, 25 parts of water are added, well kneaded, made into granules of 10-40 mesh by an extrusion granulator and dried at 40-50°C to obtain granules.
Formulation Example 2 (Granules)
95 Parts of clay mineral particles having particle diameter distribution in the range of 0.2-2 mm are put in a rotary mixer. While rotating it, 5 parts of the compound of the present invention (No. 2-173) are sprayed together with a liquid diluent, wetted uniformly and dried at 40-50°C to obtain granules.
Formulation Example 3 (Emulsifiable Concentrate)
30 Parts of the compound of the present invention (No. 2-140), 55 parts of xylene, 8 parts of polyoxyethylene alkyl phenyl ether and 7 parts of calcium alkylbenzenesulfonate are mixed and stirred to obtain an emulsifiable concentrate.
Formulation Example 4 (Wettable Powder)
15 Parts of the compound of the present invention (No. 2-333), 80 parts of a mixture of white carbon (hydrous amorphous silicon oxide fine powders) and powder clay (1:5), 2 parts of sodium alkylbenzenesulfonate and 3 parts of sodium alkyhiaphthalenesulfonate-formalin-condensate are crushed and mixed to make a wettable powder.
Formulation Example 5 (Water Dispersible Granule)
20 Parts of the compound of the present invention (No. 2-337), 30 parts of sodium ligninsulfonate, 15 parts of bentonite and 35 parts of calcined diatomaceous earth powder are well mixed, added with water, extruded with 0.3mm screen and dried to obtain water dispersible granules.

Claims

Patent Claims.
Phthalamide derivatives represented by the formula
Figure imgf000077_0001
wherein
X represents hydrogen, halogen, CrC6-alkyl, C C6-haloalkyl, nitro, cyano, -Cg- alkylsulfonyloxy, -Cβ-haloalkylsulfonyloxy, phenylsulfonyloxy, Cι-C6-alkylthio- Cι-C6-alkyl, Cι-C6-alkylsulfmyl-Cι-C6-alkyl, - -alkylsulfonyl- -Cg-alkyl, Cr C6-alkylsulfonylamino, bis(Cι-C6-alkylsulfonyl)amino or -Cβ-alkoxycarbonyl, n represents 1, 2, 3 or 4,
Y represents hydrogen, halogen, -Ce-alkyl, Ci-Cβ-haloalkyl, - -alkoxy, Ci-Cβ- haloalkoxy, Ci-Cg-alkylthio, -Ce-haloalkylthio or cyano, m represents 1, 2, 3 or 4,
R1 represents Cι-C8-alkyl, Cι-C8-alkyl which is mono- or poly-substituted by substitu- ents selected from the group consisting of cyano, nitro, -Cg-alkylammosulfonyl,
N,N-di(Cι-C6-alkyl)aminosulfonyl, Cι-C6-alkylsulfonylamino, N-Cι-C6-alkylsulfo- nyl-N-Cι-C6-alkylamino, Q-Ce-alkyl-carbonylamino, halo-C C6-alkyl, N-Ci-Cβ- alkyl-carbonyl-N-Cι-C6-alkylamino, -Cg-alkyl-thiocarbonylamino, N- -Cδ-alkyl- thiocarbonyl-N-C C6-alkylamino, Cι-C6-alkoxyimino- -C6-alkyl, Cι-C6-alkyl-ami- nocarbonyl, N,N-di(Cι-C6-alkyl)-aminocarbonyl, Cι-C6-alkyl-aminothiocarbonyl,
NjN-di^i-Ce-alky^-aminothiocarbonyl, Cι-C6-alkoxy-carbonylamino, C C6-alk- oxy-carbonyl-Ci-Cδ-alkylamino, Cι-C6-alkylamino-carbonyloxy, N,N-di(Cι-C6-al- kyl)amino-carbonyloxy, Ci-Cβ-alkoxy-thiocarbonylamino, C C6-alkoxy-thiocarbo- nyl-C C6-alkylamino, CrC6-alkylamino-thiocarbonyloxy, N,N-di(CrC6-alkyl)- amino-thiocarbonyloxy, Cι-C6-alkylthio-carbonylamino, Cι-C6-alkylthio-carbonyl-
Ci-Ce-alkylamino, C Cβ-alkylamino-carbonylthio, N,N-di(C C6-alkyl)amino-carbo- nylthio, -C6-alkylthio-thiocarbonylamino, Ci -Cδ-alkylthio-thiocarbonyl-C! -C6-al- kylamino, Q-Cβ-alkylamino- iocarbonylthio, N,N-di(Cι-C6-alkyl)amino-thiocarbo- nylthio, C3-C6-cycloalkyl, Cι-C6-alkoxy-Cι-C6-alkyl, Ci-Cβ-alkylthio-Ci- -alkyl, Cι-C6-alkylsulfinyl-Cι-C6-alkyl and Cι-C6-alkylsulfonyl-Cι-C6-alkyl, or C3-C8-cyclo- alkyl which may be substituted by substituents selected from the group consisting of
CrC4-alkyl, CrC4-alkylthio or C1-C2-alkylthio-C,-C2-alkyl,
R2 represents hydrogen or -Cg-alkyl, R3 represents hydrogen or -Cβ-alkyl,
A1 represents straight chain or branched chain Cι-C8-alkylene, CrC8-haloalkylene, C2- C8-alkenylene, C2-C8-haloalkenylene, C2-C8-alkynylene, C2-C8-haloalkynylene, - C8-alkylene-amino, -Cs-alkylene^i-Ce-alkylamino), Cι-C8-alkyleneoxy or -C8- alkylenethio, r represents 0 or 1,
A2 represents straight chain or branched chain - -alkylene, Cι-C8-haloalkylene, C2- C8-alkenylene, C2-C8-haloalkenylene, C2-C8-alkynylene or C2-C8-haloalkynylene, s represents 0 or 1, Q represents a 5- or 6-membered heterocyclic group containing 1 to 4 hetero atoms selected from 0 to 4 nitrogen atom, 0 to 1 oxygen atom, and 0 to 1 sulphur atom, however not containing an oxygen atom and a sulphur atom at the same time, and said heterocyclic group
may have one to three C— O , one to three C— S , one S— O or one ,s^n
as ring constituent, and said heterocyclic group may be optionally substituted with at least one or more substituents selected from the below-mentioned group of substituents W1 wherein said substituents may be identical or different,
W1 represents halogen, -C6-alkyl, Cι-Ce-alkoxy, Cι-C6-alkylthio, Cι-C6-alkylsulfinyl,
Cι-C6-alkylsulfonyl, C C6-haloalkyl, Cι-C6-haloalkoxy, Cι-C6-haloalkylthio, C C6- haloalkylsulfinyl, Cι-C6-haloalkylsulfonyl, C3-C6-cycloalkyl, Cι-C6-alkylthio-Cι-C6- ■ alkyl, Ci-Cg-alkylsulfinyl- -Ce-alkyl, Ci-C6-alkylsulfonyl-C C6-alkyl, E represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group may be optionally substituted with one or more substituents selected from the below-mentioned group of substituents W2 wherein said substituents may be identical or different,
W2 represents halogen, nitro, C C6-alkyl, Cι-C6-alkoxy, CrC6-alkylthio, Cι-C6- alkylsulfinyl, Cι-C6-alkylsulfonyl, Cι-C6-haloalkyl, C C6-haloalkoxy, Cι-C6-haloal- kylthio, Cι-C6-haloalkylsulfinyl, C C6-haloalkylsulfonyl, C3-C6-cycloalkyl, C C6- alkylthio-C C6-alkyl, C-Cg-alkylsulfmyl-Ci-Cs-alkyl or d-Cs-alkylsulfonyl-C Cs- alkyl, or represents C3-C5-alkylene, C3-C5-haloalkylene, oxy-C2-C4-alkylene, oxy-C2-
C4-haloalkylene, C2-C -alkyleneoxy, C2-C -haloalkyleneoxy, Cι-C3-alkylenedioxy or Cι-C3-haloalkylenedioxy, in case that W2 are two adjacent substituents.
2. Compounds according to Claim 1, wherein X represents hydrogen, halogen, CrC -alkyl, Cι-C4-haloalkyl, nitro, cyano, C C4- alkylsulfonyloxy, C C4-haloalkylsulfonyloxy, phenylsulfonyloxy, Cι-C -alkylthio- C C4-alkyl, C]-C4-alkylsulfinyl-C1-C4-alkyl, Cι-C4-alkylsulfonyl-C C4-alkyl, C C4-alkylsulfonylamino, bis(Cι-C -alkylsulfonyl)amino or Cι-C -alkoxycarbonyl, n represents 1, 2, 3 or 4,
Y represents hydrogen, halogen, C1-C4-alkyl, CrC4-haloalkyl, -C4-alkoxy, CrC4- haloalkoxy, Ct-Q-alkylthio, Cr -haloalkylthio or cyano, m represents 1, 2,
3 or 4,
R1 represents Ci-Cβ-alkyl, CrC6-alkyl which is mono- or poly-substituted by substituents selected from the group consisting of cyano, nitro, Cι-C4-alkylaminosulfonyl, N,N-di(C)-C4-alkyl)aminosulfonyl, Cι-C4-alkylsulfonylamino, N-CrC -alkylsulfo- nyl-N-C C4-alkylamino, Cι-C4-alkyl-carbonylamino, halo-CrC4-alkyl, N- -C4- altyl-carbonyl-N-Cι-C4-alkylamino, Cι-C4-alkyl-thiocarbonylamino, N-Cι-C4-alkyl- thiocarbonyl-N-Cι-C4-alkylamino, Cι-C4-alkoxyimino-Cι-C4-alkyl, Ci-Q-alkyl- aminocarbonyl, N,N-di(Cι-C4-alkyl)-aminocarbonyl, Cι-C4-alkyl-aminothiocarbonyl, N,N-di(Cι-C4-alkyl)-aminothiocarbonyl, Cι-C4-alkoxy-carbonylamino, -C4- alkoxy-carbonyl-Cι-C4-alkylamino, C1-C4-alkylamino-carbonyloxy, N,N-di( -C4- alkyl)amino-carbonyloxy, C1-C4-alkoxy-thiocarbonylamino, Cι-C4-alkoxy-thiocarbo- nyl-Cι-C4-alkylamino, Cι-C4-alkylamino-thiocarbonyloxy, N,N-di(Cι-C4-alkyl)- amino-thiocarbonyloxy, Ci -C4-alkylthio-carbonylammo, -C -alkylthio-carbonyl- Cι-C -alkylamino, Cι-C4-alkylamino-carbonylthio, N,N-di(Cι-C4-alkyl)amino-carbo- nylthio, C1-C4-alkyltMo-thiocarbonylamino, Cι-C4-alkylthio-thiocarbonyl-Cι-C4- alkylamino, Cι-C4-alkylamino-t ^carbonylthio, N,N-di(Ci-C4-alkyl)amino-thiocar- bonylthio, C3-C6-cycloalkyl, C1-C4-alkoxy-Cι-C4-alkyl, Cι-C4-alkylthio-C1-C4-alkyl, Cι-C4-alkylsulfinyl-Cι-C4-alkyl and Cι-C4-alkylsulfonyl-C1-C4-alkyl, or C3-C6- cycloalkyl which may be substituted by C C2-alkyl, C C2-alkylthio or Cι-C2- alkylthio-CrC2-alkyl,
R2 represents hydrogen or Cι-C4-alkyl, R3 represents hydrogen or Cι-C4-alkyl,
A1 represents straight chain or branched chain Cι-C6-alkylene, Cι-C6-haloalkylene, C2- Cδ-alkenylene, C2-C6-haloalkenylene, -Cβ-alkynylene, C2-C6-haloalkynylene, Ci- C6-alkylene-amino, Cι-C6-alkylene(Cι-C4-alkylamino), CrC6-alkyleneoxy or Cι-C6- alkylenethio, r represents 0 or 1,
A2 represents straight chain or branched chain Cι-C6-alkylene, C C6-haloalkylene, C2- C6-alkenylene, C2-C6-haloalkenylene, C2-C6-alkynylene or C2-C6-haloalkynylene, s represents 0 or 1,
Q represents pyridinylene, pyridazinylene, pyrimidinylene, pyrazinylene, which may be optionally substituted with at least one or more substituents selected from the below- mentioned group of substituents W1 wherein said substituents may be identical or different, or further represents the below-mentioned groups;
Figure imgf000080_0001
Qi Q2 Q3 Q4
Figure imgf000080_0002
Q5 Q6 Q7 Q8
Figure imgf000080_0003
Q15 Q16 Q17 Q18 Q19
Figure imgf000080_0004
Q20 Q21 Q22 Q23 Q24
Figure imgf000080_0005
Q25 Q26 Q27
Figure imgf000080_0006
Q28 Q29 Q30
Figure imgf000081_0001
Q35 Q36 Q37 Q38 Q39 Q40
#
^
"rt rt. N N λ
V N-N
W° w W° w
Figure imgf000081_0002
Q45 Q46 Q47
Figure imgf000081_0003
Q48 Q49 Q50 Q51 Q52
Figure imgf000081_0004
-
Figure imgf000082_0001
Q66 Q67 Q68 Q69 Q70
(wherein the bond marked with * connects with A1 and the bond marked with # connects with A2, or the bond marked with # connects with A1 and the bond marked with * connects with A2)
W1 represents halogen, d-C6-alkyl, C C6-alkoxy, Cι-C6-alkylthio, Cι-C6-alkylsulfinyl, -Cβ-alkylsulfonyl, Cι-C6-haloalkyl, Cι-C6-haloalkoxy, C C6-haloalkylthio, Cι-C6- haloalkylsulfinyl, C]-C6-haloalkylsulfonyl, C3-C6-cycloalkyl, C C6-alkylthio-Cι-C6- alkyk
Figure imgf000082_0002
CrCfi-alkylsulfonyl-d-Ce-alkyl, E represents phenyl, biphenyl, naphthyl, pyridyl, pyridazinyl, pyrimidinyl, pyrazinyl, thienyl, furyl or pyrrolyl, wherein said group may be optionally substituted with one or more substituents selected from the below-mentioned group of substituents W2 wherein said substituents may be identical or different,
W2 represents halogen, nitro, Cι-C6-alkyl, Cι-C6-alkoxy, Cι-C6-alkylthio, Cι-C6-alkylsul- finyl, Q-Cβ-alkylsulfonyl, C C6-haloalkyl, Cι-C6-haloalkoxy, Cι-C6-haloalkylthio,
Cι-C6-haloalkylsulfinyl, Cι-C6-haloalkylsulfonyl, C3-C6-cycloalkyl, Cι-C6-alkylthio- C C6-alkyl, CrC6-alkylsulfinyl-C1-C6-alkyl or C C6-alkylsulfonyl-Cι-C6-alkyl, or represents C3-C5-alkylene, C3-C5-haloalkylene, oxy-C2-C4-alkylene, oxy-C2-C4- haloalkylene, C2-C4-alkyleneoxy, C2-C4-haloalkyleneoxy, C]-C3-alkylenedioxy or C]-C3-haloalkylenedioxy, in case W2 are two adjacent substituents,
W3 represents hydrogen or has the same definition as the aforementioned W1, p represents 0, 1 or 2, q represents 0, 1, 2 or 3,
Processes for the preparation of the compounds of the formula (I) according to Claim 1, characterized in that
(a) in case that R2 in the formula (I) represents hydrogen compounds of the formula (II)
Figure imgf000082_0003
wherein R1, X and n have the same definition as mentioned in Claim 1, are reacted with compounds of the formula (DT)
Figure imgf000083_0001
wherein^3, Y, m, A1, r, Q, A2, s and E have the same definition as mentioned in
Claim 1, in the presence of inert solvents, .or
(b) in case that R3 in the formula (I) represents hydrogen atom compounds of the formula (IV).
Figure imgf000083_0002
wherein X, n, Y, m, A , r, Q, A , s and E have the same definition as mentioned in
Claim 1, are reacted with compounds of the formula (V)
R'
H- (V)
^
FT wherein R1 and R2 have the same definition as mentioned in Claim 1, in the presence of inert solvents, and if appropriate, in the presence of a base, or
(c) compounds of the formula (VI)
Figure imgf000083_0003
wherein X, n, R1 and R2 have the same definition as mentioned in Claim 1, are reacted with the compounds of the formula (HI),
Figure imgf000083_0004
wherein R3, Y, m, A1, r, Q, A2, s and E have the same definition as mentioned in
Claim 1, in the presence of inert solvents, or (d) in case that R3 in the formula (I) represents hydrogen atom, compounds of the formula (VTT)
Figure imgf000084_0001
wherein X, n, Y, m, A1, r, Q, A2, s and E have the same definition as mentioned in
Claim 1, are reacted with the compounds of the formula (V),
H-l( ( )
R2 wherein R1 and R2 have the same definition as mentioned in Claim 1, in the presence of inert solvents, or
(e) compounds of the formula (VTTT)
Figure imgf000084_0002
wherein X, n, R3, Y, m, A1, r, Q, A2, s and E have the same definition as mentioned in Claim 1,
are reacted with the compoxmds of the formula (V),
F R' H- (V)
wherein R1 and R2 have the same definition as mentioned in Claim 1, in the presence of inert solvents, or
(f) in case that R1 in the formula (I) represents Ci-Cg-alkylsulfinyl- -Cβ-alkyl or C Cβ- alkylsulfonyl- -Ce-alkyl compounds of the formula (If)
Figure imgf000085_0001
wherein Rlf represents - -alkylthio-Ci-Cβ-alkyl, and
X, n, R2, R3, Y, m, A1, r, Q, A2, s and E have the same definition as mentioned in Claim 1, are reacted with an oxidizing agent in the presence of inert solvents.
4. Pesticides, characterized in that they comprise at least one compound of the foimula (I) according to Claim 1.
5. A method of combating harmful insects characterized in that the compounds of formula (T) according to Claim 1 are allowed to act on pests and/or their habitat.
6. Use of the compounds of the formula (I) for combating harmful insects.
7. A process for preparing harmful insects compositions characterized in that the compounds of the formula (T) according to Claim 1 are mixed with extenders and/or surface active agents.
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Title
"Jikken Kagaku Kohza", vol. 24, 1992, MARUZEN, pages: 350
DATABASE CAPLUS CHEMICAL ABSTRACTS SERVICE, COLUMBUS, OHIO, US; XP002282764, retrieved from STN Database accession no. 2003:117525 *
DATABASE WPI Section Ch Week 200323, Derwent World Patents Index; Class C02, AN 2003-239459, XP002282765 *

Cited By (12)

* Cited by examiner, † Cited by third party
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WO2005095351A1 (en) * 2004-03-12 2005-10-13 Bayer Cropscience Ag N1 - ((pyrazol-1-ymethyl) -2-methylphenyl)- phatalamide derivatives and related compounds insecticides
US7674807B2 (en) 2004-03-12 2010-03-09 Bayer Cropscience Ag Heterocycle-substituted n-phenyl-phthalamide derivatives, related compounds and their use as insecticides
AU2005229339B2 (en) * 2004-03-12 2010-11-11 Bayer Cropscience Ag N1 - ((pyrazol-1-ymethyl) -2-methylphenyl)- phatalamide derivatives and related compounds insecticides
JP2008520599A (en) * 2004-11-18 2008-06-19 バイエル・クロツプサイエンス・アクチエンゲゼルシヤフト N-heterocyclylphthalic acid diamide as an insecticide
JP4918042B2 (en) * 2004-11-18 2012-04-18 バイエル・クロップサイエンス・アーゲー N-heterocyclylphthalic acid diamide as an insecticide
JP2007186507A (en) * 2005-12-15 2007-07-26 Nippon Nohyaku Co Ltd Phthalamide derivative, agricultural and horticultural insecticide and method for using the same
EP1961746A1 (en) * 2005-12-15 2008-08-27 Nihon Nohyaku Co., Ltd. Phthalamide derivative, agricultural or horticultural pesticide, and use of the pesticide
EP1961746A4 (en) * 2005-12-15 2011-03-09 Nihon Nohyaku Co Ltd Phthalamide derivative, agricultural or horticultural pesticide, and use of the pesticide
US7994339B2 (en) 2005-12-15 2011-08-09 Nihon Nohyaku Co., Ltd. Phthalamide derivative, agricultural or horticultural pesticide, and use of the pesticide
EP3560913A1 (en) 2018-04-25 2019-10-30 Dynamit Nobel GmbH Explosivstoff- und Systemtechnik Process for the production of tetrazolinones
WO2019206695A1 (en) 2018-04-25 2019-10-31 Basf Se Process for the preparation of 1-(2-methoxymethyl-3-methylphenyl)4h-tetrazolin-5-one
WO2019206696A1 (en) 2018-04-25 2019-10-31 Dynamit Nobel Gmbh Explosivstoff- Und Systemtechnik Process for the production of tetrazolinones

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AU2004220444A1 (en) 2004-09-23
BRPI0408354A (en) 2006-03-21
AU2004220444B2 (en) 2010-11-25
CN100522952C (en) 2009-08-05
CL2004000513A1 (en) 2005-03-28
JP2006520337A (en) 2006-09-07
MXPA05009725A (en) 2005-10-18
CN1759105A (en) 2006-04-12
EP1606271A1 (en) 2005-12-21
US20060223872A1 (en) 2006-10-05
KR20060006008A (en) 2006-01-18
AR043518A1 (en) 2005-08-03
JP2004277333A (en) 2004-10-07
TW200509795A (en) 2005-03-16
JP4617295B2 (en) 2011-01-19

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