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WO1999033790A1 - Insecticidal fluoro-substituted benzoylureas - Google Patents

Insecticidal fluoro-substituted benzoylureas Download PDF

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Publication number
WO1999033790A1
WO1999033790A1 PCT/IB1998/002105 IB9802105W WO9933790A1 WO 1999033790 A1 WO1999033790 A1 WO 1999033790A1 IB 9802105 W IB9802105 W IB 9802105W WO 9933790 A1 WO9933790 A1 WO 9933790A1
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WO
WIPO (PCT)
Prior art keywords
formula
fluoro
compounds
methyl
trifluoromethyl
Prior art date
Application number
PCT/IB1998/002105
Other languages
French (fr)
Inventor
Akihiko Yanagi
Ryo Watanabe
Shin-Ichi Narabu
Michiaki Shiroshita
Yuichi Otsu
Yumi Hattori
Katsuhiko Shibuya
Takahisa Abe
Original Assignee
Nihon Bayer Agrochem K.K.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nihon Bayer Agrochem K.K. filed Critical Nihon Bayer Agrochem K.K.
Priority to AU15019/99A priority Critical patent/AU1501999A/en
Publication of WO1999033790A1 publication Critical patent/WO1999033790A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C273/00—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C273/18—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas
    • C07C273/1809—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety
    • C07C273/1818—Preparation of urea or its derivatives, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups of substituted ureas with formation of the N-C(O)-N moiety from -N=C=O and XNR'R"
    • C07C273/1827—X being H
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C275/00—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C275/46—Derivatives of urea, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups containing any of the groups, X being a hetero atom, Y being any atom, e.g. acylureas
    • C07C275/48—Y being a hydrogen or a carbon atom
    • C07C275/54—Y being a carbon atom of a six-membered aromatic ring, e.g. benzoylureas
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/24—Derivatives of thiourea containing any of the groups, X being a hetero atom, Y being any atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/02—Systems containing only non-condensed rings with a three-membered ring

Definitions

  • the present invention relates to novel fluoro-substituted benzoylureas, to processes for their preparation and to their use as insecticides.
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, nitro, cyano, halogen,
  • R 4 represents a hydrogen atom, nitro, cyano, halogen, C ⁇ -alkyl, C ⁇ _3-haloalkyl,
  • R 5 represents optionally substituted C2_2o- luoroalkyl, optionally substituted C 4 . 2o-(carbon atoms in total) fluorocycloalkyl-alkyl, optionally substituted C 3 _ i Q -fluorocycloalkyl, optionally substituted C4_2o-(carbon atoms in total) fluoroalkyl-cycloalkyl or optionally substituted C 3 _2o- fluoroalkenyl,
  • X and Y each independently represent an oxygen atom or a sulfur atom, and n is 1 or 2.
  • the compounds of the above formula (I) can exist as isomers and include not only an isolated isomer but also a mixture of isomers in an arbitrary ratio.
  • the compounds of the formula (I), according to the invention can be prepared by a process in which
  • R 1 , R 2 , R 3 , R 4 , X, Y and n are defined as above,
  • R 5 is defined as above
  • R 1 , R 2 , R 3 , R 4 , X and n are defined as above,
  • R 1 , R 2 , R 3 , R 4 , R 5 and n are defined as above,
  • the fluoro-substituted benzoylureas of the formula (I) according to the invention exhibit substantially, extremely superior insecticidal activity in comparison with the previously known compounds described in the above prior art.
  • halogen in “halogen” and halogenated substituents like in “haloalkyl", “haloalkoxy and so on represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially preferably fluorine or chlorine.
  • the alkyl may be straight-chain or branched and includes, for example, methyl, ethyl,propyl, isopropyl, n-, iso-, sec- or tert-butyl, and the like.
  • haloalkyl may be straight-chain or branched and includes, for example, trifluoromethyl, 2,2,2-trifluoroethyl, and the like.
  • the alkoxy may be straight-chain or branched and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-butoxy, and the like.
  • the haloalkoxy may be straight-chain or branched and includes, for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, 2,2,2-tri- fluoroethoxy, and the like.
  • alkylthio may be straight-chain or branched and includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-, iso-, sec- or tert- butylthio, and the like.
  • haloalkylthio may be straight-chain or branched and in- eludes, for example, trifluoromethylthio, difluoromethylthio, chlorodifluoromethyl- thio, 2,2,2-trifluoroethylthio, and the like.
  • fluoroalkyl represents a straight-chain or branched alkyl radical having, if not indicated otherwise, 2 to 20 carbon atoms, which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two, substituent(s) selected from the group consisting of chlorine, bromine, phenyl, C 3 _.g-cycloalkyl and C 3 .g-fluorocycloalkyl.
  • fluoroalkyl examples include 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trifluoro- ethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 3,3,3- trifluoropropyl, 2,3,3-trifluoropropyl, 2,3,3,3-tetrafluoropropyl, 2,2,3,3 -tetrafluoro- propyl, 2,2,3,3,3-pentafluoropropyl, 3-chloro-2-fluoropropyl, 3,3-dichloro-2,2-di- fluoropropyl, 2,2,2-trifluoro- 1 -methylethyl, 2,2,2-trifluoro- 1 -(tri-fluoromethyl)ethyl, 3-chloro-3-fluoro
  • fluorocycloalkyl represents a cycloalkyl radical which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two, substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • fluorocycloalkyl examples include 2-fluoro- cyclopropyl, 2,2-difluorocyclopropyl, 2-fluoro-cyclohexyl, 2-chloro-2-fluorocyclo- propyl, 2-chloro-3-fluoro-cyclopropyl, 2,2-difluoro-l-methylcyclopropyl, 2-chloro- 2,3,3-trifluoro-l-methylcyclobutyl, and the like.
  • fluoroalkyl-cycloalkyl represents a cycloalkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by alkyl which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two substituent(s) selected from the group consisting of chlorine, bromine and C ] _ 3 -alkyl.
  • fluoroalkyl-cycloalkyl examples include l-(l,l-difluoroethyl)cyclohexyl, l-(l,l,2,2-tetrafluoroethyl)cyclohexyl, 3-tri- fluoromethylcyclohexyl, 2-trifluoromethylcyclohexyl, 1 -(trifluoromethyl)cyclo- propyl, 2-(trifluoromethyl)cyclopentyl, 2,4-bis(trifluoromethyl)cyclohexyl, 2-(tri- fluoromethyl)-l-methylcyclohexyl, and the like.
  • fluorocycloalkyl-alkyl represents an alkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by cycloalkyl substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two) substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • substituent(s) selected from the group consisting of chlorine, bromine and C j . 3 -alkyl.
  • Specific examples thereof include, for example, (perfluorocyclohexyl)methyl, 2-(
  • fluoroalkenyl represents astraight-chain or branched alkenyl radical with, if not indicated otherwise, 3 to 20 carbon atoms, which is substituted by at least one fluorine, and which may further be substituted by one or more (preferably one or two) substituent(s) selected from the group consisting of chlorine, bromine and alkoxy carbonyl.
  • Specific examples thereof include, for example, 2,3,3- trifluoro-2-propenyl, 3,4,4-trifluoro-3-butenyl, 4,4,4-trifluoro-2-butenyl, 4,4-di- fluoro-3-methylbutenyl, 4,4,5,5,6,6,7,7,7-nonafluoro-2-heptenyl, 4-trifluoromethyl- 4,5,5,6,6,6-hexafluoro-2-hexenyl, 3-(perfluorohexyl)-2-propenyl, and the like.
  • Preferred compounds of the above formula (I) are compounds, wherein
  • R 1 , R 2 and R 3 each independently represent a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, tri- fluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-tri- flu- oroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, di- fluoromethylthio or 2,2,2-trifluoroethylthio, with the proviso that all of R 1 , R 2 and R 3 do not simultaneously represent a hydrogen atom,
  • R 4 represents a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, difluoromethylthio or 2,2,2-tri- fluoroethylthio,
  • R 5 represents C 2 _ ⁇ -fluoroalkyl which may be substituted by one or more, (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine and bromine or represents C 4 _ 8 -fluorocycloalkyl- alkyl which may be substituted by one or more (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine and bromine or represents C 3 .
  • j o-fluorocycloalkyl which may be substituted by one or more (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine, bromine and methyl, or represents C 4 _ 1 o-fluoroalkyl- cycloalkyl or represents C 3 _ 5 -fluoro- alkenyl,
  • X and Y each independently represent an oxygen atom or asulfur atom, (preferably an oxygen atom) and
  • n 1 or 2 (preferably 1).
  • Particularly preferred compounds of the above formula (I) are compounds, wherein R 1 , R 2 and R 3 each independently represent a hydrogen atom, fluorine, chlorine, bromine, methoxy, trifluoromethyl, nitro or methyl, with the proviso that all of R 1 , R 2 and R 3 do not simultaneously represent a hydrogen atom,
  • R 4 represents a hydrogen atom, fluorine or trifluoromethyl
  • R 5 represents 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl,
  • X and Y represent an oxygen atom
  • n 1 or 2 (preferably 1). Specific examples of the compounds of the formula (I) according to the invention are shown in the later-described Table 1.
  • the compounds of the formula (II), used as starting materials are those wherein R 1 , R 2 , R 3 , R 4 , X, Y and n are defined as above.
  • the compounds of the formula (II) are known compounds and can be obtained, for example, by the processes similar to those described in Journal of Organic Chemistry
  • the compounds of the formula (II) include 2-fluorobenzoyl-isocyanate,
  • the compounds of the formula (III) used as starting materials are those wherein R 5 is defined as above.
  • the compounds of the formula (III) are known compounds and can be obtained, for example, by the processes described in Joumal of The American Chemical Society Vol. 72, 1950, 2786-2788 and Organic Syntheses Coll. Vol. 3, 1955, 151-156.
  • the compounds of the formula (III) include 2,2,2-trifluoroethylamine,
  • the compounds of formula (III) can be used in form of salts, for example as hydro- chlorides, hydrobromides or acetates.
  • the compounds of the formula (IV) used as the starting material are those wherein R 1 , R 2 , R 3 , R 4 , X and n are defined as above.
  • the compounds of the formula (IV) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of Medicinal
  • the compounds of the formula (V) used as the starting material are those wherein R 3 and Y are defined as above.
  • the compounds of the formula (V) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of The American Chemical Society Vol. 72, 1950, 1888-1891 or Organic Syntheses Coll. Vol 3, 1955, 599-600.
  • the compounds of the formula (VI) used as the starting material which may be mentioned, are those wherein Rl, R2, R3, R4, R5 and n are defined as above.
  • the compounds of the formula (VI) are the compounds of the invention, which are synthesized by the above processes (a) or (b).
  • Lawesson's reagent is 4-methoxyphenylthionophosphine sulfide dimer.
  • the reaction of the above-mentioned process (a) can be carried out in an appropriate diluent.
  • diluents which may be mentioned, are: aliphatic, alicyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chloroben- zene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and di- ethylene glycol dimethyl ether (DGM); nitriles such as aceton
  • the reaction of the process (a) can be carried out in the presence of an organic base or an organic lithium compound.
  • organic bases include tertiary alcoholates, tertiary amines, dial- kylaminoanilines and pyridines, such as triethylamine, 1 , 1 ,4,4-tetramethylethylene- diamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimeth- ylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabi- cyclo[5,4,0]undec-7-ene (DBU).
  • TEDA triethylamine
  • DMAP 4-dimeth- ylaminopyridine
  • DABCO 1,8-diazabi- cyclo[5,4,0]undec-7-ene
  • DBU 1,8-di
  • organic lithium compounds include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, n- butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.
  • the reaction of the process (a) can be carried out at a temperature within a substan- tially broad range, but it can generally be carried out at a temperature of about -10 to about 120°C, preferably about 0 to about 100°C. Further, the reaction should preferably be conducted under atmospheric pressure but it may optionally be operated under elevated or reduced pressure.
  • (III) is a salt
  • 1 mole of the compounds of the formula (II) can be reacted with 1 to 1.3 molar amounts of the compounds of the formula (III) in a diluent such as tetrahy- drofuran in the presence of an organic base to thereby obtain the desired compounds.
  • reaction of the above process (b) is known per se orcan be carried out by a process similar to a known one.
  • the reaction of the above-mentioned process (b) can be carried out in an appropriate diluent.
  • diluents which may be mentioned, are: aliphatic, ali- cyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pen- tane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichlo- romethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene gly- col dimethyl ether (DGM); nitriles such as
  • the reaction of the process (b) can be carried out in the presence of an inorganic alkali metal hydride or an organic lithium compound.
  • an inorganic alkali metal hydride or an organic lithium compound examples include lithium hydride, sodium hydride and potassium hydride.
  • organic lithium compounds include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, n-butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.
  • the reaction of the process (b) can be carried out at a temperature within a substantially broad range, but it can generally be carried out at a temperature of about -80 to about 200°C, preferably about -60 to about 150°C. Further, the reaction should preferably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.
  • 1 mole of the compounds of the formula (IV) can be reacted with 1 to 1.3 molar amounts of the compounds of the for- mula (V)in a diluent such as toluene, if desired in the presence of an inorganic alkali metal hydride or an organic lithium compound to obtain the desired compounds.
  • a diluent such as toluene
  • the reaction of the above process (c) is known per se or can be carried out by a process similar to a known one.
  • the reaction of the above-mentioned process (c) can be carried out in an appropriate diluent as, for example, inert solvents.
  • suitable diluents are: aromatic hydrocarbons such as benzene, toluene, xylene and pyridine; and ethers such as di- oxane, dimethoxyethane (DME) and tetrahydrofuran (THF).
  • the reaction of the process (c) can be carried out at a temperature within a substantially broad range, but it can generally be carried out at a temperature of about 30 to about 200°C, preferably about 50 to about 150°C. Further, the reaction should preferably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.
  • the compounds of the formula (I) according to the invention exhibit a powerful insecticidal activity. Further, the active compounds of the formula (I) according to the invention exhibit penetrating and translocating properties, and exhibit precise effects for combating injurious insects without causing phytotoxicity against cultivated plants.
  • the compounds according to the invention can be used for combating a broad range of various insects, particularly injurious sucking insects, biting insects, soil insects and other plant-parasitic insects as well as insects of stored cereals and hy- giene insects, and can be used for destructing them.
  • insects examples of such insects are as follows:
  • Insects from the order of the Coleoptera for example, Callosobruchus chinensis, Si- tophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotrarsa decemlineata, Diabrotica spp., Mono- chamusretematus, Lissorhoptrus oryzophilus, Aulacophora femoralis and Lyctus bruneus;
  • insects from the order of the Lepidoptera for example, Lymantria dispar, Mala- cosoma maneustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo sup- pressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Heliothis vires- cens and Phyllocnistis citrella;
  • insects from the order of the Hemiptera for example, Nephotettix cincticeps,
  • Nilaparvata lugens Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Lipaphis erysimi, Stephanitis nashi, Nezara spp., Cimex lectularius, Trialeurodes vaporariorum and Psylla spp.;
  • insects from the order of the Orthoptera for example, Blattela germanica, Periplaneta americana, Gryllotralpa africana and Locusta migratorioides;
  • insects from the order of the Isoptera for example, Deucotermes speratus and Cop- totermes formosanus;
  • insects from the order of the Diptera for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis and Culex tritaeniorhynchus.
  • acarina there may be mentioned, for example, Tetranychus kanzawai, Tetrany- chus urticae, Panonychus citri, Aculops pelekassi and Tarsonemus spp.
  • nematodes there may be mentioned, for example, Meloidogyne incognita, Bursa- phelenchus xylophilus, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp.
  • various injurious animal parasites endoparasites and ectoparasites
  • insects and helminths such as insects and helminths.
  • animal parasites examples include the following insects:
  • insects there may be mentioned, for example, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp. and Ctenocephalides spp.
  • tick there may be mentioned, for example, Ornithodoros spp., Ixodes spp. and
  • insecticide(s) the compounds useful for combatting all the insects as mentioned above, are often referred generically to as "insecticide(s)" .
  • the active compounds of the invention can be converted into customary formulations, such as solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, very fine capsules and coating compositions for seed, furthermore in formulations used with buring equipment, such as fumigating cartridges, fumigating cans and fumigating coils and the like, as well as ULV cold- and warm-mixed formulations.
  • customary formulations such as solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, very fine capsules and coating compositions for seed, furthermore in formulations used with buring equipment, such as fumigating cartridges, fumigating cans and fumigating coils and the like, as well as ULV cold- and warm-mixed formulations.
  • formulations are produced in a manner known per se, for example, by mixing the active compounds with extenders, for example, liquid solvents, liquefied gas diluents under pressure, solid diluents or carriers, optionally with the use of surface- active agents, for instance emulsifying agents and/or dispersing agents and/or foam- forming agents.
  • extenders for example, liquid solvents, liquefied gas diluents under pressure, solid diluents or carriers, optionally with the use of surface- active agents, for instance emulsifying agents and/or dispersing agents and/or foam- forming agents.
  • liquid solvents or carriers there are suitable: for example, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes; chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as butanol and glycol as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ke- tone or cyclohexanone; strongly polar solvents, such as dimethylformamide and di- methylsulfoxide; as well as water.
  • aromatic hydrocarbons such as xylene, toluene or alkyl naphthalenes
  • chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons such as chlorobenzen
  • organic solvents can be used as auxiliary solvents.
  • Liquified gaseous diluents or carriers means liquids obtained by liquefying gaseous substances which are gaseous at room temperature and under atmospheric pressure, for example aerosol propellants, such as butane, propane, nitrogen, carbon dioxide and halogenohydrocarbons.
  • ground natural minerals such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma- ceous earth
  • ground synthetic minerals such as highly-dispersed silicic acid, alumina or silicates.
  • solid carriers for granules there are suitable: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite
  • synthetic granules of inorganic and organic meals such as sawdust, coconut shells, maize cobs and tobacco stalks.
  • emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene- fatty acid alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as protein hydrolysation products.
  • emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene- fatty acid alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as protein hydrolysation products.
  • dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
  • Adhesives may also be used in formulations such as powders, granules and emul- sions, and the followings are examples of usable adhesives: for example carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.
  • colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of metals, for example iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the formulations in general can contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of the above active compounds.
  • the active compounds of the formula (I) according to the invention can be present in their commercially available formulations and in the use forms prepared with these formulations, as a mixture with other active compounds, such as insecticides, attrac- tants, sterilants, miticides, nematocides, fungicides, growth-regulating substances or herbicides.
  • active compounds such as insecticides, attrac- tants, sterilants, miticides, nematocides, fungicides, growth-regulating substances or herbicides.
  • the above insecticides include, for example, organic phosphate, carba- mates, carboxylates, chlorinated hydrocarbons, chloronicotinyls and insecticidal substances produced by microorganisms.
  • the active compounds of the formula (I) according to the invention can further be present as a mixture with synergistic agents.
  • Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
  • the content of the active compounds of the formula (I) according to the invention in their commercially available use form can be varied within wide limits, for instance within the range of from 0.0000001 to 100% by weight, preferably between 0.00001 and 1 % by weight.
  • the compounds of the formula (I) according to the invention can be employed against insects, in a customary manner appropriate for the use forms.
  • the active compounds according to the invention are extremely excellent in stability to alkali on limed substances and in residual activity on wood and soil.
  • Table 1 shows the compounds of Examples 1 and 2 together with the compounds produced in a manner similar to those of the above Examples 1 or 2 as well as the compounds which can be synthesized in a manner similar to those of the above Examples 1 or 2.
  • Emulsifier 1 part by weight of polyoxyethylene alkyl phenyl ether
  • Leaves of cabbage (Bassica oleracea) were dipped into the water solution of the active compound at the prescribed concentration. After air-drying of the solution, the treated leaves of cabbage were placed in a Petri dish (diameter: 9 cm), and ten of the third-instar larvae of common cutworms (Spodoptera Iitura) were released. The dish was then placed at an incubation chamber of 28°C. After 7 days, the number of dead larvae was examined to calculate mortality in %. Tests was successively conducted three times and the mortality in % is shown in their average.

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Abstract

Fluoro-substituted benzoylureas of formula (I) wherein R?1, R2 and R3¿ each independently represent a hydrogen atom, nitro, cyano, halogen, C¿1-3?-alkyl, C1-3-haloalkyl, C1-3-alkoxy, C1-3-haloalkoxy, C1-3-alkylthio or C1-3-haloalkylthio, with the proviso that all of R?1, R2 and R3¿ do not simultaneously represent hydrogen atoms, R4 represents a hydrogen atom, nitro, cyano, halogen, C¿1-3?-alkyl, C1-3-haloalkyl, C1-3-alkoxy, C1-3-haloalkoxy, C1-3-alkylthio or C1-3-haloalkythio, R?5¿ represents optionally substituted C¿2-20?-fluoroalkyl, optionally substituted C4-20-(carbon atoms in total) fluorocycloalkyl-alkyl, optionally substituted C3-10-fluorocycloalkyl, optionally substituted C4-20-(carbon atoms in total) fluoroalkyl-cycloalkyl or optionally substituted C3-20-fluoroalkenyl, X and Y each independently represent an oxygen atom or a sulfur atom, and n is 1 or 2, processes for their preparation, compositions containing them, and their use as insecticides.

Description

INSECTICIDAL FLUORO-SUBSTITUTED BENZOYLUREAS
The present invention relates to novel fluoro-substituted benzoylureas, to processes for their preparation and to their use as insecticides.
It has already been known that certain kinds of benzoylureas, bearing an aliphatic group, possess insecticidal activities (see Japanese Patent Laid-open No. Sho 60- 224667-A).
There have now been found fluoro-substituted benzoylureas of the formula (I),
Figure imgf000003_0001
wherein
R1 , R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen,
Cj^-alkyl, C^-haloalkyl, Cj.3-alkoxy, Cj_3-haloalkoxy, Cj.3-alkyl-thio or C1_3-haloalkylthio, with the proviso that all of R1, R2 and R3 do not simultaneously represent a hydrogen atom,
R4 represents a hydrogen atom, nitro, cyano, halogen, C^-alkyl, Cι_3-haloalkyl,
Cj_3-alkoxy,
Figure imgf000003_0002
Cj.3-alkylthio or Cj.3-haloalkylthio,
R5 represents optionally substituted C2_2o- luoroalkyl, optionally substituted C4. 2o-(carbon atoms in total) fluorocycloalkyl-alkyl, optionally substituted C3_ iQ-fluorocycloalkyl, optionally substituted C4_2o-(carbon atoms in total) fluoroalkyl-cycloalkyl or optionally substituted C3_2o- fluoroalkenyl,
X and Y each independently represent an oxygen atom or a sulfur atom, and n is 1 or 2.
The compounds of the above formula (I) can exist as isomers and include not only an isolated isomer but also a mixture of isomers in an arbitrary ratio.
The compounds of the formula (I), according to the invention, can be prepared by a process in which
a) compounds of the formula (II)
Figure imgf000004_0001
wherein R1 , R2, R3, R4, X, Y and n are defined as above,
are reacted with compounds of the formula (III) or their salts
R°
HN (III)
\
H
wherein R5 is defined as above,
in the presence of inert solvents,
or
b) compounds of the formula (IV)
Figure imgf000005_0001
wherein R1, R2, R3, R4, X and n are defined as above,
are reacted with compounds of the formula (V)
R&
/
Y: :N (V)
wherein R5 and Y are defined as above,
in the presence of inert solvents, and, if appropriate, in the presence of an inorganic alkali metal hydride or an organic lithium compound,
or
c) in a case where X and Y represent a sulfur atom:
compounds of the formula (VI)
Figure imgf000005_0002
wherein R1, R2, R3, R4, R5 and n are defined as above,
are reacted with phosphorus pentasulfide or Lawesson's reagent in the presence of inert solvents.
The fluorosubstituted benzoylureas of the formula (I), according to the invention, exhibit a powerful insecticidal activity.
The fluoro-substituted benzoylureas of the formula (I) according to the invention, un- expectedly, exhibit substantially, extremely superior insecticidal activity in comparison with the previously known compounds described in the above prior art.
In this specification, when the optionally substituted radical or the radical "which may be substituted is substituted by more than one substituent, these substituents may be same or different from one another.
In this specification, the halogen in "halogen" and halogenated substituents like in "haloalkyl", "haloalkoxy and so on, represents fluorine, chlorine, bromine or iodine, preferably fluorine, chlorine or bromine, especially preferably fluorine or chlorine.
In this specification, the alkyl may be straight-chain or branched and includes, for example, methyl, ethyl,propyl, isopropyl, n-, iso-, sec- or tert-butyl, and the like.
In this specification, the haloalkyl may be straight-chain or branched and includes, for example, trifluoromethyl, 2,2,2-trifluoroethyl, and the like.
In this specification, the alkoxy may be straight-chain or branched and includes, for example, methoxy, ethoxy, propoxy, isopropoxy, n-, iso-, sec- or tert-butoxy, and the like. In this specification, the haloalkoxy may be straight-chain or branched and includes, for example, difluoromethoxy, trifluoromethoxy, chlorodifluoromethoxy, 2,2,2-tri- fluoroethoxy, and the like.
In this specification, the "alkylthio" may be straight-chain or branched and includes, for example, methylthio, ethylthio, propylthio, isopropylthio, n-, iso-, sec- or tert- butylthio, and the like.
In this specification, the haloalkylthio may be straight-chain or branched and in- eludes, for example, trifluoromethylthio, difluoromethylthio, chlorodifluoromethyl- thio, 2,2,2-trifluoroethylthio, and the like.
In this specification, the "fluoroalkyl" represents a straight-chain or branched alkyl radical having, if not indicated otherwise, 2 to 20 carbon atoms, which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two, substituent(s) selected from the group consisting of chlorine, bromine, phenyl, C3_.g-cycloalkyl and C3.g-fluorocycloalkyl. Examples of "fluoroalkyl" include 2-fluoroethyl, 2,2-difluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2,2-trifluoro- ethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 2,3-difluoropropyl, 3,3,3- trifluoropropyl, 2,3,3-trifluoropropyl, 2,3,3,3-tetrafluoropropyl, 2,2,3,3 -tetrafluoro- propyl, 2,2,3,3,3-pentafluoropropyl, 3-chloro-2-fluoropropyl, 3,3-dichloro-2,2-di- fluoropropyl, 2,2,2-trifluoro- 1 -methylethyl, 2,2,2-trifluoro- 1 -(tri-fluoromethyl)ethyl, 3-chloro-3-fluoropropyl, 3,3-dichloro-3-fluoropropyl, 3,3-difluoropropyl, 3-chloro- 3,3-difluoropropyl, 2-fluoro-l -methylethyl, 2-fluoro-l-(fluoromethyl)ethyl, 2-chloro- l-(fluoromethyl)ethyl, 4,4,4-trifluorobutyl, 3,3,4,4-tetra-fluorobutyl, 2,2,3,4,4,4- hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 4,4-dichloro-4-fluoro butyl, 3,4-di- chloro-3,4,4-trifluorobutyl, 2,2,3,3, 3-pentafluoro-l-methylpropyl, 2-fluoro-l,l-di- methy lethyl, 2-fluoro- 1 -(fluoromethy 1)- 1 -methylethyl, 2-fluoro- 1,1- bis(fluoromethyl)ethyl, 2,2,2-trifluoro- 1 , 1 -dimethylethyl, 2,3 ,3 ,3 -tetrafluoro- 1 -meth- ylpropyl, 1 -(trifluoromethyl)propyl, 3,3,3-trifluoro-l-methyl-propyl, 2,2,2-trifluoro-
1 -methyl- l-(trifluoromethyl)ethyl, 3,3,3-trifluoro-2-(trifluoromethyl)propyl, 2,2,2- - o -
trifluoro- 1 , 1 -bis(trifluoromethyl)propyl, 3,3-dichloro-3-fluoro-2-methylpropyl, 2- chloro-3 ,3 ,3-trifluoro- 1 -methylpropyl, 2,3 ,3 ,3-tetrafluoro- 1 -methylpropyl, 3 ,3-di- chloro-3 -fluoro-2-methylpropyl, 3 -chloro-3 ,3 -difluoro-2-methylpropyl, 3,3 ,3-tri- fluoro-2-methylpropyl, 2,3-difluoro-2-(fluoromethyl)propyl, 3 ,3 ,3-trifluoro- 1 -(tri- fluoromethyl)propyl, 4,4,5, 5,5-pentafluoropentyl, 2,2,3,3,4,4,5,5-octafluoropentyl,
2,2,3,3,4,4,5,5,5-nonafluoropentyl, 2,2,3,3,4,4,4-heptafluoro-l-methylbutyl, 4,4,4- trifluoro-2-methylbutyl, 2,3-difluoro-3-methylbutyl, 3,4,4,4-tetrafluoro-3-(trifluo- romethyl)butyl, 2,2,3,3,3-pentafluoro- 1 , 1 -dimethylpropyl, 3,3,3-trifluoro-2-methyl- 2-(trifluoromethy l)propyl, 2,2-difluoro- 1 , 1 -dimethylpropyl, 2,2,3 ,3 -tetrafluoro- 1,1- dimethylpropyl, 3, 3 -dichloro-2,2-difluoro- 1,1 -dimethylpropyl, 3,3,3-trifluoro-l,l- dimethylpropyl, 2-methyl-l-(trifluoromethyl)propyl, 3,3,4,4,5, 5,6,6,6-nonafluoro- hexyl, 3,4,4,5,5,5-hexafluoro-3-(trifluoromethyl)pentyl, 4,5,5,5-tetrafluoro-4-(trifluo- romethyl)pentyl, 1 H, 1 H,7H-dodecafluoroheptyl, 1 H, 1 H-tridecafluoroheptyl,
1 H, 1 H,2H,2H-perfluoro-5-methylhexyl, 3,4,4,5,5, 5-hexafluoro-3-(trifluoromethyl) 1 - methylpentyl, 7,7,8,8,8-pentafluorooctyl, lH,lH,2H,2H-perfluorooctyl, lH,lH-per- fluorooctyl, 1 -(trifluoromethyl)heptyl, 4,4,5,5,6,6,7,7,8, 8,9,9,9-tridecanefluorononyl, 1 H, 1 H,9H-hexadecafluorononyl, 1 H, 1 H-perfluorononyl, 1 -(trifluoromethyl)octyl, 3 ,3 ,4,4,5,5,6,6,7,7,8,8,9,9, 10,10,10-heptadecafluorodecyl, 1 H, 1 H-perfluorodecyl
3,3,4,4,5, 5,6,6,6-nonafluoro-l-(perfluorobutyl)hexyl, l-butyl-3,4,4,5,5,5-hexa- fluoro3-(trifluoromethyl)pentyl, 1H,1H,1 lH-perfluoroundecyl, and the like.
In this specification, the "fluorocycloalkyl" represents a cycloalkyl radical which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two, substituent(s) selected from the group consisting of chlorine, bromine and Cj.3-alkyl. Examples of "fluorocycloalkyl" include 2-fluoro- cyclopropyl, 2,2-difluorocyclopropyl, 2-fluoro-cyclohexyl, 2-chloro-2-fluorocyclo- propyl, 2-chloro-3-fluoro-cyclopropyl, 2,2-difluoro-l-methylcyclopropyl, 2-chloro- 2,3,3-trifluoro-l-methylcyclobutyl, and the like.
In this specification, the "fluoroalkyl-cycloalkyl"represents a cycloalkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by alkyl which is substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two substituent(s) selected from the group consisting of chlorine, bromine and C]_3-alkyl. Examples of fluoroalkyl-cycloalkyl include l-(l,l-difluoroethyl)cyclohexyl, l-(l,l,2,2-tetrafluoroethyl)cyclohexyl, 3-tri- fluoromethylcyclohexyl, 2-trifluoromethylcyclohexyl, 1 -(trifluoromethyl)cyclo- propyl, 2-(trifluoromethyl)cyclopentyl, 2,4-bis(trifluoromethyl)cyclohexyl, 2-(tri- fluoromethyl)-l-methylcyclohexyl, and the like.
In this specification, the "fluorocycloalkyl-alkyl" represents an alkyl radical with, if not indicated otherwise, 4 to 20 carbon atoms in total, which is substituted by cycloalkyl substituted by at least one fluorine, and which may further be substituted by one or more, preferably one or two) substituent(s) selected from the group consisting of chlorine, bromine and Cj.3-alkyl. Specific examples thereof include, for example, (perfluorocyclohexyl)methyl, 2-( 1 -fluorocyclohexyl)ethyl, 2-( 1 ,2-difluorocyclo- hexyl)ethyl, and the like.
In this specification, the "fluoroalkenyl" represents astraight-chain or branched alkenyl radical with, if not indicated otherwise, 3 to 20 carbon atoms, which is substituted by at least one fluorine, and which may further be substituted by one or more (preferably one or two) substituent(s) selected from the group consisting of chlorine, bromine and alkoxy carbonyl. Specific examples thereof include, for example, 2,3,3- trifluoro-2-propenyl, 3,4,4-trifluoro-3-butenyl, 4,4,4-trifluoro-2-butenyl, 4,4-di- fluoro-3-methylbutenyl, 4,4,5,5,6,6,7,7,7-nonafluoro-2-heptenyl, 4-trifluoromethyl- 4,5,5,6,6,6-hexafluoro-2-hexenyl, 3-(perfluorohexyl)-2-propenyl, and the like.
In this specification "examples" are given without limiting the scope of the invention.
Preferred compounds of the above formula (I) are compounds, wherein
R1, R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, tri- fluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-tri- flu- oroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, di- fluoromethylthio or 2,2,2-trifluoroethylthio, with the proviso that all of R1, R2 and R3 do not simultaneously represent a hydrogen atom,
R4 represents a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, difluoromethylthio or 2,2,2-tri- fluoroethylthio,
R5 represents C2_π -fluoroalkyl which may be substituted by one or more, (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine and bromine or represents C4_8-fluorocycloalkyl- alkyl which may be substituted by one or more (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine and bromine or represents C3.jo-fluorocycloalkyl which may be substituted by one or more (preferably one or two, especially preferably one) substituent(s) selected from the group consisting of chlorine, bromine and methyl, or represents C4_1o-fluoroalkyl- cycloalkyl or represents C3_5-fluoro- alkenyl,
X and Y each independently represent an oxygen atom or asulfur atom, (preferably an oxygen atom) and
n is 1 or 2 (preferably 1).
Particularly preferred compounds of the above formula (I) are compounds, wherein R1, R2 and R3 each independently represent a hydrogen atom, fluorine, chlorine, bromine, methoxy, trifluoromethyl, nitro or methyl, with the proviso that all of R1, R2 and R3 do not simultaneously represent a hydrogen atom,
R4 represents a hydrogen atom, fluorine or trifluoromethyl,
R5 represents 2-fluoroethyl, 2,2,2-trifluoroethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-difluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl,
2,2,3,3,3-pentafluoropropyl, 4,4,4-trifluorobutyl, 2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl, 2,2,3,3,4,4,5,5-octafluoropentyl, 2-fluoro-l- methylethyl, 2-chloro- 1 -(fluoromethy l)ethyl, 2-fluoro- 1 -(fluoromethyl)ethy 1, 2,2,2-trifluoro- 1 -methylethyl, 2-fluoro- 1 , 1 -dimethylethyl, 2-fluoro- 1 , 1 -bis- (fluoromethyl)ethyl, 2,2,2-trifluoro- 1 , 1 -dimethylethyl, 3 ,3 ,3 -trifluoro- 1 , 1 -dimethylpropyl, 3,3,4,4,5,5,6,6,6-nonafluorohexyl, lH,lH,7H-dodecafluoro- heptyl, lH,lH-perfluorooctyl, 2-fluorocyclopropyl, 2-chloro-2-fluorocyclo- propyl, 2,2-difluorocyclopropyl, 2,2-difluoro-l-methylcyclopropyl, 2-(trifluo- romethyl)cyclopentyl, 2,4-bis(trifluoromethyl)cyclohexyl, 2,3,3-trifluoro-2- propenyl or 3,4,4-trifluoro-3butenyl, 2-chloro-2,2-difluoroethyl, 2-chloro-3- fluorocyclopropyl, 2,2,2-trifluoro-l -methyl- 1-trifluoromethyl-ethyl, 3,3,3-tri- fluoro-2-trifluoromethyl-propyl, 2,2,3,3,4,4,4-heptafluoro-l -methyl-butyl,
3,3,3-trifluoro-2-methyl-2-trifluoromethyl-propyl, 4,4-difluoro-3-methyl-3- butenyl, 3-trifluoromethyl-cyclohexyl, 2-ethoxycarbonyl- 1 -trifluoromethyl- ethylenyl, 2-tri-fluoromethylcyclohexyl, 2-fluoro- 1 -fluoromethyl- 1 -methylethyl, lH,lH,2H,2H-perfluorooctyl, 1-trifluoromethyloctyl, 3,4-dichloro- 3,4,4-trifluorobutyl, 2-fluorocyclohexyl, 2,3-difluoropropyl, 2,3,3-trifluoro- propyl, lH,lH-perfluorononyl, lH,lH,l lH-perfluoroundecyl.
X and Y represent an oxygen atom, and
n is 1 or 2 (preferably 1). Specific examples of the compounds of the formula (I) according to the invention are shown in the later-described Table 1.
The course of the reaction in the above-mentioned process (a) is represented by the following reaction equation when, for example, the starting materials are 2,6-di- fluorobenzoyl isocyanate and 2,2,3,3,3-pentafluoroρropylamine:
Figure imgf000012_0001
The course of the reaction in the above-mentioned process (b) is represented by the following reaction equation when, for example, the starting materials are 2,6-di- fluoro-benzamide and 2,2,3,3,3-pentafluoro-propyl isocyanate:
Figure imgf000012_0002
The course of the reaction in the above-mentioned process (c) is represented by the following reaction equation when, for example, the starting materials are 1- (2,2,3,3,3-pentafluoropropyl)-3-(2,6-difluorobenzoyl) urea and phosphorus penta- sulfide:
Figure imgf000013_0001
In the above-mentioned process (a), the compounds of the formula (II), used as starting materials are those wherein R1, R2, R3, R4, X, Y and n are defined as above.
The compounds of the formula (II) are known compounds and can be obtained, for example, by the processes similar to those described in Journal of Organic Chemistry
Vol. 27, 1962, 3742-3743; ib. Vol. 30, 1965, 4306-4307; Journal of the American Chemical Society Vol. 59, 1973, 2011-2013; ib. Vol. 61, 1939, 632-633; ib. Vol. 62, 1940, 1595-1596 and Organic Syntheses Coll. Vol. 3, 1955, 735-736.
As examples, the compounds of the formula (II) include 2-fluorobenzoyl-isocyanate,
2-chlorobenzoyl-isocyanate, 2,4-difluorobenzoyl-isocyanate, 2-fluoro-4-chloro- benzoyl-isocyanate, 2,6-difluorobenzoyl-isocyanate, 2-chloro-6-fluorobenzoyl-iso- cyanate, 2,6-dichlorobenzoyl-isocyanate, 2,4,6-trifluorobenzoyl-isocyanate, and the like.
In the above-mentioned process (a), the compounds of the formula (III) used as starting materials are those wherein R5 is defined as above. The compounds of the formula (III) are known compounds and can be obtained, for example, by the processes described in Joumal of The American Chemical Society Vol. 72, 1950, 2786-2788 and Organic Syntheses Coll. Vol. 3, 1955, 151-156.
As examples, the compounds of the formula (III) include 2,2,2-trifluoroethylamine,
2,2-difluoropropylamine, 3,3,3-trifluoropropylamine, 2,2,3,3,3-pentafluoropropyl- amine, 2,2,3,3,4,4,4-heptafluorobutylamine, 2,2,3,3,4,4,5, 5-octafluoropentylamine, 1 -fluoro-2-propylamine, 1 -chloro-3 -fluoro-2-propylamine, 1 ,3 -difluoro-2-propyl- amine, 1,1,1 -trifluoro-2-propylamine, 1 -fluoro-2-methy 1-2-propy lamine, 1 ,3 -di- fluoro-2-methyl-2-propylamine, 1 ,3 -difluoro-2-(fluoromethyl)-2-propy lamine, 1,1,1- trifluoro-2-methyl-2-propylamine, 3,3 ,3 -trifluoro- 1 , 1 -dimethylpropylamine, 1,1,1 -tri- fluoro-3 -methyl-butylamine, 2-fluoro- 1 -cyclopropylamine, 2,2-difluoro- 1 -cyclo- propylamine, 2,2-difluoro- 1 -methyl- 1 -cyclopropylamine, 1 -(trifluoromethyl)- 1 - cyclopropylamine, 2-chloro-2,3,3-trifluoro-l -methyl- 1 -cyclobutylamine, 2-(trifluo- romethyl)-l-cyclopenty lamine, 2,4-di(trifluoromethyl)-l-cyclohexylamine, 3,4,4-tri- fluoro-3-buten- 1 -ylamine.
The compounds of formula (III) can be used in form of salts, for example as hydro- chlorides, hydrobromides or acetates.
In the above process (b), the compounds of the formula (IV) used as the starting material are those wherein R1, R2, R3, R4, X and n are defined as above.
The compounds of the formula (IV) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of Medicinal
Chemistry Vol. 11, 1963, 814-819 or Organic Syntheses Coll. Vol. 3, 1955, 490-492.
In the above process (b), the compounds of the formula (V) used as the starting material are those wherein R3 and Y are defined as above. The compounds of the formula (V) are known compounds and can be synthesized, for example, by the processes similar to those described in Journal of The American Chemical Society Vol. 72, 1950, 1888-1891 or Organic Syntheses Coll. Vol 3, 1955, 599-600.
In the above process (c), the compounds of the formula (VI) used as the starting material, which may be mentioned, are those wherein Rl, R2, R3, R4, R5 and n are defined as above.
The compounds of the formula (VI) are the compounds of the invention, which are synthesized by the above processes (a) or (b).
In the process (c), Lawesson's reagent is 4-methoxyphenylthionophosphine sulfide dimer.
The reaction of the above-mentioned process (a) can be carried out in an appropriate diluent. Examples of usable diluents, which may be mentioned, are: aliphatic, alicyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pentane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichloromethane, chloroform, carbon tetrachloride, 1 ,2-dichloroethane, chloroben- zene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and di- ethylene glycol dimethyl ether (DGM); nitriles such as acetonitrile, propionitrile and acrylonitrile; esters such as ethyl acetate and amyl acetate; acid amides such as di- methylformamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3- dimethyl-2-imidazolidinone and hexamethylphosphoric triamide (HMPA); sulfones and sulfoxides such as dimethyl sulfoxide (DMSO) and sulfolan; and bases such as pyridine.
When the compound of the formula (III) is a salt, the reaction of the process (a) can be carried out in the presence of an organic base or an organic lithium compound. Examples of usable organic bases include tertiary alcoholates, tertiary amines, dial- kylaminoanilines and pyridines, such as triethylamine, 1 , 1 ,4,4-tetramethylethylene- diamine (TMEDA), N,N-dimethylaniline, N,N-diethylaniline, pyridine, 4-dimeth- ylaminopyridine (DMAP), l,4-diazabicyclo[2,2,2]octane (DABCO) and 1,8-diazabi- cyclo[5,4,0]undec-7-ene (DBU). Examples of organic lithium compounds include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, n- butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.
The reaction of the process (a) can be carried out at a temperature within a substan- tially broad range, but it can generally be carried out at a temperature of about -10 to about 120°C, preferably about 0 to about 100°C. Further, the reaction should preferably be conducted under atmospheric pressure but it may optionally be operated under elevated or reduced pressure.
For carrying out the process (a), for instance, when the compounds of the formula
(III) is not a salt, 1 mole of the compounds of the formula (II) can be reacted with 1 to 1.3 molar amounts of the compounds of the formula (III) in a diluent such as toluene to obtain the desired compounds.
For carrying out the process (a), for instance, when the compounds of the formula
(III) is a salt, 1 mole of the compounds of the formula (II) can be reacted with 1 to 1.3 molar amounts of the compounds of the formula (III) in a diluent such as tetrahy- drofuran in the presence of an organic base to thereby obtain the desired compounds.
The reaction of the above process (b) is known per se orcan be carried out by a process similar to a known one.
The reaction of the above-mentioned process (b) can be carried out in an appropriate diluent. Examples of usable diluents, which may be mentioned, are: aliphatic, ali- cyclic or aromatic hydrocarbons (which may optionally be chlorinated) such as pen- tane, hexane, cyclohexane, petroleum ether, ligroin, benzene, toluene, xylene, dichlo- romethane, chloroform, carbon tetrachloride, 1,2-dichloroethane, chlorobenzene and dichlorobenzene; ethers such as ethyl ether, methyl ethyl ether, isopropyl ether, butyl ether, dioxane, dimethoxyethane (DME), tetrahydrofuran (THF) and diethylene gly- col dimethyl ether (DGM); nitriles such as acetonitrile, propionitrile and acryloni- trile; esters such as ethyl acetate and amyl acetate; acid amides such as dimethyl- formamide (DMF), dimethylacetamide (DMA), N-methylpyrrolidone, 1,3-dimethyl- 2-imidazolidinone and hexamethylphosphoric triamide (HMPA); sulfones and sulf- oxides such as dimethyl sulfoxide (DMSO) and sulfolan; and bases such as pyridine.
The reaction of the process (b) can be carried out in the presence of an inorganic alkali metal hydride or an organic lithium compound. Examples of usable inorganic alkali metal hydrides include lithium hydride, sodium hydride and potassium hydride. Examples of organic lithium compounds include methyllithium, n-butyllithium, sec-butyllithium, tert-butyllithium, phenyllithium, n-butyllithium DABCO, n-butyllithium DBU and n-butyllithium TMEDA.
The reaction of the process (b) can be carried out at a temperature within a substantially broad range, but it can generally be carried out at a temperature of about -80 to about 200°C, preferably about -60 to about 150°C. Further, the reaction should preferably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.
For carrying out the process (b), for instance, 1 mole of the compounds of the formula (IV) can be reacted with 1 to 1.3 molar amounts of the compounds of the for- mula (V)in a diluent such as toluene, if desired in the presence of an inorganic alkali metal hydride or an organic lithium compound to obtain the desired compounds.
The reaction of the above process (c) is known per se or can be carried out by a process similar to a known one. The reaction of the above-mentioned process (c) can be carried out in an appropriate diluent as, for example, inert solvents. Examples of usable diluents are: aromatic hydrocarbons such as benzene, toluene, xylene and pyridine; and ethers such as di- oxane, dimethoxyethane (DME) and tetrahydrofuran (THF).
The reaction of the process (c) can be carried out at a temperature within a substantially broad range, but it can generally be carried out at a temperature of about 30 to about 200°C, preferably about 50 to about 150°C. Further, the reaction should preferably be conducted under normal pressure but it may optionally be operated under elevated or reduced pressure.
For carrying out the process (c), for instance, 1 mole of the compounds of the formula (VI) can be reacted with 0.5 to 2 molar amounts of phosphorus pentasulfide or Lawesson's reagent to obtain the aimed compounds.
The compounds of the formula (I) according to the invention exhibit a powerful insecticidal activity. Further, the active compounds of the formula (I) according to the invention exhibit penetrating and translocating properties, and exhibit precise effects for combating injurious insects without causing phytotoxicity against cultivated plants.
Further, the compounds according to the invention can be used for combating a broad range of various insects, particularly injurious sucking insects, biting insects, soil insects and other plant-parasitic insects as well as insects of stored cereals and hy- giene insects, and can be used for destructing them.
Examples of such insects are as follows:
Insects from the order of the Coleoptera, for example, Callosobruchus chinensis, Si- tophilus zeamais, Tribolium castaneum, Epilachna vigintioctomaculata, Agriotes fuscicollis, Anomala rufocuprea, Leptinotrarsa decemlineata, Diabrotica spp., Mono- chamus altematus, Lissorhoptrus oryzophilus, Aulacophora femoralis and Lyctus bruneus;
insects from the order of the Lepidoptera, for example, Lymantria dispar, Mala- cosoma maneustria, Pieris rapae, Spodoptera litura, Mamestra brassicae, Chilo sup- pressalis, Pyrausta nubilalis, Ephestia cautella, Adoxophyes orana, Carpocapsa pomonella, Agrotis fucosa, Galleria mellonella, Plutella xylostella, Heliothis vires- cens and Phyllocnistis citrella;
insects from the order of the Hemiptera, for example, Nephotettix cincticeps,
Nilaparvata lugens, Pseudococcus comstocki, Unaspis yanonensis, Myzus persicae, Aphis pomi, Aphis gossypii, Lipaphis erysimi, Stephanitis nashi, Nezara spp., Cimex lectularius, Trialeurodes vaporariorum and Psylla spp.;
insects from the order of the Orthoptera, for example, Blattela germanica, Periplaneta americana, Gryllotralpa africana and Locusta migratorioides;
insects from the order of the Isoptera, for example, Deucotermes speratus and Cop- totermes formosanus; and
insects from the order of the Diptera, for example, Musca domestica, Aedes aegypti, Hylemia platura, Culex pipiens, Anopheles sinensis and Culex tritaeniorhynchus.
As acarina, there may be mentioned, for example, Tetranychus kanzawai, Tetrany- chus urticae, Panonychus citri, Aculops pelekassi and Tarsonemus spp.
As nematodes, there may be mentioned, for example, Meloidogyne incognita, Bursa- phelenchus xylophilus, Aphelenchoides besseyi, Heterodera glycines and Pratylenchus spp. Further, in the pharmaceutical field of veterinary medicine, there may be mentioned various injurious animal parasites (endoparasites and ectoparasites), such as insects and helminths.
Examples of such animal parasites include the following insects:
As insects, there may be mentioned, for example, Gastrophilus spp., Stomoxys spp., Trichodectes spp., Rhodnius spp. and Ctenocephalides spp.
As tick, there may be mentioned, for example, Ornithodoros spp., Ixodes spp. and
Boophilus spp.
In this specification, the compounds useful for combatting all the insects as mentioned above, are often referred generically to as "insecticide(s)" .
In the case of the use as insecticides, the active compounds of the invention can be converted into customary formulations, such as solutions, wettable powders, emulsions, suspensions, powders, foams, pastes, tablets, granules, aerosols, natural and synthetic materials impregnated with active compounds, very fine capsules and coating compositions for seed, furthermore in formulations used with buring equipment, such as fumigating cartridges, fumigating cans and fumigating coils and the like, as well as ULV cold- and warm-mixed formulations.
These formulations are produced in a manner known per se, for example, by mixing the active compounds with extenders, for example, liquid solvents, liquefied gas diluents under pressure, solid diluents or carriers, optionally with the use of surface- active agents, for instance emulsifying agents and/or dispersing agents and/or foam- forming agents.
As liquid solvents or carriers, there are suitable: for example, aromatic hydrocarbons, such as xylene, toluene or alkyl naphthalenes; chlorinated aromatic hydrocarbons and chlorinated aliphatic hydrocarbons, such as chlorobenzenes, chloroethylenes or methylene chloride; aliphatic hydrocarbons, such as cyclohexane or paraffins, for example mineral oil fractions; alcohols, such as butanol and glycol as well as their ethers and esters; ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ke- tone or cyclohexanone; strongly polar solvents, such as dimethylformamide and di- methylsulfoxide; as well as water.
In the case of the use of water as the extender, organic solvents can be used as auxiliary solvents.
"Liquefied gaseous diluents or carriers" means liquids obtained by liquefying gaseous substances which are gaseous at room temperature and under atmospheric pressure, for example aerosol propellants, such as butane, propane, nitrogen, carbon dioxide and halogenohydrocarbons.
As solid diluents or carriers there are suitable: for example, ground natural minerals, such as kaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite or diatoma- ceous earth, and ground synthetic minerals, such as highly-dispersed silicic acid, alumina or silicates.
As solid carriers for granules there are suitable: for example, crushed and fractionated natural rocks such as calcite, marble, pumice, sepiolite and dolomite, as well as synthetic granules of inorganic and organic meals, and granules of organic material such as sawdust, coconut shells, maize cobs and tobacco stalks.
As emulsifying and/or foam-forming agents there are suitable: for example non-ionic and anionic emulsifiers, such as polyoxyethylene-fatty acid esters, polyoxyethylene- fatty acid alcohol ethers, for example alkylaryl polyglycol ethers, alkylsulfonates, alkylsulfates, arylsulfonates as well as protein hydrolysation products. As dispersing agents there are suitable: for example lignin-sulphite waste liquors and methylcellulose.
Adhesives may also be used in formulations such as powders, granules and emul- sions, and the followings are examples of usable adhesives: for example carboxymethylcellulose and natural and synthetic polymers such as gum arabic, polyvinyl alcohol and polyvinyl acetate.
It is possible to use colorants such as inorganic pigments, for example iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of metals, for example iron, manganese, boron, copper, cobalt, molybdenum and zinc.
The formulations in general can contain between 0.1 and 95% by weight, preferably between 0.5 and 90% by weight of the above active compounds.
The active compounds of the formula (I) according to the invention can be present in their commercially available formulations and in the use forms prepared with these formulations, as a mixture with other active compounds, such as insecticides, attrac- tants, sterilants, miticides, nematocides, fungicides, growth-regulating substances or herbicides. The above insecticides include, for example, organic phosphate, carba- mates, carboxylates, chlorinated hydrocarbons, chloronicotinyls and insecticidal substances produced by microorganisms.
The active compounds of the formula (I) according to the invention can further be present as a mixture with synergistic agents. Synergistic agents are compounds which increase the action of the active compounds, without it being necessary for the synergistic agent added to be active itself.
The content of the active compounds of the formula (I) according to the invention in their commercially available use form can be varied within wide limits, for instance within the range of from 0.0000001 to 100% by weight, preferably between 0.00001 and 1 % by weight.
The compounds of the formula (I) according to the invention can be employed against insects, in a customary manner appropriate for the use forms. For combating hygiene insects and insects of stored cereals, the active compounds according to the invention are extremely excellent in stability to alkali on limed substances and in residual activity on wood and soil.
Then, the following Examples illustrate the invention, but they should not be regarded as limiting the scope of the invention.
Examples
Example 1
Figure imgf000024_0001
To a suspension of 2,6-difluorobenzamide (1.57 g) in 1 ,2-dichloroethane (15 ml) , oxalyl chloride (1.65 g) is added dropwise. The mixture is heated under reflux for 30 minutes and the solvent is distilled off. To the residue, toluene (20 ml) is added and a toluene (10 ml) solution of 2,2,3,3,3-pentafluoropropylamine (1.64 g) is added drop- wise under cooling with ice. The mixture is stirred at room temperature for 5 hours, and then it is diluted with hexane (60 ml). The precipitates are filtered off and air- dried to obtain l-(2,2,3,3,3-pentafluoropropyl)-3-(2,6-difluorobenzoyl)urea (3.02 g) as colorless crystals. melting point: 156 - 158°C
Example 2
Figure imgf000024_0002
To a suspension of 3,4,4-trifluoro-3-butenylamine hydrochloride (0.89 g) in anhydrous tetrahydrofuran (20 ml), sodium tert-butoxide (0,62 g) is added at room temperature. A solution of 2,6-difluorobenzoyl isocyanate prepared from 2,6-difluoro- benzamide (0.79 g) in anhydrous tetrahydrofuran (10 ml) is added dropwise under cooling with ice. After stirring the mixture at room temperature for 12 hours, the sol- vent is distilled off under reduced pressure. Then, water is added and the mixture is extracted with ethyl acetate. The extract is dried over anhydrous sodium sulfate. After distilling off the solvent, the residue is subjected to column chromatography on silica gel (ether: hexane = 1 :4) to obtain l-(3,4,4-trifluoro-3-butenyl)-3-(2,6-di- fluorobenzoyl)urea (0.94 g) as colorless crystals. melting point: 149 - 151°C
The following Table 1 shows the compounds of Examples 1 and 2 together with the compounds produced in a manner similar to those of the above Examples 1 or 2 as well as the compounds which can be synthesized in a manner similar to those of the above Examples 1 or 2.
Table 1
Figure imgf000026_0001
Figure imgf000026_0002
Figure imgf000027_0001
Figure imgf000028_0001
Figure imgf000029_0001
Figure imgf000030_0001
Figure imgf000031_0001
Biological Test Examples: Test against Spodoptera Iitura larvae
Preparation of test solutions
Solvent: 3 parts by weight of xylol
Emulsifier: 1 part by weight of polyoxyethylene alkyl phenyl ether
To produce a suitable preparation of the active compound, 1 part by weight of the active compound was mixed with the stated amount of solvent containing the stated amount of emulsifier, and the mixture was diluted with water to the prescribed concentration.
Testing procedure
Leaves of cabbage (Bassica oleracea) were dipped into the water solution of the active compound at the prescribed concentration. After air-drying of the solution, the treated leaves of cabbage were placed in a Petri dish (diameter: 9 cm), and ten of the third-instar larvae of common cutworms (Spodoptera Iitura) were released. The dish was then placed at an incubation chamber of 28°C. After 7 days, the number of dead larvae was examined to calculate mortality in %. Tests was successively conducted three times and the mortality in % is shown in their average.
Results
Compounds Nos. 2, 10, 11, 16, 21, 30 and 32 as test examples exhibited 100 % of destruction at the concentration of 100 ppm.

Claims

CLAIMS:
1) Compounds of the formula (I):
Figure imgf000033_0001
wherein
R1, R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen, Cj.3-alkyl, C 1.3 -haloalkyl, Cj.3-alkoxy, C1.3- haloalkoxy,
Figure imgf000033_0002
or C1.3-haloalkylthio, with the proviso that all of R1, R2 and R3 do not simultaneously represent hydrogen atoms, R4 represents a hydrogen atom, nitro, cyano, halogen, Cj .3 -alkyl, C1.3- haloalkyl, C^-alkoxy, Cj.3 -haloalkoxy, C].3-alkylthio or C ] .3-haloalkylthio,
R5 represents optionally substituted C2.2o-flu°roalkyl, optionally substituted C4_2o-(carbon atoms in total) fluorocycloalkyl-alkyl, optionally substituted C3_ιø-fιuorocycloalkyl, optionally substituted C4_2o-(carbon atoms in total) fluoroalkyl-cycloalkyl or optionally substituted C3.2o-fluoroalkenyl,
X and Y each independently represent an oxygen atom or a sulfur atom, and
n is 1 and 2.
2) Compounds of formula (I) according to claim 1 , wherein
R1, R2 and R3 each independently represent a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoro- methyl, methoxy, trifluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-trifluoroethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, difluoromethylthio or 2,2,2-trifluoroethylthio, with the proviso that all of R1, R2 and R3 do not simultaneously repre- sent a hydrogen atom,
R4 represents a hydrogen atom, nitro, cyano, halogen, methyl, trifluoromethyl, chlorodifluoromethyl, difluoromethyl, methoxy, trifluoromethoxy, chlorodifluoromethoxy, difluoromethoxy, 2,2,2-trifluoro- ethoxy, methylthio, trifluoromethylthio, chlorodifluoromethylthio, difluoromethylthio or 2,2,2-trifluoroethylthio,
R5 represents C2.1 1 -fluoroalkyl which may be substituted by one or more substituent(s) selected from the group consisting of chlorine, bromine or C4_g-(carbon atoms in total) fluorocycloalkyl-alkyl which may be substituted by one or more substituent(s) selected from the group consisting of chlorine, bromine or C3_jo-fluorocycloalkyl which may be substituted by one or more substituent(s) selected from the group consisting of chlorine, bromine, methyl, C4.] 0-(carbon atoms in total) fluoroalkyl-cycloalkyl and C3_4-fluoroalkenyl,
X and Y each independently represent an oxygen atom or a sulfur atom, and
is 1 or 2.
3) The compounds or formula (I) according to claim 1 , wherein R1, R2 and R3 each independently represent a hydrogen atom, fluorine, chlorine, bromine, methoxy, trifluoromethyl, nitro or methyl, with the proviso that all of Rl, R2 and R3 do not simultaneously represent a hy- drogen atom,
R4 represents a hydrogen atom, fluorine or trifluoromethyl,
R5 represents 2,2,2-trifluoroethyl, 3-fluoropropyl, 2-fluoropropyl, 2,2-di- fluoropropyl, 3,3,3-trifluoropropyl, 2,2,3,3-tetrafluoropropyl,
2,2,3, 3,3-pentafluoropropyl, 4,4,4-trifluorobutyl,
2,2,3,4,4,4-hexafluorobutyl, 2,2,3,3,4,4,4-heptafluorobutyl,
2,2,3, 3,4,4,5, 5-octafluoropentyl, 2-fluoro- 1 -methylethyl, 2-chloro- 1 - (fluoromethyl)ethyl, 2-fluoro- 1 -(fluoromethyl)ethyl, 2,2,2-trifluoro- 1 - methylethyl, 2-fluoro- 1,1 -dimethylethyl, 2-fluoro-l,l-bis-
(fluoromethyl)ethyl, 2,2,2-trifluoro- 1 , 1 -dimethylethyl,
3 ,3 ,3 -trifluoro- 1 , 1 dimethylpropyl, 3 ,3 ,4,4,5 ,5 ,6,6,6-nonafluorohexyl, lH,lH,7H-dodecafluoroheptyl, lH,lH-perfluorooctyl, 2-fluorocyclo- propyl, 2,2-difluorocyclopropyl, 2,2- difluoro-1-methylcyclopropyl, 2-trifluoromethyl)cyclopentyl, 2,4- bis(trifluoromethyl)cyclohexyl, 2,3,3-trifluoro-2-propenyl or 3,4,4-tri- fluoro-3butenyl, 2-chloro-2,2-difluoroethyl, 2-chloro-3-fluorocyclo- propyl, 2,2,2-trifluoro- 1 -methyl- 1 -trifluoromethyl-ethyl, 3 ,3 ,3 -tri- fluoro-2-trifluoromethyl-propyl, 2,2,3,3,4,4,4-heptafluoro- 1 -methyl- butyl,3,3,3-trifluoro-2-methyl-2-trifluoromethylropyl, 4,4-difluoro-3- methyl-3 -butenyl, 3 -trifluoromethy 1-cyclohexyl, 2-ethoxycarbonyl- 1 - trifluoromethyl-ethylenyl, 2-trifluoromethylcyclohexyl, 2-fluoro- 1 - fluoromethyl-1 -methyl-ethyl, lH,lH,2H,2H-perfluorooctyl, 1- trifluoromethyloctyl, 3,4-dichloro-3,4,4-trifluorobutyl, 2-fluorocyclo- hexyl, 2,3-difluoropropyl, 2,3,3-trifluoropropyl, 1H,1H- perfluorononyl, 1 H, 1 H, 11 H-perfluoroundecyl. X and Y represent an oxygen atom or a sulfur atoms, and
is 1 or 2.
4) Process for the preparation of the compounds of the formula (I) according to claim 1 , characterized in that
a) compounds of the formula (II)
Figure imgf000036_0001
wherein
R1, R2, R3, R4, X, Y and n are defined as in claim 1, are reacted with compounds of the formula (III) or their salts
R°
HN :
H (III)
wherein R5 is defined as above,
in the presence of inert solvents,
or b) compounds of the formula (IV)
Figure imgf000037_0001
wherein
R1, R2, R3, R4, X and n are defined as above,
are reacted with compounds of the formula (V)
R5 7 Y C~=N (V)
wherein R5 and Y are defined as above,
in the presence of inert solvents, and if appropriate, in the presence of an inorganic alkali metal hydride or an organic lithium compound,
or
c) in a case where X and Y represent a sulfur atom:
compounds of the formula (VI)
Figure imgf000038_0001
wherein
R1, R2, R3, R4, R5 and n are defined as above,
are reacted with phosphorus pentasulfide or Lawesson's reagent in the presence of inert solvents.
5) Insecticidal compositions characterized in that they contain at least one fluoro-substituted benzoylurea of the formula (I).
6) Method of combating harmful insects, characterized in that fluoro-substituted benzoylureas of the formula (I) are allowed to act on harmful insects and/or their habitat.
7) Use of fluoro-substituted benzoylureas of the formula (I) for combating harmful insects.
8) Process for the preparation of insecticidal compositions, characterized in that fluoro-subsituted benzoylureas of the formula (I) are mixed with extenders and/or surface active agents.
PCT/IB1998/002105 1997-12-26 1998-12-22 Insecticidal fluoro-substituted benzoylureas WO1999033790A1 (en)

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