WO1994005633A1 - 3-cyano-4-halogeno-2-(subst phenyl)-pyrroles utilises comme pesticides et fongicides - Google Patents

3-cyano-4-halogeno-2-(subst phenyl)-pyrroles utilises comme pesticides et fongicides Download PDF

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Publication number
WO1994005633A1
WO1994005633A1 PCT/EP1993/002231 EP9302231W WO9405633A1 WO 1994005633 A1 WO1994005633 A1 WO 1994005633A1 EP 9302231 W EP9302231 W EP 9302231W WO 9405633 A1 WO9405633 A1 WO 9405633A1
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formula
halo
compound
alkyl
salt
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PCT/EP1993/002231
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English (en)
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Dieter DÜRR
Josef Ehrenfreund
Roger Graham Hall
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Ciba-Geigy Ag
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Priority to AU49506/93A priority Critical patent/AU4950693A/en
Publication of WO1994005633A1 publication Critical patent/WO1994005633A1/fr

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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having no bond to a nitrogen atom
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/36—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom five-membered rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
    • C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D207/30—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members
    • C07D207/34—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms

Definitions

  • n is 1, 2, 3 or 4; when n is greater than 1, the radicals R 3 are identical or different;
  • R 1 is halogen or halo-C 1 -C 9 alkyl
  • R 2 is halogen
  • R 3 is hydrogen, cyano, nitro, halogen, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio,
  • R 4 is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkenyl, halo-C 3 -C 4 alkenyl, C 3 -C 4 alkynyl, cyano, C 1 -C 4 alkylthio, C 1 -C 4 alkanesulfinyl, C 1 -C 4 alkanesulfonyl, halo-C 1 -C 4 alkanesulfonyl, di-C 1 -C 4 alkylaminosulfonyl, di-C 1 -C 4 alkylaminocarbonyl, or a C 1 -C 4 alkyl group substituted by one or more substituents selected from the group consisting of halogen, C 1 -C 4 alkoxy, hydroxy, C 1 -C 4 alkylthio, C 2 -C 6 alkoxyalkoxy, Cj ⁇ alkanesulfinyl, C 1 -C 4 alkanesulfon
  • substituents to be substituted by halogen C 1 -C 4 alkyl, C 1 -C 4 alkoxy, halo-C 1 -C 4 alkyl, halo-C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 1 -C 4 alkanesuifinyl, C 1 -C 4 alkanesulfonyl, haloC 1 -C 4 alkylthio, halo- C 1 -C 4 alkanesulfinyl, halo-C 1 -C 4 alkanesulfonyl, cyano or by nitro;
  • R 6 is C 1 -C 6 alkyl or halo-C 1 -C 6 alkyl
  • R 5 is not -CF 3 , -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , -OCF 2 CHFCl or -OC 2 F 5 when R 1 is
  • R 5 is not halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy when R 1 is -CF 2 -halo-C 1 -C 8 alkyl, in free form or in salt form, to a process for the preparation of those compounds and to the use of those compounds, to pesticides comprising an active ingredient selected from those compounds, in free form or in agrochemically acceptable salt form, to a process for the preparation of those compositions and to the use of those compositions, to plant propagation material treated with those compositions, to a method of controlling pests, to intermediates and the salts thereof for the preparation of the compounds of formula I, and to processes for the preparation of those intermediates.
  • Compounds of formula I having at least one basic centre are capable of forming, for example, acid addition salts.
  • Those salts are formed, for example, with strong inorganic acids, such as mineral acids, for example perchloric acid, sulfuric acid, nitric acid, nitrous acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C 1 -C 4 alkanecarboxylic acids, for example acetic acid, or saturated or unsaturated dicarboxylic acids, for example oxalic, malonic, succinic, maleic, fumaric or phthalic acid, or hydroxycarboxylic acids, for example ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, for example halo-substituted,
  • C 1 -C 4 alkanesulfonic or arylsulfonic acids for example methanesulfonic or p-toluene sulfonic acid.
  • compounds of formula I having at least one acidic group are capable of forming salts with bases.
  • Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethylamine, diethylamine, triethylamine or dimethylpropylamine, or a mono-, di- or tri-hydroxy-lower alkylamine, for example mono-, di- or tri-ethanolamine. Where appropriate, corresponding internal salts may also be formed.
  • metal salts such as alkali metal or alkaline earth metal salts, for example sodium, potassium or magnesium salts
  • salts with ammonia or an organic amine such as morpholine, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, for example ethylamine, diethylamine, trieth
  • Halogen - per se or as a structural element of groups and compounds, such as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl - is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine and most especially fluorine.
  • Halogen R 2 is especially chlorine or bromine, more especially bromine.
  • carbon-containing groups and compounds each contain from 1 up to and including 9, preferably from 1 up to and including 6, especially from 1 up to and including 4, more especially 1 or 2, carbon atoms.
  • Alkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkyl, alkoxy, alkoxyalkoxy, haloalkoxy, alkylthio, haloalkylthio, alkanesulfinyl, haloalkanesulfinyl, alkanesulfonyl, haloalkanesulfonyl, dialkylaminosulfonyl, dialkylaminocarbonyl, alkylcarbonyl, alkoxycarbonyl and alkylcarbonyloxy - in each case taking due account of the number of carbon atoms in the corresponding group or compound - is either straight-chained, i.e.
  • Alkenyl, haloalkenyl, alkenylcarbonyloxy and alkynyl are straight-chained or branched and each contain two or preferably one unsaturated carbon-carbon bond(s). The double or triple bonds of those substituents are separated from the remainder of the compound of formula I preferably by at least one saturated carbon atom.
  • the following may be mentioned by way of example: allyl, methallyl, but-2-en-1-yl, but-3-en-2-yl, allylcarbonyloxy, propargyl, but-2-yn-1-yl and but-3-yn-1-yl.
  • Halo-substituted carbon-containing groups and compounds such as haloalkyl, haloalkenyl, haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl, may be partially halogenated or perhalogenated, it being possible in the case of poly-halogenation for the halogen substituents to be identical or different.
  • haloalkyl - as a group per se and as a structural element of other groups and compounds, such as haloalkoxy, haloalkylthio, haloalkanesulfinyl and haloalkanesulfonyl - are methyl mono- to tri-substituted by fluorine, chlorine and/or by bromine, such as CHF 2 , CF 2 Cl, CFCl 2 or CF 3 ; ethyl mono- to penta-substituted by fluorine, chlorine and/or by bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCl 3 , CF 2 CHCl 2 , CF 2 CHF 2 , CF 2 CFCl 2 , CF 2 CHBr 2 , CF 2 CHClF, CF 2 CF 2 Br, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl mono- to fluor
  • Haloalkyl R 1 is preferably exclusively fluorinated, especially perfluorinated.
  • Examples of haloalkenyl are 2-chloroprop-2-en-1-yl,
  • dialkylaminosulfonyl and dialkylammocarbonyl substituents may in each case be identical or different The following may be mentioned by way of example: -SO 2 -N(CH 3 ) 2 , -SO 2 -N(C 2 H 5 ) 2 , -SO 2 -N(CH 3 )C 2 H 5 , -SO 2 -N(C 3 H 7 ) 2 ,
  • alkoxy group bonded to the remainder of the compound of formula I is substituted by a further alkoxy group, and the two carbon chains, each independently of the other, may be straight or branched and together include from 2 to 6 carbon atoms.
  • Examples are methoxymethoxy, methoxyethoxy, 2-ethoxyethoxy, ethoxymethoxy, isopropoxymethoxy, 3-methoxypropoxy, n-butoxymethoxy and 2-(n-propoxy)ethoxy.
  • bridges formed by two substituents R 3 together when those bridges are substituted, either one of the hydrogen atoms in the unsubstituted basic structure has been replaced by an alkyl, alkoxy or haloalkyl substituent or one or more than one, especially all, of the hydrogen atoms in the unsubstituted basic structure has(have) been replaced by identical or different halogen atoms.
  • substituted bridges are -O-CF 2 -O-, e.g. 2,3-O-CF 2 -O- or 3,4-O-CF 2 -O-,
  • the alkyl basic structure carries preferably two or, especially, one of the above-mentioned substituents; in the case of a halo-substituted alkyl group R 4 , however, one or more than one, for example all, of the hydrogen atoms in the unsubstituted alkyl basic structure has(have) been replaced by identical or different halogen atoms.
  • substituted alkyl group R 4 contains a substituted phenyl nucleus, that phenyl nucleus carries preferably two or, especially, one of the above-mentioned substituents; in the case of a halo-substituted phenyl nucleus, however, 1, 2, 3, 4 or all of the phenyl-hydrogen atoms may have been replaced by identical or different halogen atoms.
  • the alkyl basic structure is preferably a methyl group.
  • R 1 is halogen or perfluoro-C 1 -C 9 alkyl, especially chlorine or perfluoro-C 1 -C 4 alkyl, more especially chlorine, CF 3 or C 2 F 5 , and most especially CF 3 ;
  • R 2 is chlorine or bromine, especially bromine
  • n 1 or 2; when n is 2, the radicals R 3 are identical or different, and
  • R 3 is hydrogen, halogen, halo-C 1 -C 4 alkyl, halo-C 1 -C 4 alkoxy, cyano, C 1 -C 4 alkyl,
  • n is especially 1 and
  • R 3 is especially hydrogen, halogen, halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy, R 3 is more especially hydrogen, trifluoromethyl, trifluoromethoxy or chlorine, preferably chlorine or hydrogen, and
  • R 3 is most especially hydrogen
  • R 4 is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkynyl, C 1 -C 4 alkanesulfonyl, di-C 1 -C 4 alkylaminosulfonyl, or a C 1 -C 4 alkyl group substituted by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio, C 2 -C 6 alkoxyalkoxy, C 1 -C 4 alkanesulfonyl, C 1 -C 4 alkylcarbonyl, C j -C 4 alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy, and is especially hydrogen, C 1 -C 4 alkyl, or a C 1 -C 4 alkyl group substituted by halogen, C 1 -C 4 alkoxy or by C 2 -C 6 alkoxyalkoxy, and is preferably hydrogen, C 1 -C 4 alkyl, hal
  • R 6 is C 1 -C 4 alkyl or halo-C 1 -C 4 alkyl, especially a compound of formula I wherein R 6 is C 1 -C 2 alkyl or halo-C 1 -C 2 alkyl, more especially trifluoromethyl or pentafluoroethyl, most especially CF 3 ,
  • the group -O-SO 2 -R 6 being especially in the 4-position
  • R 5 is halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy, especially fluoro-C 1 -C 2 alkyl, fluoroC 1 -C 3 alkoxy or fluoro-bromo-C 1 -C 3 alkoxy;
  • R 1 is halogen or perfluoro-C 1 -C 9 alkyl
  • R 2 is chlorine or bromine
  • n 1 or 2
  • R 3 is hydrogen, halogen, halo-C 1 -C 4 alkyl, halo-C 1 -C 4 alkoxy, cyano, C 1 -C 4 alkyl, C 1 -C 4 alkoxy, C 1 -C 4 alkylthio or C 1 -C 4 alkanesulfonyl and/or two substituents R 3 bonded to adjacent carbon atoms of the phenyl ring are together -O-C(halo) 2 -O-;
  • R 4 is hydrogen, C 1 -C 4 alkyl, C 3 -C 4 alkynyl, C 1 -C 4 alkanesulfonyl, di-C 1 -C 4 alkylaminosulfonyl, or a C 1 -C 4 alkyl group substituted by halogen, C 1 -C 4 alkoxy, C 1 -C 4 alkyl- thio, C 2 -C 6 alkoxyalkoxy, C 1 -C 4 alkanesulfonyl, C 1 -C 4 alkylcarbonyl, C 1 -C 4 alkoxycarbonyl, cyano, mono-halophenyl or by phenoxy, and
  • R 1 is chlorine or perfluoro-C 1 -C 4 alkyl
  • R 2 is chlorine or bromine
  • n 1,
  • R 3 is hydrogen, halogen, halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy
  • R 4 is hydrogen, C 1 -C 4 alkyl, or a C 1 -C 4 alkyl group substituted by halogen, C 1 -C 4 alkoxy or by C 2 -C 6 alkoxyalkoxy and
  • R 1 is chlorine, -CF 3 or -C 2 F 5 ,
  • R 2 is chlorine or bromine
  • n 1,
  • R 3 is hydrogen, trifluoromethyl, trifluoromethoxy or chlorine
  • R 4 is hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl
  • R 6 is trifluoromethyl
  • R 1 is -CF 3 or -C 2 F 5 ,
  • R 2 is chlorine or bromine
  • n 1,
  • R 3 is hydrogen, trifluoromethyl, trifluoromethoxy or chlorine
  • R 4 is hydrogen, methyl, halomethyl, methoxymethyl or ethoxymethyl
  • R 1 is -CF 3 ,
  • R 2 is chlorine or bromine
  • n 1,
  • R 3 is hydrogen
  • R 3 is chlorine bonded in the 3-position.
  • the invention relates further to a process for the preparation of a compound of formula I or one of the salts thereof, which - taking account of the proviso that, in the compounds of formulae I, II and V, R 5 is not -CF 3 , -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , -OCF 2 CHFCl or -OC 2 F 5 when R 1 is -CF 3 or halogen,
  • R 5 is not halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy when R j is -CF 2 -halo-C 1 -C 8 alkyl comprises, for example, a) introducing the halogen substituent R 2 into the 4-position of the pyrrole ring of a compound of formula
  • R 1 , R 3 , R 4 , R 5 and n are as defined for formula I, or into a salt thereof, by reaction with a halogenating agent, preferably in the presence of a base, or b) for the preparation of a compound of formula I wherein R 4 is other than hydrogen, or a salt thereof, reacting, preferably in the presence of a base, a compound of formula I wherein R 4 is hydrogen, or a salt thereof, obtainable, for example, in accordance with Variant a), with a compound of formula
  • R 1 , R 2 , R 3 , R 4 , R 6 and n are as defined for formula I, or a salt thereof, with a compound of formula
  • Y-SO 2 R 6 (IV) which is known or can be prepared analogously to corresponding known compounds and wherein R 6 has one of the definitions given for formula I and Y is a leaving group, preferably a halogen atom, or d) for the preparation of a compound of formula I wherein R 4 is methyl or a group R 2 CH 2 -, or a salt thereof, reacting a compound of formula
  • R 1 , R 3 , R 5 and n are as defined for formula I, or a salt thereof, with a halogenating agent, where appropriate in the presence of a base, and where appropriate in the presence of a radical initiator, or e) for the preparation of a compound of formula I wherein R 5 is halo-C 1 -C 6 alkoxy, reacting, preferably in the presence of a base, a compound of formula
  • R 1 , R 2 , R 3 and n are as defined for formula l and R 4 is other than hydrogen, or a salt thereof, with a halo-C 1 -C 6 alkane or a halo-C 1 -C 6 alkene, which are known, and in each case, if desired, converting a compound of formula I obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula I, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula I obtainable in accordance with the process into a salt or converting a salt of a compound of formula I obtainable in accordance with the process into the free compound of formula I or into a different salt.
  • reaction described hereinbefore and hereinafter are carried out in a manner known per se, for example in the absence or, generally, in the presence of a suitable solvent or diluent or a mixture thereof, the reaction being carried out as required with cooling, at room temperature or with heating, for example in a temperature range of from approximately -80°C to the boiling temperature of the reaction medium, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • a suitable solvent or diluent or a mixture thereof for example in a temperature range of from approximately -80°C to the boiling temperature of the reaction medium, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, in an inert gas atmosphere and/or under anhydrous conditions.
  • Especially advantageous reaction conditions can be found in the Examples.
  • Suitable halogenating agents are, for example, elemental halogens, such as elemental chlorine, bromine or iodine, hypochlorites, such as sodium hypochlorite, sulfuryl halides, such as sulfuryl chloride or sulfuryl bromide, N-haloamides, such as N-chloro-p-toluenesulfonamide or the sodium salt thereof, or N-halosuccinimides, such as N-chlorosuccinimide or N-bromosuccinimide.
  • elemental halogens such as elemental chlorine, bromine or iodine
  • hypochlorites such as sodium hypochlorite
  • sulfuryl halides such as sulfuryl chloride or sulfuryl bromide
  • N-haloamides such as N-chloro-p-toluenesulfonamide or the sodium salt thereof
  • N-halosuccinimides such as N-chlorosuccinimide or N-bromosucc
  • bases suitable for facilitating the halogenation reaction are alkali metal or alkaline earth metal hydroxides, hydrides, amides, alkoxides, acetates, carbonates, dialkylamides or alkylsilylamides; alkylamines, alkylenediamines, optionally N-alkylated, unsaturated or saturated, cycloalkylamines, basic heterocycles, ammonium hydroxide and carbocyclic amines.
  • Examples are sodium hydroxide, hydride, amide, methoxide, acetate or carbonate, potassium-tert-butoxide, hydroxide, carbonate or hydride, lithium diisopropylamide, potassium-bis(trimethylsilyl)amide, calcium hydride, triethylamine, diisopropylethylamine, triethylenediamine, cyclohexylamine, N-cyclohexyl-N,N-dimethylamine, N,N-diethylaniline, pyridine, 4-(N,N-dimethylamino)pyridine, quinuclidine, N-methylmorpholine, benzyl-trimethyl-ammonium hydroxide and l,5-diazabicyclo[5.4.0]-undec-5-ene (DBU).
  • the reactants can be reacted with one another as such, Le. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachlorome thane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetra
  • sulfoxides such as dimethylsulfoxide
  • acids for example strong organic carboxylic acids, such as unsubstituted or substituted, for example halo-substituted, C 1 -C 4 alkanecarboxylic acids, for example formic acid, acetic acid or propionic acid; or water.
  • bases such as such triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, used in excess, to serve as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately +130°C, and in many cases in the range from room temperature to the reflux temperature of the reaction mixture. In most cases the reaction mixture is heated automatically by liberated heat of reaction. As a final step, in order to complete the halogenation reaction, the reaction mixture is advantageously heated for a short time under reflux.
  • the reaction is carried out at room temperature in a mixture of glacial acetic acid and sodium acetate with bromine, and in another specific embodiment in dimethylformamide with N-chlorosuccinimide.
  • Examples of suitable leaving groups X in compounds of formula in are hydroxy,
  • Suitable bases for facilitating the HX removal are, for example, of the type indicated under Variant a).
  • the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or a mixture thereof is advantageous.
  • solvents or diluents are: aromatic, aliphatic and alicyclic hydrocarbons and halohydrocarbons, such as benzene, toluene, xylene, mesitylene, Tetralin, chlorobenzene, dichlorobenzene, bromobenzene, petroleum ether, hexane, cyclohexane, dichloromethane, trichloromethane, tetrachloromethane, dichloroethane, trichloroethene or tetrachloroethene; esters, such as ethyl acetate; ethers, such as diethyl ether, diisopropyl ether, dibutyl ether, tert-butyl methyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol dimethyl ether, dimethoxy diethyl ether, tetra
  • reaction is carried out in the presence of a base
  • bases such as such triethylamine, pyridine, N-methylmorpholine or N,N-diethylaniline, used in excess, to serve as solvents or diluents.
  • the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately
  • the reaction is carried out in tetrahydrofuran in the presence of potassium tert-butoxide with chloromethyl ethyl ether.
  • Suitable bases for facilitating the HY removal are, for example, of the type indicated under Variant a).
  • the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are those mentioned under Variant a).
  • the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately +130°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • reaction is carried out in glacial acetic acid in the presence of triethylamine.
  • Suitable halogenating agents are, for example, of the type indicated under Variant a).
  • Suitable bases for facilitating the reaction with the halogenating agent are, for example, of the type indicated under Variant a).
  • radical initiators examples include peroxo compounds, such as dibenzoyl peroxide or di-tert-butyl peroxide, azo compounds, such as 2,2'-azobisisobutyronitrile, and light
  • the reactants can be reacted with one another as such, i.e. without the addition of a solvent or diluent, for example in the melt. In most cases, however, the addition of an inert solvent or diluent or of a mixture thereof is advantageous. Examples of such solvents or diluents are of the type mentioned under Variant b).
  • the reaction is advantageously carried out in a temperature range from approximately 0°C to approximately +180°C, preferably from approximately +10°C to approximately +130°C, in many cases in the range from room temperature to the reflux temperature of the reaction mixture.
  • a third equivalent of halogenating agent is required.
  • the term "equivalent” is to be understood to include not only the precise amount that corresponds exactly to one equivalent, but also a certain range, for example about 10 %, above and below that precise amount. It is possible to isolate compound A and/or compound B, but the reaction is preferably carried out as a one-pot reaction without the isolation of compounds A and B. It is also possible to add the whole amount of halogenating agent at the beginning of the reaction, but the halogenating agent is preferably added in portions, for example in several portions each of one equivalent.
  • the mono-halogenation of the methyl group R 4 of compound B is preferably carried out in the presence of a radical initiator.
  • Suitable alkylating agents are haloalkanes mid haloalkenes, for example bromotrifluoromethane, dibromo-difluoromethane, 1,2-dibromo-1,1,2,2-tetrafluoroethane, tetrafluoroethylene, hexafluoropropylene, bromopentafluoroethane or chlorotrifluoroethylene.
  • the compounds of formula Ila used in Process Variants c) and e), in free form or in salt form, are also novel and the invention relates also to those compounds. They can be prepared in accordance with methods known per se, for example by means of a reaction analogous to Synthesis Variant e) above, or by converting a compound of formula IIa obtainable in accordance with the process or by another method in a manner known per se into a different compound of formula II by replacing one or more substituents of the starting compound II by (a) different substituent(s) of the invention in customary manner. Special preference is given within the scope of the invention to the compounds of formula II mentioned in Examples 14 and 17.
  • the invention relates also to a process for the preparation of compounds of formulaII, in free form or in salt form, which - taking account of the proviso that, in compounds of formulae II and VI of the following Synthesis Variants f) and g),
  • R 5 is not -CF 3 , -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , -OCF 2 CHFCl or -OC 2 F 5 when Rj is -CF 3 or halogen,
  • R 5 is not halo-C 1 -C 4 alkyl or halo-C 1 -C 4 alkoxy when R 1 is -CF 2 -halo-C 1 -C 8 alkyl - comprises, for example, f) for the preparation of a compound of formula II wherein R 4 is hydrogen, or of a salt thereof, reacting a compound of formula
  • R 1 , R 3 , R 5 and n are as defined for formula I, or a salt thereof, with 2-chloroacrylonitrile, preferably in a high-boiling polar solvent, such as nitromethane, preferably in the presence of a base, such as triethylamine and at the reflux temperature of the reaction mixture, or g) for the preparation of a compound of formula II wherein R 4 is other than hydrogen, or a salt thereof, reacting a compound of formula II wherein R 4 is hydrogen, or a salt thereof, obtainable, for example in accordance with Variant f), preferably in the presence of a base, for example of the type indicated under Variant a), with a compound of formula
  • R 4 has one of the definitions given for formula I with the exception of hydrogen and X is a leaving group, for example of the type indicated under Variant b), or where appropriate with a salt thereof, or h) for the preparation of a compound of formula
  • R 1 , R 2 and R 4 are as defined for formula I, n is 1 and R 3 is halogen, reacting a compound of formula
  • R 1 , R 2 and R 4 are as defined for formula I, or a salt thereof, with a halogenating agent, and in each case, if desired, converting a compound of formula II obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula II, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula II obtainable in accordance with the process into a salt or converting a salt of a compound of formula II obtainable in accordance with the process into the free compound of formula II or into a different salt
  • the compounds VI in free form or in salt form, are known or can be prepared analogously to known compounds.
  • the invention relates also to a process for the preparation of compounds of formula V, in free form or in salt form, which comprises, for example, i) reacting a compound of formula
  • R 1 , R 3 , R 5 and n are as defined for formula I, with the proviso that R 5 is not -CF 3 , -OCF 3 , -OCHF 2 , -OCF 2 CHF 2 , -OCF 2 CHFCl or -OC 2 F 5 when R 1 is -CF 3 or halogen, or a salt thereof, with acrylonitrile, preferably in a high-boiling polar solvent, such as acetonitrile, in the presence of an acid anhydride, such as acetic anhydride, and at the reflux temperature of the reaction mixture, and, if desired, converting a compound of formula V obtainable in accordance with the process or by another method, in free form or in salt form, into a different compound of formula V, separating a mixture of isomers obtainable in accordance with the process and isolating the desired isomer, and/or converting a free compound of formula V obtainable in accordance with the process into a salt or converting
  • a compound of formula I, II or V obtainable in accordance with the process or by another method can be converted in a manner known per se into a different compound of formula I, II or V by replacing one or more substituents of the starting compound of formula I, II or V in customary manner by (a) different substituent(s) of the invention.
  • Y-SO 2 R 6 (IV); - halogen R 3 can be introduced into unsubstituted positions of the phenyl ring;
  • R 3 and/or R 4 can be oxidised to sulfinyl or sulfonyl groups R 3 and/or R 4 or sulfinyl groups R 3 and/or R 4 can be oxidised to sulfonyl groups R 3 and/or R 4 ;
  • R 4 can be mono-halogenated to mono-halomethyl groups R 4 ;
  • - mono-halomethyl groups R 4 can be converted into monoalkoxymethyl groups R 4 by replacing the halogen substituent by an alkoxy group, or
  • Salts of compounds of formula I, II and V can be prepared in a manner known per se.
  • acid addition salts of compounds of formula I, II and V are obtained by treatment with a suitable acid or a suitable ion exchange reagent, and salts with bases are obtained by treatment with a suitable base or a suitable ion exchange reagent
  • Salts of compounds of formula I, II and V can be converted into the free compounds of formula I, II and V in customary manner: acid addition salts, for example, by treatment with a suitable basic agent or a suitable ion exchange reagent and salts with bases, for example, by treatment with a suitable acid or a suitable ion exchange reagent
  • Salts of compounds of formula I, II and V can be converted into different salts of compounds of formula I, II and V in a manner known per se: acid addition salts, for example, can be converted into different acid addition salts, for example by treatment of a salt of an inorganic acid, such as a hydrochloride, with a suitable metal salt such as a sodium, barium or silver salt, of an acid, for example with silver acetate, in a suitable solvent in which an inorganic salt being formed, for example silver chloride, is insoluble and therefore is eliminated from the reaction mixture.
  • a salt of an inorganic acid such as a hydrochloride
  • a suitable metal salt such as a sodium, barium or silver salt
  • the compounds of formula of formula I, II and V and their salts may be in the form of one of the possible isomers or as a mixture thereof, for example according to the number of asymmetric carbon atoms occurring in the molecule and the absolute and relative configuration thereof and/or according to the configuration of non-aromatic double bonds occurring in the molecule, they may be in the form of pure isomers, such as antipodes and/or diastereoisomers, or in the form of mixtures of isomers, such as mixtures of enantiomers, for example racemates, mixtures of diastereoisomers or mixtures of racemates; the invention relates both to the pure isomers and to all possible mixtures of isomers and this is to be understood hereinbefore and hereinafter, even if stereochemical details are not specifically mentioned in each case.
  • Mixtures of diastereoisomers and mixtures of racemates of compounds I, in free form or in salt form, that are obtainable in accordance with the process depending upon the starting materials and procedures chosen, or by other means, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physicochemical differences between the constituents, for example by fractional crystallisation, distillation and/or chromatography.
  • the compounds of formula I, II and V and their salts can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents that may be used for the crystallisation of compounds of formula I in solid form.
  • the invention relates to all those forms of the process according to which a compound obtainable as starting material or intermediate at any stage of the process is used as starting material and all or some of the remaining steps are carried out, or a starting material is used in the form of a derivative or a salt and/or its racemates or antipodes or, especially, is formed under the reaction conditions.
  • the invention relates especially to the preparation processes described in Examples 13 to 17 and A1 to A5.
  • the compounds of formula I according to the invention are valuable preventive and/or curative active ingredients having a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants.
  • the compounds of the invention are effective against all or individual development stages of normally sensitive animal pests, but also of resistant animal pests, such as insects and representatives of the order Acarina, and phytopathogenic fungi.
  • the insecticidal and/or acaricidal action of the compounds of the invention may manifest itself directly, i.e. in the mortality of the pests, which occurs immediately or only after some time, for example during moulting, or indirectly, for example in reduced oviposition and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %.
  • the mentioned animal pests include, for example: of the order Lepidoptera, for example,
  • Euxoa spp. Grapholita spp., Hedya nubiferana, Heliothis spp., Hellula undalis, Hyphantria cunea, Keiferia lycopersicella, Leucoptera scitella, Lithocollethis spp., Lobesia botrana,
  • Lymantria spp. Lyonetia spp., Malacosoma spp., Mamestra brassicae, Manduca sexta,
  • Operophtera spp. Ostrinia nubilalis, Pammene spp., Pandemis spp., Panolis flammea,
  • Synanthedon spp. Thaumetopoea spp., Tortrix spp., Trichoplusia ni and Yponomeuta spp.;
  • Agriotes spp. Anthonomus spp., Atomaria linearis, Chaetocnema tibialis, Cosmopolites spp., Curculio spp., Dermestes spp., Diabrotica spp., Epilachna spp., Eremnus spp.,
  • Otiorhynchus spp. Phlyctinus spp., Popillia spp., Psylliodes spp., Rhizopertha spp.,
  • Haematopinus spp. Linognathus spp., Pediculus spp., Pemphigus spp. and Phylloxera spp.;
  • Thysanoptera for example,
  • Leptocorisa spp. Leptocorisa spp., Nezara spp., Piesma spp., Rhodnius spp., Sahlbergella singularis,
  • Aleurothrixus floccosus Aleurothrixus floccosus, Aleyrodes brassicae, Aonidiella spp., Aphididae, Aphis spp.,
  • Aspidiotus spp. Bemisia tabaci, Ceroplaster spp., Chrysomphalus aonidium,
  • Erythroneura spp. Gascardia spp., Laodelphax spp., Lecanium corni, Lepidosaphes spp.,
  • Macrosiphus spp. Myzus spp., Nephotettix spp., Nilaparvata spp., Paratoria spp.,
  • Pemphigus spp. Planococcus spp., Pseudaulacaspis spp., Pseudococcus spp., Psylla spp.,
  • Hoplocampa spp. Lasius spp., Monomorium pharaonis, Neodiprion spp., Solenopsis spp. and Vespa spp.;
  • Aedes spp. Antherigona soccata, Bibio hortulanus, Calliphora erythrocephala, Ceratitis spp., Chrysomyia spp., Culex spp., Cuterebra spp., Dacus spp., Drosophila melanogaster,
  • Boophilus spp. Brevipalpus spp., Bryobia praetiosa, Calipitrimerus spp., Chorioptes spp.,
  • Dermanyssus gallinae Eotetranychus carpini, Eriophyes spp., Hyalomma spp., Ixodes spp., Olygonychus pratensis, Omithodoros spp., Panonychus spp., Phyllocoptruta oleivora,
  • the mentioned phytopathogenic fungi include, for example:
  • Botrytis spp. Pyricularia spp., Helminthosporium spp., Fusarium spp., Septoria spp.,
  • Rhizoctonia spp. Hemileia spp. and Puccinia spp.;
  • Venturia spp. Erysiphe spp., Podosphaera spp., Monilinia spp. and Uncinula spp.; and of the class of the Oomycetes, for example,
  • Target crops are especially cereals, such as wheat barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit such as pomes, stone fruit and soft fruit such as apples, pears, plums, peaches, almonds, cherries, or berries, for example strawberries, raspberries or blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans and groundnuts; cucumber plants, such as marrows, cucumber and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruit such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocados, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane
  • the compounds of the invention are suitable especially for controlling insects and representatives of the order Acarina, especially plant-destructive feeding insects, such as Anthonomus grandis, Diabrotica balteata, Heliothis virescens larvae, Plutella xylostella and Spodoptera littoralis larvae, and spider mites, such as Tetranychus spp., in cotton, fruit, maize, soybean, rape and vegetable crops.
  • Further areas of use of the compounds according to the invention are the protection of stored goods and stocks and materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type.
  • the invention therefore relates also to pesticides, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • pesticides such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, coatable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules or encapsulations in polymer substances, comprising - at least - one of the compounds of the invention, the type of formulation being chosen in accordance with the intended objectives and prevailing circumstances.
  • the active ingredient is used in those compositions in pure form, a solid active ingredient, for example, in a specific particle size, or preferably together with - at least - one of the adjuvants customary in formulation technology, such as extenders, for example solvents or solid carriers, or surface-active compounds (surfactants).
  • extenders for example solvents or solid carriers, or surface-active compounds (surfactants).
  • Suitable solvents are, for example: optionally partially hydrogenated aromatic hydrocarbons, preferably the fractions of alkylbenzenes containing 8 to 12 carbon atoms, such as xylene mixtures, alkylated naphthalenes or tetrahydronaphthalene, aliphatic or cycloaliphatic hydrocarbons, such as paraffins or cyclohexane, alcohols, such as ethanol, propanol or butanol, glycols and their ethers and esters, such as propylene glycol, dipropylene glycol ether, ethylene glycol or ethylene glycol monomethyl or monoethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-methylpyrrolid-2-one, dimethyl sulfoxide or N,N-dimethylformamide, water, vegetable oils or epoxidised vegetable oils, such as rape oil, castor oil,
  • the solid carriers used are normally natural mineral fillers such as calcite, talcum, kaolin, montmorillonite or attapulgite.
  • Suitable granulated adsorptive carriers are porous types, such as pumice, broken brick, sepiolite or bentonite; and suitable nonsorbent carriers are calcite or sand.
  • suitable nonsorbent carriers are calcite or sand.
  • a great number of granulated materials of inorganic or organic nature can be used, especially dolomite or pulverised plant residues.
  • suitable surface-active compounds are non-ionic, cationic and/or anionic surfactants or mixtures of surfactants having good emulsifying, dispersing and wetting properties.
  • the surfactants listed below are to be regarded merely as examples; many more surfactants customarily employed in formulation technology and suitable for use according to the invention are described in the relevant literature.
  • Non-ionic surfactants are preferably polyglycol ether derivatives of aliphatic or cycloaliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, said derivatives containing 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon moiety and 6 to 18 carbon atoms in the alkyl moiety of the alkylphenols.
  • non-ionic surfactants are water-soluble adducts of polyethylene oxide with polypropylene glycol, ethylenediaminopolypropylene glycol and alkylpolypropylene glycol containing 1 to 10 carbon atoms in the alkyl chain, which adducts contain 20 to 250 ethylene glycol ether groups and 10 to 100 propylene glycol ether groups. These compounds usually contain 1 to 5 ethylene glycol units per propylene glycol unit
  • non-ionic surfactants are nonylphenol polyethoxyethanols, castor oil polyglycol ethers, polypropylene/polyethylene oxide adducts, tributylphenoxypolyethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Fatty acid esters of polyoxyethylene sorbitan, e.g. polyoxyethylene sorbitan trioleate, are also suitable non-ionic surfactants.
  • Cationic surfactants are preferably quaternary ammonium salts which contain, as substituent at least one C 8 -C 22 alkyl radical and, as further substituents, unsubstituted or halogenated lower alkyl, benzyl or hydroxy-lower alkyl radicals.
  • the salts are preferably in the form of halides, methyl sulfates or ethyl sulfates. Examples are stearyltrimethylammonium chloride and benzyldi(2-chloroethyl)ethylammonium bromide.
  • Suitable soaps are the alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts of higher fatty acids (C 10 -C 22 ), e.g. the sodium or potassium salts of oleic or stearic acid or of natural fatty acid mixtures which can be obtained e.g. from coconut oil or tall oil; mention may also be made of fatty acid methyltaurin salts. More frequently, however, synthetic surfactants are used, especially fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates or sulfates are usually in the form of alkali metal salts, alkaline earth metal salts or unsubstituted or substituted ammonium salts and generally contain a C 8 -C 22 alkyl radical, which also includes the alkyl moiety of acyl radicals; there may be mentioned by way of example the sodium or calcium salt of lignosulfonic acid, of dodecyl sulfate or of a mixture of fatty alcohol sulfates obtained from natural fatty acids. These compounds also comprise the salts of sulfated and sulfonated fatty alcohol/ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and one fatty acid radical containing approximately 8 to 22 carbon atoms.
  • alkylarylsulfonates are the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, dibutylnaphthalenesulfonic acid or of a condensate of naphthalenesulfonic acid and formaldehyde.
  • corresponding phosphates e.g. salts of the phosphoric acid ester of an adduct of p-nonylphenol with 4 to 14 mol of ethylene oxide, or phospholipids.
  • compositions usually comprise 0.1 to 99 %, preferably 0.1 to 95 %, of active ingredient and 1 to 99.9 %, preferably 5 to 99.9 %, of - at least - one solid or liquid adjuvant, it generally being possible for 0 to 25 %, preferably 0.1 to 20 %, of the composition to be surfactants (in each case percentages are by weight).
  • surfactants in each case percentages are by weight.
  • Emulsifiable concentrates are:
  • active ingredient 1 to 90 %, preferably 5 to 20 %
  • surfactant 1 to 30 %, preferably 10 to 20 %
  • solvent 5 to 98 %, preferably 70 to 85 %
  • active ingredient 0.1 to 10 %, preferably 0.1 to 1 %
  • solid carrier 99.9 to 90 %, preferably 99.9 to 99 %
  • active ingredient 5 to 75 %, preferably 10 to 50 %
  • active ingredient 0.5 to 90 %, preferably 1 to 80 %
  • surfactant 0.5 to 20 %, preferably 1 to 15 %
  • solid carrier 5 to 99 %, preferably 15 to 98 %
  • active ingredient 0.5 to 30 %, preferably 3 to 15 %
  • solid carrier 99.5 to 70 %, preferably 97 to 85 %
  • compositions according to the invention can be substantially broadened and adapted to prevailing circumstances by the addition of other insecticidal, acaricidal and/or fungicidal active ingredients.
  • suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
  • suitable additional active ingredients include representatives of the following classes of compounds: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carbamates, pyrethroids, chlorinated hydrocarbons, and Bacillus thuringiensis preparations.
  • the compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, for example vegetable oils or epoxidised vegetable oils (e.g.
  • epoxidised coconut oil, rape oil or soybean oil epoxidised coconut oil, rape oil or soybean oil
  • antifoams for example silicone oil, preservatives, viscosity regulators, binders and/or tackifiers, as well as fertilisers or other active ingredients for obtaining special effects, for example bactericides, nematicides, molluscicides or selective herbicides.
  • compositions according to the invention are prepared in known manner, in the absence of adjuvants, for example by grinding and/or sieving a solid active ingredient or mixture of active ingredients, for example to a specific particle size, and in the presence of at least one adjuvant for example by intimately mixing and/or grinding the active ingredient or mixture of active ingredients with the adjuvants).
  • the invention relates also to that process for the preparation of the compositions according to the invention and to the use of the compounds of formula I for the preparation of those compositions.
  • the invention relates also to the methods of application of the compositions, i.e. the methods of controlling pests of the mentioned type, such as spraying, atomising, dusting, coating, dressing, scattering or pouring, which are selected in accordance with the intended objectives and prevailing circumstances, and to the use of the compositions for controlling pests of the mentioned type.
  • Typical rates of concentration are from 0.1 to 1000 ppm, preferably from 0.1 to 500 ppm, of active ingredient.
  • the rates of application per hectare are generally from 1 to 2000 g of active ingredient per hectare, especially from 10 to 1000 g/ha, preferably from 20 to 600 g/ha.
  • a preferred method of application in the area of plant protection is application to the foliage of the plants (foliar application), the number of applications and the rate of application depending on the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) if the locus of the plants is impregnated with a liquid formulation or if the active ingredient is incorporated in solid form into the locus of the plants, for example into the soil, e.g. in granular form (soil application). In paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • compositions according to the invention are also suitable for protecting plant propagation material, e.g. seed material, such as fruit tubers or grains, or plant cuttings, from fungal infections and animal pests.
  • the propagation material can be treated with the formulation before planting: seed, for example, can be dressed before being sown.
  • the compounds of the invention can also be applied to grains (coating), either by impregnating the grains with a liquid formulation or by coating them with a solid formulation.
  • the formulation can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • the invention relates also to that method of treating plant propagation material and to the plant propagation material thus treated.
  • Example 17 The other compounds listed in Tables 1 to 3 can also be prepared in a manner analogous to that described in Examples II to 16. Melting points are given in °C.
  • Example A5 The other compounds listed in Tables 4 to 6 can also be prepared in a manner analogous to that described in Examples Al to A4. Melting points are given in °C.
  • Example F1 Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol
  • Emulsions of any desired concentration can be prepared from such concentrates by dilution with water.
  • Example F2 Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl
  • N-methyl-2-pyrrolidone 20 % - - epoxidised coconut oil - - 1 % 5 % petroleum fraction
  • Example F3 Granules a) b) c) d) active ingredient 5% 10% 8% 21% kaolin 94% - 79% 54% highly dispersed silicic acid 1% - 13% 7% attapulgite - 90% - 18%
  • Example F4 Dusts a) b)
  • Example F5 Wettable powders a) b) c)
  • the active ingredient is mixed with the adjuvants and thoroughly ground in a suitable mill, affording wettable powders which can be diluted with water to give suspensions of the desired concentration.
  • Example F6 Emulsifiable concentrate
  • xylene mixture 50 % Emulsions of any required concentration can be obtained from this concentrate by dilution with water.
  • Example F7 Dusts a) b)
  • Ready-for-use dusts are obtained by mixing the active ingredient with the carrier and grinding the mature in a suitable mill.
  • Example F8 Extruder granules
  • the active ingredient is mixed and ground with the adjuvants, and the mixture is moistened with water.
  • the mixture is extruded and granulated, and then dried in a stream of air.
  • Example F9 Coated granules
  • the finely ground active ingredient is uniformly applied, in a mixer, to the kaolin moistened with polyethylene glycol. Non-dusty coated granules are obtained in this manner.
  • silicone oil in the form of a 75 %
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired concentration can be obtained by dilution with water.
  • Example B2 Action against Nilaparvata lugens
  • Rice plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the rice plants are populated with cicada larvae in the 2nd and 3rd stages. Evaluation is made 21 days later. The percentage reduction in the population (% activity) is determined by comparing the number of surviving cicadas on the treated plants with that on untreated plants.
  • Maize seedlings are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the maize seedlings are populated with 10 Diabrotica balteata larvae in the second stage and placed in a plastics container.
  • the percentage reduction in the population is determined by comparing the number of dead larvae on the treated plants with that on untreated plants.
  • Example B4 Action against Anthonomus grandis adults
  • Young cotton plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cotton plants are populated with 10 Anthonomus grandis adults and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead beetles and the feeding damage on the treated plants with that on untreated plants.
  • Example B5 Action against Heliothis virescens caterpillars
  • Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Heliothis virescens caterpillars in the first stage and placed in a plastics container.
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B6 Action against Spodoptera littoralis caterpillars
  • Young soybean plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the soybean plants are populated with 10 Spodoptera littoralis caterpillars in the third stage and placed in a plastics container.
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B7 Action against Crocidolomia binotalis caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 Crocidolomia binotalis caterpillars in the third stage and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in the population or the percentage reduction in feeding damage (% activity) is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • Example B8 Systemic action against Nilaparvata lugens
  • Pots containing rice plants are placed in an aqueous emulsion comprising 400 ppm of the test compound.
  • the rice plants are then populated with larvae in the 2nd and 3rd stages. Evaluation is made 6 days later.
  • the percentage reduction in the population is determined by comparing the number of cicadas on the treated plants with that on untreated plants.
  • Young bean plants are populated with Tetranychus urticae females which are removed after 24 hours.
  • the plants that are populated with eggs are sprayed with an aqueous emulsion comprising 400 ppm of test compound.
  • the plants are then incubated for 6 days at 25°C and then evaluated.
  • the percentage reduction in the population is determined by comparing the number of dead eggs, larvae and adults on the treated plants with that on untreated plants.
  • Example B 11 Action against Blattella germanica
  • a 0.1 % solution of test compound in acetone is introduced into a Petri dish until the amount corresponds to a rate of application of 2 g/m 2 .
  • 20 Blattella germanica nymphs (final nymph stage) are introduced into the prepared dish and exposed to the action of the test compound for 2 hours.
  • the nymphs are then narcotised with CO 2 , introduced into a fresh Petri dish and kept in the dark at 25°C and 50 to 70 % humidity. After 48 hours the insecticidal action is evaluated by determining the mortality rate.
  • Example B12 Action against Lucilia cuprina blowflies
  • test tubes Small portions of freshly deposited eggs of the blowfly species Lucilia cuprina (30 to 50 eggs) are placed in test tubes in which 4 ml of nutrient medium have previously been mixed with 1 ml of test solution comprising 16 ppm of test compound. After inoculation of the culture medium, the test tubes are closed with a cotton wool plug and incubated in an incubator at 30°C for 4 days. By that time, larvae approximately 1 cm long (stage 3) have developed in the untreated medium. If the compound is active, by that time the larvae are either dead or clearly retarded. Evaluation is made after 96 hours.
  • Example B 13 Action against Musca domestica
  • a sugar cube is so treated with a solution of the test compound that the concentration of test compound in the sugar, after drying overnight, is 250 ppm.
  • the treated cube is placed on an aluminium dish with a wet cotton wool swab and 10 Musca domestica adults of an OP resistant strain, covered with a glass beaker and incubated at 25°C. After 24 hours the mortality rate is determined.
  • Example B14 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion comprising 400 ppm of test compound. After the spray coating has dried, the cabbage plants are populated with 10 Plutella xylostella caterpillars in the third stage and placed in a plastics container.
  • the percentage reduction in the population or the percentage reduction in feeding damage is determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.

Abstract

On peut utiliser comme ingrédients agrochimiques actifs et préparer d'une manière connue en soi, sous forme libre ou sous forme de sel, des composés de la formule (I), dans laquelle n représente 1, 2, 3 ou 4; lorsque n est supérieur à 1, les radicaux R3 sont identiques ou différents; R1 représente halogène ou halo-alkyle C1-C9; R2 représente halogène; R3 représente hydrogène, cyano, nitro, halogène, alkyle C1-C4, alcoxy C1-C4, alkylthio C1-C4, alcanesulfinyle C1-C4, alcanesulfonyle C1-C4, halo-alkyle C1-C4, halo-alcoxy C1-C4, halo-alkylthio C1-C4, halo-alcanesulfinyle C1-C4 ou halo-alcanesulfonyle C1-C4 et/ou deux substituants R3 fixés à des atomes de carbone adjacents du cycle phényle forment ensemble un pont non substitué ou substitué choisi dans le groupe de ponts constitué par -O-CH2-O-, -O-CH2-CH2-, -O-CH2-CH2-O-, -O-CH2-CH2-CH2- et -CH=CH-CH=CH-; R4 représente hydrogène, alkyle C1-C4, alcényle C3-C4, halo-alcényle C3-C4, alkynyl C3-C4, cyano, alkylthio C1-C4, alcanesulfinyle C1-C4, alcanesulfonyle C1-C4, halo-alcanesulfonyle C1-C4, dialkylaminosulfonyle C1-C4, dialkylaminocarbonyle C1-C4 ou un groupe alkyle C1-C4 substitué; R5 représente halo-alkyle C1-C6, halo-alcoxy C1-C6 ou -OS(=O)2R6, et R6 représente alkyle C1-C6 ou halo-alkyle C?1-C6.
PCT/EP1993/002231 1992-09-01 1993-08-20 3-cyano-4-halogeno-2-(subst phenyl)-pyrroles utilises comme pesticides et fongicides WO1994005633A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU49506/93A AU4950693A (en) 1992-09-01 1993-08-20 3-cyano-4-halogeno-2-(subst.phenyl)-pyrroles as pesticides and fungicides

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
CH2730/92-2 1992-09-01
CH273092 1992-09-01
CH510/93-7 1993-02-18
CH51093 1993-02-18

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WO1994005633A1 true WO1994005633A1 (fr) 1994-03-17

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PCT/EP1993/002231 WO1994005633A1 (fr) 1992-09-01 1993-08-20 3-cyano-4-halogeno-2-(subst phenyl)-pyrroles utilises comme pesticides et fongicides

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CN (1) CN1087336A (fr)
AU (1) AU4950693A (fr)
IL (1) IL106811A0 (fr)
MX (1) MX9305347A (fr)
WO (1) WO1994005633A1 (fr)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995018122A2 (fr) * 1993-12-30 1995-07-06 Ciba-Geigy Ag Pyrroles heteroaryles
US6919470B2 (en) 2000-03-30 2005-07-19 Bayer Aktiengesellschaft Aryl and heteroaryl sulfonates
WO2016125621A1 (fr) * 2015-02-03 2016-08-11 住友化学株式会社 Composé benzimidazole, et application de celui-ci pour lutter contre les arthropodes nuisibles
WO2016125622A1 (fr) * 2015-02-03 2016-08-11 住友化学株式会社 Composé benzoxazole, et application de celui-ci pour lutter contre les arthropodes nuisibles

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104418789A (zh) * 2013-08-26 2015-03-18 南开大学 对氯苄基吡咯类化合物及其制备和在防治虫螨菌方面的应用

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347488A1 (fr) * 1988-06-23 1989-12-27 American Cyanamid Company Arylpyrroles comme agents insecticides, acaricides et nématicides et procédé pour leur préparation
EP0434940A2 (fr) * 1989-12-08 1991-07-03 American Cyanamid Company Arylpyrroles N-oxygénés comme agents insecticides, acaricides et nématicides
EP0480204A1 (fr) * 1990-09-25 1992-04-15 Fujisawa Pharmaceutical Co., Ltd. Dérivés d'imidazole, antagonistes sélectives et efficaces du récepteur d'angiotensin II
EP0484614A2 (fr) * 1990-05-11 1992-05-13 American Cyanamid Company Arylepyrroles N-acylés comme agents insecticides, acaricides, nématicides et molluscicides
EP0530147A1 (fr) * 1991-08-28 1993-03-03 Ciba-Geigy Ag 3-Cyano-2-phényl-pyrroles comme pesticides
EP0545103A1 (fr) * 1991-12-04 1993-06-09 American Cyanamid Company Pyrroles, substitués en position 1 par un groupe thioalkyle substitué, comme insecticides, accaricides et molluscicides

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0347488A1 (fr) * 1988-06-23 1989-12-27 American Cyanamid Company Arylpyrroles comme agents insecticides, acaricides et nématicides et procédé pour leur préparation
EP0434940A2 (fr) * 1989-12-08 1991-07-03 American Cyanamid Company Arylpyrroles N-oxygénés comme agents insecticides, acaricides et nématicides
EP0484614A2 (fr) * 1990-05-11 1992-05-13 American Cyanamid Company Arylepyrroles N-acylés comme agents insecticides, acaricides, nématicides et molluscicides
EP0480204A1 (fr) * 1990-09-25 1992-04-15 Fujisawa Pharmaceutical Co., Ltd. Dérivés d'imidazole, antagonistes sélectives et efficaces du récepteur d'angiotensin II
EP0530147A1 (fr) * 1991-08-28 1993-03-03 Ciba-Geigy Ag 3-Cyano-2-phényl-pyrroles comme pesticides
EP0545103A1 (fr) * 1991-12-04 1993-06-09 American Cyanamid Company Pyrroles, substitués en position 1 par un groupe thioalkyle substitué, comme insecticides, accaricides et molluscicides

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1995018122A2 (fr) * 1993-12-30 1995-07-06 Ciba-Geigy Ag Pyrroles heteroaryles
WO1995018122A3 (fr) * 1993-12-30 1995-08-10 Ciba Geigy Ag Pyrroles heteroaryles
US6919470B2 (en) 2000-03-30 2005-07-19 Bayer Aktiengesellschaft Aryl and heteroaryl sulfonates
WO2016125621A1 (fr) * 2015-02-03 2016-08-11 住友化学株式会社 Composé benzimidazole, et application de celui-ci pour lutter contre les arthropodes nuisibles
WO2016125622A1 (fr) * 2015-02-03 2016-08-11 住友化学株式会社 Composé benzoxazole, et application de celui-ci pour lutter contre les arthropodes nuisibles

Also Published As

Publication number Publication date
AU4950693A (en) 1994-03-29
CN1087336A (zh) 1994-06-01
IL106811A0 (en) 1993-12-08
MX9305347A (es) 1994-03-31

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