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WO1999033790A1 - Benzoyl uree a substitution fluor d'usage insecticide - Google Patents

Benzoyl uree a substitution fluor d'usage insecticide 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
English (en)
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/fr

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Classifications

    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Cette invention, qui a trait à des benzoyls urée à substitution fluor correspondants à la formule (I), concerne également des procédés visant à leur préparation, des compositions les contenant ainsi que l'usage qui en est fait en tant qu'insecticides. Dans la formule (I), R?1, R2 et R3¿ représentent, chacun de manière indépendante, un atome d'hydrogène, un nitro, un cyano, un halogène, un alkyle comportant de 1 à 3 atomes de carbone, un haloalkyle comportant de 1 à 3 atomes de carbone, un haloalcoxy comportant de 1 à 3 atomes de carbone, un alkylthio comportant de 1 à 3 atomes de carbone ou un haloalkylthio comportant de 1 à 3 atomes de carbone, à condition que R?1, R2 et R3¿ ne représentent pas en même temps des atomes d'hydrogène, R4 représente un atome d'hydrogène un nitro, un cyano, un halogène, un alkyle comportant de 1 à 3 atomes de carbone, un haloalkyle comportant de 1 à 3 atomes de carbone, un haloalcoxy comportant de 1 à 3 atomes de carbone, un alkylthio comportant de 1 à 3 atomes de carbone ou un haloalkylthio comportant de 1 à 3 atomes de carbone, R5 représente un fluoroalkyle comportant de 2 à 20 atomes de carbone, éventuellement substitué, un fluorocycloalkyl-alkyle comportant de 4 à 20 atomes de carbone au total, éventuellement substitué, un fluorocycloalkyle comportant de 3 à 10 atomes de carbone, éventuellement substitué, un fluorocycloalkyl-cycloalkyle comportant de 4 à 20 atomes de carbone au total, éventuellement substitué ou un fluoroalcényle comportant de 3 à 20 atomes de carbone, éventuellement substitué, et X et Y représentent, chacun de manière indépendante, un atome d'oxygène ou un atome de soufre.
PCT/IB1998/002105 1997-12-26 1998-12-22 Benzoyl uree a substitution fluor d'usage insecticide WO1999033790A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU15019/99A AU1501999A (en) 1997-12-26 1998-12-22 Insecticidal fluoro-substituted benzoylureas

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JP36696797 1997-12-26
JP9/366967 1997-12-26
JP10228554A JPH11240859A (ja) 1997-12-26 1998-07-30 フルオロ置換ベンゾイルウレア類及び有害生物防除剤
JP10/228554 1998-07-30

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JP (1) JPH11240859A (fr)
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EP2124921A4 (fr) * 2007-01-17 2010-04-14 Siga Technologies Inc Semi-carbazides de sulfonyle, semi-carbazides de carbonyle, semi-carbazides et urées, compositions pharmaceutiques de ceux-ci, et procédé de traitement des virus de fièvre hémorragique, y compris des infections associées à des arénavirus
EP1827446A4 (fr) * 2004-12-06 2011-01-12 Siga Technologies Inc Semicarbazides de sulfonyle, semicarbazides et urees, leurs compositions pharmaceutiques et methodes pour traiter des virus a fievre hemorragique virale, y compris des infections associees a des adenavirus
US8410149B2 (en) 2004-12-06 2013-04-02 Siga Technologies Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
CN113166039A (zh) * 2018-12-05 2021-07-23 大金工业株式会社 氟乙烯基酰胺化合物的制造方法

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JP5902575B2 (ja) * 2012-07-20 2016-04-13 国立大学法人お茶の水女子大学 光学活性含フッ素アミン化合物の製造方法並びに光学活性含フッ素アミン化合物

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EP0019156A1 (fr) * 1979-05-12 1980-11-26 Bayer Ag Urées substituées, procédé pour leur préparation et leur utilisation comme bactéricides à usage végétal
EP0154508A2 (fr) * 1984-02-27 1985-09-11 Takeda Chemical Industries, Ltd. Thiophénylurées, leur préparation et utilisation
JPS60224667A (ja) * 1984-04-20 1985-11-09 Takeda Chem Ind Ltd 新規な尿素誘導体

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EP0019156A1 (fr) * 1979-05-12 1980-11-26 Bayer Ag Urées substituées, procédé pour leur préparation et leur utilisation comme bactéricides à usage végétal
EP0154508A2 (fr) * 1984-02-27 1985-09-11 Takeda Chemical Industries, Ltd. Thiophénylurées, leur préparation et utilisation
JPS60224667A (ja) * 1984-04-20 1985-11-09 Takeda Chem Ind Ltd 新規な尿素誘導体

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EP1827446A4 (fr) * 2004-12-06 2011-01-12 Siga Technologies Inc Semicarbazides de sulfonyle, semicarbazides et urees, leurs compositions pharmaceutiques et methodes pour traiter des virus a fievre hemorragique virale, y compris des infections associees a des adenavirus
US7994221B2 (en) 2004-12-06 2011-08-09 Siga Technologies, Inc. Sulfonyl semicarbazides, carbonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US8410149B2 (en) 2004-12-06 2013-04-02 Siga Technologies Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US8642596B2 (en) 2004-12-06 2014-02-04 Siga Technologies, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arena viruses
US8658697B2 (en) 2004-12-06 2014-02-25 Siga Technologies, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US8664274B2 (en) 2004-12-06 2014-03-04 Siga Technologies, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arena viruses
US9067873B2 (en) 2004-12-06 2015-06-30 Kineta Four, LLC Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with arenaviruses
US9115065B2 (en) 2004-12-06 2015-08-25 Kineta, Inc. Sulfonyl semicarbazides, semicarbazides and ureas, pharmaceutical compositions thereof, and methods for treating hemorrhagic fever viruses, including infections associated with Arenaviruses
EP2124921A4 (fr) * 2007-01-17 2010-04-14 Siga Technologies Inc Semi-carbazides de sulfonyle, semi-carbazides de carbonyle, semi-carbazides et urées, compositions pharmaceutiques de ceux-ci, et procédé de traitement des virus de fièvre hémorragique, y compris des infections associées à des arénavirus
CN113166039A (zh) * 2018-12-05 2021-07-23 大金工业株式会社 氟乙烯基酰胺化合物的制造方法
EP3892611A4 (fr) * 2018-12-05 2022-11-09 Daikin Industries, Ltd. Procédé de production d'un composé amide fluorovinylique
US12281075B2 (en) 2018-12-05 2025-04-22 Daikin Industries, Ltd. Method for producing fluorovinyl amide compound

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JPH11240859A (ja) 1999-09-07

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