WO2005019147A2 - Pesticidally active phenol derivatives - Google Patents

Pesticidally active phenol derivatives Download PDF

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Publication number
WO2005019147A2
WO2005019147A2 PCT/EP2004/009500 EP2004009500W WO2005019147A2 WO 2005019147 A2 WO2005019147 A2 WO 2005019147A2 EP 2004009500 W EP2004009500 W EP 2004009500W WO 2005019147 A2 WO2005019147 A2 WO 2005019147A2
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spp
alkyl
crc
formula
compound
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PCT/EP2004/009500
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French (fr)
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WO2005019147A3 (en
Inventor
Werner Zambach
Stephan Trah
Roger Graham Hall
William Lutz
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Syngenta Participations AG
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Syngenta Participations AG
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Priority to EP04764476A priority Critical patent/EP1659863A2/en
Priority to JP2006524326A priority patent/JP2007503416A/en
Priority to US10/568,993 priority patent/US7638514B2/en
Publication of WO2005019147A2 publication Critical patent/WO2005019147A2/en
Publication of WO2005019147A3 publication Critical patent/WO2005019147A3/en
Anticipated expiration legal-status Critical
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    • C07C205/37—Compounds containing nitro groups bound to a carbon skeleton the carbon skeleton being further substituted by etherified hydroxy groups having nitro groups and etherified hydroxy groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton to carbon atoms of the same non-condensed six-membered aromatic ring or to carbon atoms of six-membered aromatic rings being part of the same condensed ring system the oxygen atom of at least one of the etherified hydroxy groups being further bound to an acyclic carbon atom
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    • C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
    • C07D295/08—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms
    • C07D295/096—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly bound oxygen or sulfur atoms with the ring nitrogen atoms and the oxygen or sulfur atoms separated by carbocyclic rings or by carbon chains interrupted by carbocyclic rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/06—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to the ring carbon atoms
    • C07D333/22—Radicals substituted by doubly bound hetero atoms, or by two hetero atoms other than halogen singly bound to the same carbon atom
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/04—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings directly linked by a ring-member-to-ring-member bond
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te

Definitions

  • the present invention relates (1) to a compound of formula
  • X T and X 2 are each independently of the other fluorine, chlorine or bromine;
  • a T and A 2 are each independently of the other a bond or a CrC 6 alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C 3 -C 8 cycloalkyl;
  • a 3 is a d-C ⁇ alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C 3 -C 8 cycloalkyl;
  • R-i and R 2 are each independently of the other halogen, OH, SH, CN, nitro, C-,-C 6 alkyl, d-Cehaloalkyl, C-rC 6 alkyl-carbonyl, C 2 -C 6 alkenyl, C 2 -C 6 haloalkenyl, C 2 -C 6 alkynyl, Ci-Cealkoxy
  • Certain dihaloallyl derivatives are proposed in the literature as active ingredients in pesticidal compositions.
  • the biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, especially for controlling insects and members of the order Acarina, that problem surprisingly being solved by the provision of the present compounds of formula (I).
  • the compounds of formula (I) and, where applicable, their tautomers are able to form salts, e.g. acid addition salts.
  • the latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g.
  • organic carboxylic acids such as unsubstituted or substituted, e.g. halo-substituted, d-C 4 alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g.
  • salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morph- oline, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g.
  • Halogen as a group per se and as a structural element of other groups and compounds, such as of haloalkyl, halocycloalkyl, haloalkenyi, haloalkynyl and haloalkoxy, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, especially chlorine.
  • carbon-containing groups and compounds each contain from 1 up to and including 20, preferably from 1 up to and including 18, especially from 1 up to and including 10, more especially from 1 up to and including 6, especially from 1 up to and including 4, more especially from 1 up to and including 3, very especially 1 or 2, carbon atoms; methyl is especially preferred.
  • Alkylene is a straight-chain or branched bridging member and is especially -CH 2 -, -CH 2 CH -, -CH 2 -CH 2 -CH 2 -, -CH -CH 2 -CH -CH 2 -, -CH 2 -CH 2 -CH 2 -CH 2 _ , -CH(CH 3 )-, -CH 2 (CH 3 )CH 2 -CH 2 -, -CH(C 2 H 5 )-, -C(CH 3 ) 2 -, -CH(CH 3 )CH 2 -, -CH(CH 3 )CH(CH 3 )- or Alkyl, as a group per se and as a structural element of other groups and compounds, such as of haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfonyl and al
  • Alkenyl and alkynyl - as groups per se and as structural elements of other groups and compounds, such as of haloalkenyl, haloalkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy or haloalkynyloxy - are straight-chain or branched and each contains two or preferably one unsaturated carbon-carbon bond(s).
  • haloalkenyl, haloalkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy or haloalkynyloxy - are straight-chain or branched and each contains two or preferably one unsaturated carbon-carbon bond(s).
  • Cycloalkyl - as a group per se and as a structural element of other groups and compound ' s, such as of cycloalkylalkyl - is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and cyclohexyl, and especially cyclopropyl, are preferred.
  • Halo-substituted carbon-containing groups and compounds, such as haloalkyl and haloalkoxy may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different.
  • haloalkyl - as a group per se and as a structural element of other groups and compounds, such as of haloalkoxy - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF 2 , CF 3 or CH 2 CI; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH 2 CF 3 , CF 2 CF 3 , CF 2 CCI 3 , CF 2 CHCI 2 , CF 2 CHF 2 , CF 2 CFCI 2 , CH 2 CH 2 CI, CF 2 CHBr 2 , CF 2 CHCIF, CF 2 CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH 2 CHBrCH 2 Br, CF 2 CHFCF 3 , CH 2 CF 2 CF 3 , CF 2 CF 2 CF 3
  • Aryl is especially phenyl or naphthyl, preferably phenyl.
  • Heterocyclyl is to be understood as being a five- to seven-membered monocyclic ring containing from one to four hetero atoms selected from the group consisting of N, O and S, or a bicyclic ring system which may contain either in only one ring - such as, for example, in quinolyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl - or in both rings - such as, for example, in pteridinyl or purinyl - independently of one another, one or more hetero atoms selected from N, O and S.
  • Preferred embodiments within the scope of the invention are (2) compounds according to (1) of formula (I) wherein A 3 is a straight-chain alkylene bridge, especially methylene, ethylene, propylene or butylene; more especially methylene; (3) compounds according to (1) or (2) of formula (I) wherein Q is oxygen; (4) compounds according to (1) to (3) of formula (I) wherein Y is oxygen; (5) compounds according to (1) to (4) of formula (I) wherein R ⁇ and R 2 are each independently of the other CN, nitro, d-C 6 alkyl, C ⁇ -C 6 haloalkyl, fluorine, chlorine or bromine; especially chlorine; (6) compounds according to (1) to (5) of formula (I) wherein R 3 is hydrogen; (7) compounds according to (1) to (6) of formula (I) wherein X-i and X 2 are chlorine or bromine, especially chlorine; (8) compounds according to (1) to (7) of formula (I) wherein R 4 and R 5 are H, methyl, fluorine or chlorine; (9) compounds according to
  • L 3 is a leaving group, preferably chlorine or bromine, and Hal is chlorine or bromine; or (g 2 ) for the preparation of a compound of formula (I) wherein X ⁇ and X 2 are chlorine or bromine, a compound of formula (IV) is reacted in the presence of a base with a compound of formula
  • the invention relates also to (h) a process for the preparation of a compound of formula (I), as defined under (1), and wherein Q is O, NR 7 or S, and R 7 is as defined for formula (I) under (1 ), wherein a compound of formula
  • a ⁇ A 2 , A 3 , T, W, R 4 and R 5 are as defined for formula (I) under (1), and L is a leaving group, is reacted in the presence of a base with a compound of formula
  • R ⁇ R 2 , R 3 and m are as defined for formula (I) under (1)
  • Q is O, NR 7 or S and Z is one of the radicals Z to Z 6 as defined for formulae (II) to (VII) above
  • R 7 is as defined for formula (I) under (1)
  • the resulting compound of formula wherein E, T, W, Q, A-,, A 2 , A 3 , R 1 t R 2 , R 3 , R 4 , R 5 and m are as defined for formula (I) under (1) and Z is one of the radicals Zi to Z 6 as defined for formulae (II) to (VII) above, is, as necessary, that is to say according to the meaning of the radical Z, reacted further analogously to one or more of process steps (a) to (g).
  • Z in compound X/a has the same meanings as Zi in the compound of formula (II)
  • Z in compound X/b has the same meanings as Z 2 in formula (III), and so on.
  • the invention relates also to (i) a process for the preparation of a compound of formula (I) as defined under (1 ) above, wherein a compound of formula (VIII) as defined above, is reacted analogously to process step (h) with a compound of formula
  • R ⁇ R 2 , R 3 , Q, Xi, X 2 , Y and m are as defined for formula (I) under (1).
  • D is a halogen atom, especially chlorine
  • the radicals Z are as defined above for the compounds X/a to X/f; that is to say, Z in the compound of formula XIII/a has the same meanings as Z-i in the compound of formula (II), and Z in compound Xlll/b has the same meanings as Z 2 in formula (III), and so on.
  • the invention relates also to (l-i) a process for the preparation of a compound of formula
  • E, T, A ⁇ and A 2 are as defined for formula (I) and R 41 and R 51 are CrC 6 alkyl, C C 3 haloalkyl, CrC 6 alkoxy-CrC 6 alkyl, C 3 -C 8 cycloalkyl, or C 3 -Cscycloalkyl-CrC 6 alkyl, wherein a compound of formula
  • E, T, A T and A 2 are as defined for formula (I), R 41 and R 42 are as defined above for formula (XII) or are halogen, and R is C C 6 alkyl, wherein a compound of formula wherein E, T, A-,, A 2 and R are as defined for formula (Xlld), is reacted with a tetrahalomethane in the presence of triphenylphosphine or with an alkyltriphenyl- phosphonium salt in the presence of a base.
  • the invention relates also to (m-i) a process for the preparation of a compound of formula
  • the invention relates also to a process for the preparation of a compound of formula (I), wherein W is a bond and A 3 is CH 2 , wherein a compound of formula (XVIII) is processed further analogously to one of process steps (I-,) to (l 3 ) and steps (a) to (g).
  • process steps (a) to (g) and (I-,) to (l 3 ) may be carried out in any desired order, that is to say, for example, there are carried out first two steps analogously to steps (a) and (b), then, for example, step (l 2 ), and subsequently the steps analogously to steps (c) to (g).
  • the invention relates also to (n) a process for the preparation of a compound of formula
  • compounds of formula (I) wherein the bridging members Q, T and W are O, NR 7 or S can be obtained by reacting a starting compound that contains a leaving group at the appropriate position with another starting compound that contains OH, SH or NHR 7 at the position to be bridged.
  • Such starting compounds are, for example, the compounds of formulae (VIII), (XIX), (XXI), (XXII), (XXIII) and (XXIV), some of which are known and some of which are novel. Where novel, the invention relates also to such compounds.
  • Further suitable compounds that are also novel, to which the invention also relates are, for example, the compounds of formulae
  • a starting material that carries an aldehyde or a keto function can be combined with a starting material that carries a hydroxylamine function at the appropriate position.
  • Such preparation processes require, in addition to the above-mentioned compounds of formula (XII), for example, intermediates of the following formulae:
  • halogens such as fluorine, chlorine, bromine, iodine,
  • Especially preferred as a leaving group are chlorine or bromine, mesylate, triflate, tosylate, especially chlorine; or chloride or bromide, especially chloride.
  • oxidising agents there are used, for example, hydrogen peroxide, a peracid, such as peracetic acid, trifluoroperacetic acid, 3-chloroperbenzoic acid or a mixture, such as sodium perborate in acetic acid.
  • an inorganic base such as NaOH or KOH
  • aminolysis with a primary amine, such as n-butylamine can be carried out in a hydrocarbon, such as toluene or benzene, at temperatures of from 0°C to 150°C, preferably at from 20°C to 80°C.
  • the preferred reaction temperature is from 0°C to 120°C, especially from 20°C to 80°C.
  • a strong mineral acid for example hydrochloric acid, sulfuric acid or 4- toluenesulfonic acid.
  • the reaction is carried out in an inert solvent such as, for example, benzene or toluene, or an ether, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, at temperatures of from 0°C to 150°C, preferably at from 20°C to 80°C.
  • an inert solvent such as, for example, benzene or toluene
  • an ether such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran
  • dichlorovinyl compounds it is also possible for the process to be carried out in dimethylformamide, benzene, toluene, or in an ether, at temperatures of from 0°C to 120°C, preferably from 20°C to 80°C, and in the presence of trichloroacetic acid/ sodium trichloroacetate, then by addition of acetic anhydride, optionally with the addition of base, for example triethylamine, and finally by addition of zinc and acetic acid.
  • dimethylformamide, benzene, toluene, or in an ether at temperatures of from 0°C to 120°C, preferably from 20°C to 80°C, and in the presence of trichloroacetic acid/ sodium trichloroacetate, then by addition of acetic anhydride, optionally with the addition of base, for example triethylamine, and finally by addition of zinc and acetic acid.
  • a coupling reagent for example azodicar- boxylic acid diethyl or diisopropyl ester and triphenylphospine, can be used.
  • a halogenated hydrocarbon such as methylene chloride
  • an ether such as dioxane or tetrahydrofuran
  • the reaction may be carried out, on the one hand, in an alcohol, such as methanol or ethanol, in dimethylformamide, N-methylpyrrolidone or tetrahydrofuran as solvent, in the presence of a base, such as diethylamine, diisopropylamine, piperidine, KOH, NaOH or sodium methylate, at a temperature of from -70°C to the boiling temperature of the solvent; or, on the other hand, for example, the reaction may be carried out in acetic acid at from 20°C to 120°C in the presence of ammonium acetate.
  • a base such as diethylamine, diisopropylamine, piperidine, KOH, NaOH or sodium methylate
  • an ether such as dioxane, tetrahydrofuran or dimethoxyethane
  • aromatic solvent such as toluene or xylene
  • an ether such as dioxane, tetrahydrofuran or dimethoxyethane
  • an amide such as dimethylformamide, dimethylacet- amide or N-methylpyrrolidone
  • aromatic solvent such as toluene or xylene
  • a nitrile such as acetonitrile
  • a base such as potassium or sodium carbonate.
  • the invention relates especially to the preparation processes described in Examples P1 to P11.
  • salts of compounds of formula (I) with bases are obtained by treatment of the free compounds with a suitable base or with a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner, for example by treatment with a suitable acid or with a suitable ion exchange reagent.
  • Salts of compounds of formula (I) can be converted in a manner known per se into other salts of a compound of formula (I).
  • the compounds of formula (I), in free form or in salt form, may be in the form of one of the possible isomers or in the form of a mixture thereof, for example, depending upon the number of asymmetric carbon atoms occurring in the molecule and their absolute and relative configuration, and/or depending upon the configuration of non-aromatic double bonds occurring in the molecule, in the form of pure isomers, such as enantiomers 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 is to be interpreted as such hereinbefore and hereinafter, even if stereochemical details are not mentioned specifically in every case.
  • Mixtures of diastereoisomers, mixtures of racemates and mixtures of double bond isomers of compounds of formula (I), in free form or in salt form, that are obtainable by the process according to the invention - depending upon the starting materials and procedures chosen - or by some other method, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by means of fractional crystallisation, distillation and/or chromato- graphy.
  • enantiomers such as racemates
  • Mixtures of enantiomers, such as racemates, that are obtainable in a corresponding manner can be resolved into the enantiomers by known methods, for example by recrystal- lisation from an optically active solvent, by chromatography on chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, only one enantiomer being complexed, or by conversion into diastereoisomeric salts and separation of the mixture of diastereoisomers so obtained, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be freed by the action of suitable agents.
  • HPLC high pressure liquid chromatography
  • the compounds of formula (I), in free form or salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents which may have been used for the crystallisation of compounds present in solid form.
  • the invention relates to all those embodiments 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 some or all of the remaining steps are carried out or a starting material is used in the form of a derivative or salt and/or its racemates or enantiomers or, especially, is formed under the reaction conditions.
  • the compounds of formula (1) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants.
  • the active ingredients according to 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 members of the order Acarina.
  • the insecticidal or acaricidal activity of the active ingredients according to the invention may manifest itself directly, i.e.
  • Abagrotis spp. Abraxas spp., Acantholeucania spp., Acanthoplusia spp., Acarus spp., Acarus siro, Aceria spp., Aceria sheldoni, Acleris spp., Acoloithus spp., Acompsia spp., Acossus spp., Acria spp., Acrobasis spp., Acrocercops spp., Acrolepia spp., Acrolepiopsis spp., Acronicta spp., Acropolitis spp., Actebia spp., Aculus spp., Aculus pointedendali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp., Aegeria spp., Aethes spp.
  • Such pests include, for example, root knot nematodes, cyst- forming nematodes and also stem and leaf nematodes; especially of Heterodera spp., e.g. Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., e.g. Globodera rostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita and Meloidogyne javanica; Radopholus spp., e.g. Radopholus similis; Pratylenchus, e.g.
  • Pratylenchus neglectans and Pratylenchus penetrans Pratylenchus penetrans
  • Tylenchulus e.g. Tylenchulus semipenetrans
  • Longidorus, Trichodorus, Xiphinema, Ditylenchus, Apheen- choides and Anguina especially Meloidogyne, e.g. Meloidogyne incognita, and Heterodera, e.g. Heterodera glycines.
  • An especially important aspect of the present invention is the use of the compounds of formula (I) according to the invention in the protection of plants against parasitic feeding pests.
  • Suitable additives include, for example, representatives of the following classes of active ingredient: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carba- mates, pyrethroids, chlorinated hydrocarbons, neonicotinoids and Bacillus thuringiensis preparations.
  • Examples of especially suitable mixing partners include: azamethiphos; chlorfenvin- phos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; dio- fenolan; a compound obtainable from the Bacillus thuringiensis strain GC91 or from strain NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azin
  • the compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases plant parts that grow later are still protected against those pests.
  • Target crops include especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g.
  • strawberries, raspberries and blackberries leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals.
  • the invention therefore relates also to pesticidal compositions, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules and encapsulations of polymer substances, that comprise at least one of the compounds according to the invention, the choice of formulation being made in accordance with the intended objectives and the 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, e.g.
  • Solvents are, for example: non-hydrogenated or partly hydrogenated aromatic hydrocarbons, preferably fractions C 8 to C 12 of alkylbenzenes, 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 ethers and esters thereof, such as propylene glycol, dipropyiene glycol ether, ethylene glycol or ethylene glycol monomethyl or -ethyl ether, ketones, such as cyclohexanone, isophorone or diacetone alcohol, strongly polar solvents, such as N-
  • the solid carriers used are as a rule natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acids or highly disperse absorbent polymers can also be added to improve the physical properties.
  • Granular adsorptive granule carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-sorbent carrier materials are calcite or sand. A large number of granular materials of inorganic or organic nature can furthermore be used, in particular dolomite or comminuted plant residues.
  • Surface-active compounds are, depending on the nature of the active compound to be formulated, nonionic, cationic and/or anionic surfactants or surfactant mixtures with good emulsifying, dispersing and wetting properties.
  • the surfactants listed below are to be regarded only as examples; many other surfactants which are customary in formulation technology and are suitable according to the invention are described in the relevant literature.
  • Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols.
  • Substances which are furthermore suitable are water-soluble polyethylene oxide adducts, containing 20 to 250 ethylene glycol ether and 10 to 100 propylene glycol ether groups, on propylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain.
  • the compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit.
  • examples are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypoly- ethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol.
  • Other substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate.
  • the cationic surfactants are, in particular, quaternary ammonium salts which contain, as substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals.
  • the salts are preferably in the form of halides, methyl-sulfates or ethyl-sulfates. Examples are stearyl-trimethyl-ammoniurn chloride and benzyl-di-(2-chloroethyl)-ethyl- ammonium bromide.
  • Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds.
  • Suitable soaps are the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C 10 -C 22 ), such as the sodium or potassium salts of oleic or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and furthermore also the fatty acid methyl-taurine salts.
  • synthetic surfactants are more frequently used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates.
  • the fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and in general have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts.
  • the sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 C atoms.
  • Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product.
  • Corresponding phosphates such as salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, can further also be used.
  • Emulsifiable concentrates 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%
  • Dusts active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%
  • Suspension concentrates active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: 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%
  • Granules 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 may also comprise further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxi- dised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers as well as fertilisers or other active ingredients for obtaining special effects, e.g. acaricides, bactericides, fungicides, nematicides, mollus- cicides or selective herbicides.
  • the crop protection products according to the invention are prepared in known manner, in the absence of adjuvants, e.g.
  • the invention relates likewise to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions.
  • the invention relates also to the methods of application of the crop protection products, i.e.
  • 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 crop protection is application to the foliage of the plants (foliar application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question.
  • the active ingredient can also penetrate the plants through the roots (systemic action) when the locus of the plants is impregnated with a liquid formulation or when 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 the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field.
  • the crop protection products according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against animal pests.
  • the propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
  • compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seed, such as fruits, tubers or grains, or plant seedlings, against animal pests.
  • the propagation material can be treated with the composition before being planted: seed, for example, can be dressed before being sown.
  • the active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation.
  • the composition 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 such methods of treating plant propagation material and to the plant propagation material so treated.
  • the following Examples serve to illustrate the invention. They do not limit the invention.
  • Example P1 Preparation of 3,3-dichloro-N- ⁇ 3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)- phenoxy]-propyl ⁇ -2-(4-trifluoromethyl-phenyl)-acrylamide
  • P1.1 680 mg of oxo-(4-trifluoromethyl-phenyl)-acetic acid ethyl ester and 2.2 g of tri- phenylphosphine are introduced into 8 ml of acetonitrile.
  • reaction mixture is cooled to 50°C and a solution of 500 mg of 1-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-3-(4-tri- fluoromethyl-phenoxy)-propan-2-one in 5 ml of toluene is added in the course of 5 minutes. After 2 hours at 80°C, the reaction mixture is filtered, diluted with ethyl acetate and washed with water. After concentration of the organic phase and purification over silica gel, the title compound is obtained.
  • Example P4 Preparation of 1 ,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[3,3-dichloro-2- (4-trifiuoromethyl-phenoxymethyl)-allyloxy]-benzene
  • Example P5 Preparation of 1 ,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[4-(4-fluoro- phenyl)-pent-4-enyloxy]-benzene P5.1) 2.0 g of 2-(3-chloro-propyl)-2-(4-fluoro-phenyl)-[1 ,3]dioxolane are added to a suspension of 2.36 g of 2,6-dichioro-4-(3,3-dichloro-allyloxy)-phenol, 1.7 g of potassium carbonate and 120 mg of potassium iodide in 50 ml of acetone. The mixture is then stirred for 48 hours at 60°C.
  • reaction mixture is concentrated and the residue is taken up in water and extracted with ethyl acetate. After concentration of the organic phase and purification over silica gel, 2- ⁇ 3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ⁇ -2-(4- fluoro-phenyl)-[1 ,3]dioxolane is obtained.
  • Example P6 Preparation of 2-(4-fluoro-phenyl)-3-methyl-but-2-enoic acid ⁇ 3-[2,6-di- chloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl ⁇ -amide
  • Example P7 The further Examples in the following Tables can also be prepared in a manner analogous to that described above.
  • Table 1 Compounds of formula
  • Table 2 A compound of general formula X-, and X 2 are chlorine and the substituent R for each compound corresponds to A.146 of Table A.
  • Table 3 A compound of general formula X-i and X 2 are chlorine and the substituent R for each compound corresponds to A.146 of Table A.
  • Table 4 A compound of general formula Xi and X 2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 5 A compound of general formula X-i and X 2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 6 A compound of general formula X and X 2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 7 A compound of general formula X 1 and X 2 are bromine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 8 A compound of general formula X ⁇ and X 2 are bromine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 9 A compound of general formula X T and X 2 are bromine and the substituent R for each compound corresponds 1 to A.146 of Table A.
  • Table 10 A compound of general formula (Id) wherein X n and X 2 are bromine and the substituent R for each compound corresponds to a line A.1 to A.146 of Table A.
  • Table 11 A compound of general formula (le) wherein X ⁇ and X 2 are bromine and the substituent R for each compound corresponds to a line A.1 to A.146 of Table A.
  • Table B Compounds of formulae
  • Table 12 A compound of general formula (If) wherein X-i and X 2 are chlorine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B.
  • Table 13 A compound of general formula (Ig) wherein and X 2 are chlorine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B.
  • Table 14 A compound of general formula (If) wherein Xi and X 2 are bromine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B.
  • Table 15 A compound of general formula (Ig) wherein and X 2 are bromine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B.
  • Example F1 Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol EO) 5% - - tributylphenol polyethylene glycol ether (30 mol EO) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
  • Example F2 Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (MW 400) - 70% - -
  • 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%
  • the active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.
  • Example B1 Action against Heliothis virescens caterpillars
  • the soybean plants are populated with 10 caterpillars of Heliothis virescens in the first stage and placed in a plastics container. Evaluation is made 6 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.
  • the compounds of the Tables exhibit good activity against Heliothis virescens in this test.
  • the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to 1.37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.
  • Example B2 Action against Plutella xylostella caterpillars
  • Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound. After the spray-coating has dried, the cabbage plants are populated with 10 caterpillars of Plutella xylostella in the third stage and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.
  • the compounds of the Tables exhibit good activity against Plutella xylostella in this test.
  • the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to 1.37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.
  • Example B3 Action against Spodoptera littoralis
  • Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound and, after the spray-coating has dried, the plants are populated with 10 caterpillars of Spodoptera littoralis in the first stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
  • the compounds of the Tables exhibit good activity against Spodoptera littoralis in this test.
  • the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to .37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.

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Abstract

There are described compounds of formula (I) wherein X1 and X2 are each independently of the other fluorine, chlorine or bromine; A1 and A2 are, for example, a bond or a C1-C6alkylene bridge; A3 is a C1-C6alkylene bridge; R1 and R2 are, for example, halogen, OH, SH, CN, nitro, C1-C6alkyl, C1-C6haloalkyl, C1-C6alkyl-carbonyl, C2­C6alkenyl, C2-C6haloalkenyl or C3-C6alkynyl; R,3 is, for example, H, halogen, OH, SH, CN, nitro, C1-C6alkyl or C1-C6haloaikyl; R4 and R5 are, for example, H, halogen, cyano, nitro, C1-C6alkyl or C1-C3haloalkyl; m is 1 or 2; Y is, for example, O, S, SO or SO2; Q is, for example, O, S, SO or SO2; W is, for example, a bond, O, S, SO, S02, -C(=O)-O- or -O-C(=O)-; T is, for example, a bond, O, S, SO, SO2, -C(=O)-O- or -O-C(=O)-; and E is aryl unsubstituted or substituted from one to five times or heterocyclyl unsubstituted or, depending upon the possibilities of substitution on the ring, substituted from one to four times; and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form, a process for the preparation of those compounds and their use, pesticidal compositions in which the active ingredient has been selected from those compounds and agrochemically acceptable salts thereof, a process for the preparation of those compositions and their use, plant propagation material treated with those compositions, and a method of controlling pests.

Description

Pesticidally active phenol derivatives
The present invention relates (1) to a compound of formula
Figure imgf000002_0001
wherein XT and X2 are each independently of the other fluorine, chlorine or bromine; AT and A2 are each independently of the other a bond or a CrC6alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C3-C8cycloalkyl; A3 is a d-Cδalkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C3-C8cycloalkyl; R-i and R2 are each independently of the other halogen, OH, SH, CN, nitro, C-,-C6alkyl, d-Cehaloalkyl, C-rC6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, Ci-Cealkoxy, d-Cβhaloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, C2-C6haloalkynyloxy, -(S=O)C-,-C6alkyl, -S(=O)2-C1-C6alkyl or CτC6alkoxycarbonyl; R3 is H, halogen, OH, SH, CN, nitro, C.,-C6alkyl, C-rCehaloalkyi, C C6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C C6alkoxy, d-Cehaloalkoxy, C2-C6alken- yloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy,
Figure imgf000002_0002
-S(=O)2-C1-C6alkyl, CrC6alkoxycarbonyl or C2-C6haloalkynyloxy; the substituents R3 being independent of one another when m is 2; R4 and R5 are each independently of the other H, halogen, cyano, nitro, d-Cβalkyl, CrQjhaloalkyl, d-Cβalkoxy-C-rCealkyl, CTCsalkyl-carbonyl, CrC3haloalkylcarbonyl, C C6alkoxycarbonyl, C3-C8cycloalkyl, Ca-Cβcycloalkyl-Ci-Cealkyl or C3-C8cycloalkylcarbonyl; m is 1 or 2; Y is O, NR6, S, SO or S02; Q is O, NR7, S, SO or S02; W is a bond, O, NR7, S, SO, S02, -C(=O)-O-, -0-C(=0)-, -C(R8)=N-0-, -C(=0)-NR9- or -NR9-C(=0)-; T is a bond, O, NR7, S, SO, S02, -C(=0)-0-, -0-C(=O)-, -C(=0)-NR9- or -NR9-C(=0)- or -C(R8)=N-0-; R6 and R7 are each independently of the other H, d-C6alkyl, d-C3haloalkyl, Cι-C6alkyl-carbonyl, d-C3haloalkylcarbonyl, d-Cealkoxy-d-Cealkyl, C C6alkoxycarbonyl, C3-C8cycloalkyl, C3-C8cycloalkyl-C C6alkyl or C3-C8cycloalkylcarbonyl; R8 is H, C C6alkyl, d-C3haloalkyl, d-Cealkoxy-d-Cealkyl or C3-C8cycloalkyl; R9 is H, Cι-C6alkyl, d-C3haloalkyl, d-C6alkyl-carbonyl, C C3haloalkylcarbonyl, C Cealkoxy-C Cealkyl, d-C6alkoxycarbonyl or C3-C8cycloalkyl; and E is aryl unsubstituted or substituted from one to five times or heterocyclyl unsubstituted or, depending upon the possibilities of substitution on the ring, substituted from one to four times; and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form, to a process for the preparation of those compounds, E/Z isomers and tautomers and to their use in the control of pests, to pesticidal compositions in which the active ingredient has been selected from those compounds, E/Z isomers and tautomers, and to a process for the preparation of those compositions and to their use, to intermediates and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in free form or in salt form, for the preparation of those compounds, where applicable to tautomers, in free form or in salt form, of those intermediates and to a process for the preparation of those intermediates and their tautomers and to their use. Certain dihaloallyl derivatives are proposed in the literature as active ingredients in pesticidal compositions. The biological properties of those known compounds are not entirely satisfactory in the field of pest control, however, for which reason there is a need to provide further compounds having pesticidal properties, especially for controlling insects and members of the order Acarina, that problem surprisingly being solved by the provision of the present compounds of formula (I). The compounds of formula (I) and, where applicable, their tautomers are able to form salts, e.g. acid addition salts. The latter are formed, for example, with strong inorganic acids, such as mineral acids, e.g. sulfuric acid, a phosphoric acid or a hydrohalic acid, with strong organic carboxylic acids, such as unsubstituted or substituted, e.g. halo-substituted, d-C4alkanecarboxylic acids, for example acetic acid, saturated or unsaturated dicarboxylic acids, e.g. oxalic, malonic, maleic, fumaric or phthalic acid, hydroxycarboxylic acids, e.g. ascorbic, lactic, malic, tartaric or citric acid, or benzoic acid, or with organic sulfonic acids, such as unsubstituted or substituted, e.g. halo-substituted, d-C4alkane- or aryl-sulfonic acids, e.g. methane- or p-toluene-suifonic acid. Furthermore, compounds of formula (I) having at least one acid group are able to form salts with bases. Suitable salts with bases are, for example, metal salts, such as alkali metal or alkaline earth metal salts, e.g. sodium, potassium or magnesium salts, or salts with ammonia or an organic amine, such as morph- oline, piperidine, pyrrolidine, a mono-, di- or tri-lower alkylamine, e.g. ethyl-, diethyl-, triethyl- or dimethyl-propyl-amine, or a mono-, di- or tri-hydroxy-lower alkylamine, e.g. mono-, di- or tri-ethanolamine. It may also be possible for corresponding internal salts to be formed. The free form is preferred. Of the salts of compounds of formula (I), preference is given to agro- chemically advantageous salts. Hereinabove and hereinbelow any reference to the free compounds of formula (I) or to their salts is to be understood as including, where appropriate, the corresponding salts or the free compounds of formula (I), respectively. The same applies to tautomers of compounds of formula (I) and their salts. The general terms used hereinabove and hereinbelow have the meanings given below, unless defined otherwise. Halogen, as a group per se and as a structural element of other groups and compounds, such as of haloalkyl, halocycloalkyl, haloalkenyi, haloalkynyl and haloalkoxy, is fluorine, chlorine, bromine or iodine, especially fluorine, chlorine or bromine, more especially fluorine or chlorine, especially chlorine. Unless defined otherwise, carbon-containing groups and compounds each contain from 1 up to and including 20, preferably from 1 up to and including 18, especially from 1 up to and including 10, more especially from 1 up to and including 6, especially from 1 up to and including 4, more especially from 1 up to and including 3, very especially 1 or 2, carbon atoms; methyl is especially preferred. Alkylene is a straight-chain or branched bridging member and is especially -CH2-, -CH2CH -, -CH2-CH2-CH2-, -CH -CH2-CH -CH2-, -CH2-CH2-CH2-CH2-CH2 _, -CH(CH3)-, -CH2(CH3)CH2-CH2-, -CH(C2H5)-, -C(CH3)2-, -CH(CH3)CH2-, -CH(CH3)CH(CH3)- or
Figure imgf000004_0001
Alkyl, as a group per se and as a structural element of other groups and compounds, such as of haloalkyl, alkoxy, alkoxyalkyl, haloalkoxy, alkoxycarbonyl, alkylthio, haloalkylthio, alkylsulfonyl and alkylsulfonyloxy, is - in each case giving due consideration to the number of carbon atoms contained in the group or compound in question - either straight-chain, e.g. methyl, ethyl, n-propyl, n-butyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, n-hexadecyl or n-octa- decyl, or branched, e.g. isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl or isohexyl. Alkenyl and alkynyl - as groups per se and as structural elements of other groups and compounds, such as of haloalkenyl, haloalkynyl, alkenyloxy, haloalkenyloxy, alkynyloxy or haloalkynyloxy - are straight-chain or branched and each contains two or preferably one unsaturated carbon-carbon bond(s). There may be mentioned by way of example vinyl, prop- 2-en-1-yl, 2-methylprop-2-en-1-yl, but-2-en-1-yl, but-3-en-1-yl, prop-2-yn-1-yl, but-2-yn-1-yl and but-3-yn-1-yl. Cycloalkyl - as a group per se and as a structural element of other groups and compound's, such as of cycloalkylalkyl - is cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. Cyclopentyl and cyclohexyl, and especially cyclopropyl, are preferred. Halo-substituted carbon-containing groups and compounds, such as haloalkyl and haloalkoxy, may be partially halogenated or perhalogenated, the halogen substituents in the case of polyhalogenation being the same or different. Examples of haloalkyl - as a group per se and as a structural element of other groups and compounds, such as of haloalkoxy - are methyl substituted from one to three times by fluorine, chlorine and/or bromine, such as CHF2, CF3 or CH2CI; ethyl substituted from one to five times by fluorine, chlorine and/or bromine, such as CH2CF3, CF2CF3, CF2CCI3, CF2CHCI2, CF2CHF2, CF2CFCI2, CH2CH2CI, CF2CHBr2, CF2CHCIF, CF2CHBrF or CCIFCHCIF; propyl or isopropyl substituted from one to seven times by fluorine, chlorine and/or bromine, such as CH2CHBrCH2Br, CF2CHFCF3, CH2CF2CF3, CF2CF2CF3, CH(CF3)2 or CH2CH2CH2CI; and butyl or an isomer thereof substituted from one to nine times by fluorine, chorine and/or bromine, such as CF(CF3)CHFCF3, CF2(CF2)2CF3 or CH2(CF2)2CF3. Aryl is especially phenyl or naphthyl, preferably phenyl. Heterocyclyl is to be understood as being a five- to seven-membered monocyclic ring containing from one to four hetero atoms selected from the group consisting of N, O and S, or a bicyclic ring system which may contain either in only one ring - such as, for example, in quinolyl, quinoxalinyl, indolinyl, benzothiophenyl or benzofuranyl - or in both rings - such as, for example, in pteridinyl or purinyl - independently of one another, one or more hetero atoms selected from N, O and S. Preference is given to pyridyl, pyrimidyl, triazinyl, tetrazolyl, thienyl, furyl, tetrahydrofuranyl, pyranyl, tetrahydropyranyl, oxazolyl, isoxazolyl, oxazolinyl, isoxazolinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, benzoxazolyl, thiadiazolyl, oxadiazolyl, benzothienyl, quinolyl, quinoxalinyl, benzofuranyl, benzimidazolyl, benz- othiazolyl, indolyl, coumarinyl and indazolyl, each of which is preferably bonded by way of a carbon atom; special preference is given to pyridyl, thienyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, 1 ,2,3-triazolyl, 1 ,2,4-triazolyl, 1 ,3,4-thiadiazolyl, 1 ,2,4-thiadiazolyl, oxazolyl, isoxazolyl, 1 ,2,4-oxadiazolyl and tetrazolyl. Preferred embodiments within the scope of the invention are (2) compounds according to (1) of formula (I) wherein A3 is a straight-chain alkylene bridge, especially methylene, ethylene, propylene or butylene; more especially methylene; (3) compounds according to (1) or (2) of formula (I) wherein Q is oxygen; (4) compounds according to (1) to (3) of formula (I) wherein Y is oxygen; (5) compounds according to (1) to (4) of formula (I) wherein R^ and R2 are each independently of the other CN, nitro, d-C6alkyl, Cι-C6haloalkyl, fluorine, chlorine or bromine; especially chlorine; (6) compounds according to (1) to (5) of formula (I) wherein R3 is hydrogen; (7) compounds according to (1) to (6) of formula (I) wherein X-i and X2 are chlorine or bromine, especially chlorine; (8) compounds according to (1) to (7) of formula (I) wherein R4 and R5 are H, methyl, fluorine or chlorine; (9) compounds according to (1) to (8) of formula (I) wherein W is a bond; (10) compounds according to (1) to (9) of formula (I) wherein W is -C(=O)-O-, -C(R8)=N-O- or -C(=O)-NR9-, the carbonyl or imino group being bonded to the central olefin bond of the compound of formula (I), and the oxygen atom or the -NRg- group of the bridging members W being bonded to A3; (11) compounds according to (1) to (10) of formula (I) wherein the group A T-A2 is a bond; (12) compounds according to (1) to (11) of formula (I) wherein the group ArT-A2 is -O-d-Cealkylene, especially -0-CH2-; (13) compounds according to (1) to (12) of formula (I) wherein E is phenyl; (14) compounds according to (1) to (12) of formula (I) wherein E is pyridyl, pyrimidyl, tetrazolyl, thienyl, oxazolyl, isoxazolyl, oxazolinyl, isoxazolinyl, pyrrolyl, pyrazolyl, imidazolyl, thiazolyl, triazolyl, benzoxazolyl, thiadiazolyl and oxadiazolyl; (15) compounds according to (1) to (14) of formula (I) wherein the substituents of E are each independently of the other(s) selected from the group consisting of halogen, OH, SH, =0, =S, CN, nitro, C C6alkyl, CrC6haloalkyl, CrC6alkoxy-CrCealkyl, C2-C6alkenyl- oxy-CrC6alkyl, C2-C6alkynyloxy-CrC6alkyl, CrC6haloalkoxy-CrC6alkyl, C2-C6haloalkenyl- oxy-CrC6alkyl, C2-C6haloalkynyloxy-CrCealkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, CrC6cyanoalkoxy, C C6haloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C6haloalkynyloxy, -(S=O)-CrC6alkyl, -S(=0)2-CrC6alkyl, CrC6alkyl-N(R10)2, wherein the two R10s are independent of one another; -C(Rιι)=NOR12, -C(=NOR12)-C(R11)=NOR12, C1-C6alkyl-C(R11)=NOR12) -(CH2)n-UrC(=0)-U2R13, -N(R14)R15, -C(R18)=C(R19)R20, aryl, heterocyclyl and heterocyclyloxy; the aryl, heterocyclyl and heterocyclyloxy radicals being unsubstituted or substituted by from one to three identical or different substituents selected from halogen, OH, SH, =0, =S, CN, nitro, d-C6alkyl, CrC6haloalkyl, CrC6alkoxy-CrC6alkyl, C2-C6alkenyl- oxy-d-C6alkyl, C2-C6alkynyloxy-CrC6alkyl, CrC6haloalkoxy-CrC6alkyl, C2-C6haloalkenyl- oxy-CrC6alkyl, C2-C6haloalkynyloxy-CrC6alkyl, C2-C6alkenyl, C2-C6haloalkenyi, C2-C6alkynyl, C2-C6haloalkynyl, CrC6alkoxy, CrC6cyanoalkoxy, CrC6haloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C6haloalkynyloxy, -(S=O)-CrC6alkyl, -S(=0)2-CrC6alkyl, CrC6-alkyl-N(R 0)2 wherein the two R10s are independent of one another; -C(R11)=NOR12, -C(=NOR12)-C(R11)=NOR12, C1-C6alkyl-C(R11)=NOR12, -(CH2)n-UrC(=0)-U2R13, -N(R14)R15 and -C(R18)=C(R19)R20; LI-, and U2 are each independently of the other a bond, O or NR7; n is 0, 1 , 2, 3 or 4; R10 is H, C C6alkyl, d-C-ehaloalkyl, Cι-C6alkyl-carbonyl, CrC6haloalkylcarbonyl, CrC6alkoxy-CrC6alkyl, Crdalkoxycarbonyl, C3-C8cycloalkyl or C3-C8cycloalkylcarbonyl; Rn and R13 are each independently of the other H, CrC6alkyl, CrC6haloalkyl, C C6cyanoalkyl, CrCealkoxy-CrC6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C3-C6haloalkynyl, aryl, benzyl, heterocyclyl; or aryl, benzyl or heterocyclyl, each substituted by from one to three identical or different substituents selected from halogen, OH, SH, =0, =S, CN, nitro, C C6alkyl, C C6haloalkyl, CrC6alkoxy-CrC6alkyl, C2-C6alkenyloxy-CrC6alkyl, C2-C6alkynyloxy-CrC6alkyl, CrC6haloalkoxy-CrC6alkyl, C2-Cehaloaikenyloxy-CrC6alkyl, C2-C6haloalkynyloxy-CrC6alkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C2-C6halo- alkynyl, CrC6alkoxy, CrC6cyanoalkoxy, d-C6haloalkoxy, C2-C6alkenyloxy, C2-C6halo- alkenyloxy, C3-C6alkynyloxy, C3-C6haloalkynyloxy, -(S=O)-CrC6alkyl, -S(=0)2-C C6alkyl and CrC6-alkyl-N(R 0)2 wherein the two R10s are independent of one another; R12 is H, CrC6alkyl, CrCehaloalkyl, CrC6alkoxy-CrC6alkyl, C2-C6alkenyl, C2-C6halo- alkenyl, C2-C6alkynyl or C2-C6haloalkynyl; R1 and R-ι5 are each independently of the other H, d-C6alkyl, C3-C8cycloalkyl, C3-C8cycloalkyl-CrC6alkyl, CrCehaloalkyl, CrC6alkoxy, CrC6haloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, -C(=O)R16, -C(=S)R16, phenyl, benzyl; or phenyl, phenylcarbonyl or benzyl which are each substituted in the aromatic ring by from one to five identical or different substituents selected from the group consisting of halogen, d-C6alkyl, halo-CrC6alkyl, C C6alkoxy, halo-CrC6alkoxy, hydroxy, cyano and nitro; or R14 and R 5 together form a straight-chain or branched alkylene bridge having from four to eight members, wherein a CH2 group may have been replaced by O, S or NR17, and the alkylene bridge is unsubstituted or substituted by from one to four identical or different substituents selected from C3-C8cycloalkyl, C3-C8cycloalkyl-C C6alkyl and C C3haloalkyl; R16 is CrC6alkyl, C C6haloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, C C6alkoxy, CrCehaloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, C3-C6cycloalkyl, phenyl, benzyl; or phenyl or benzyl, each unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, CrC6alkyl, CrCehaloalkyl, CrC6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, CrC6alkoxy, CrC6haloalkoxy, d-C6alkoxycarbonyl, d-C3haloalkoxycarbonyl and C2-C6halo- alkenyloxy; R17 is H, CrC6alkyl, CrC3haloalkyl, d-C3haloalkylcarbonyl, d-C6alkoxyalkyl, d-C6alkyl-carbonyl or C3-C8cycloalkyl; R18 is H, CrC6alkyl, halo-CrC6alkyl, CrCealkoxy-CrCealkyl, C3-C6cycloalkyl or phenoxy-CrC6alkyl; or together with R19 is a bond; R19 is CN, N02, -C(=NOR22)-R2ι, -(C=0)-R23l R24-0-CrC6alkyl, -CH(O-R26)2, or together with R18 is a bond; R20 is H, CrC6aIkyl, CrCehaloalkyl, C3-C6cycloalkyl, CrC6alkoxy, d-C3haloalkoxy, CrC6alkylamino, C2-C6alkenyl, C2-C6alkynyl, C2-C6haloalkenyl or C2-C6haloalkynyl; or R1 and R20 together with the carbon atom to which they are bonded form a five- to seven-membered ring, which may contain from one to three hetero atoms selected from O, N and S, and which is unsubstituted or substituted by from one to three identical or different substituents selected from halogen, OH, =O, SH, =S, =N-OH, =N-O-C C6alkyl, CN, nitro, CrC6alkyl, CrCehaloalkyl, d-C6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, d-C6alkoxy and CrCehaloalkoxy; R21 is H, CrC6alkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl or C2-C6haloalkynyl; R22 is H, C C6alkyl, C3-C6cycloalkyl-CrC6alkyl, C2-C6alkenyl or C3-C6alkynyl; R23 is H, OH, C C12alkyl, Crdalkoxy, d-C12haloalkyl, C C6haloalkoxy, -N(R25)2, C3-C6cycloalkyI, aryl, aryloxy, benzyloxy, heterocyclyl or heterocyclyloxy; and R24 is H, CrC6alkyl, CrCehaloalkyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkynyl, C3-C6cycloalkyl, C3-C6cycloalkyl-CrC6alkyl or CrC6alkoxy-CrCealkyl; the two R25s are each independently of the other H, d-d2alkyl or benzyl; and the two R26s are each independently of the other CrC12alkyl or benzyl or together form a C -C6alkylene bridge. Special preference is given to the compounds listed in the Tables. The invention relates also to a process for the preparation of a compound of formula (I), or a salt thereof, wherein (a) a compound of formula
Figure imgf000009_0001
wherein E, W, Q, T, A-,, A2, A3, Rι, R2, R3, R , R5 and m are as defined for formula (I) under (1 ), Z-, is -C(=0)R27 and R27 is H or CrC6alkyl, is converted in the presence of an oxidising agent, especially a peracid, into a compound of formula G-Z2a (Ilia), wherein Z2a is 0-C(=0)-CrC6alkyl, and G denotes the part of the formula in the brackets designated G in formula (II); either (b) a compound of formula (Ilia) above or of formula G-Z2b (1Mb), wherein G denotes the part of the formula in the brackets designated G in formula (II), Z2b is a radical of formula -Y-C(=O)R28, Y is as defined for formula (I) under (1), and R28 is d-C12alkyl unsubstituted or substituted by from one to three identical or different halogen substituents, or is phenyl unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, C C6alkyl, CrC6haloalkyl, CrC6alkylcarbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkynyl, CrC6alkoxy, CrCehaloalkoxy, CrC6alkoxycarbonyl and C2-C6haloalkenyloxy, is converted by hydrolytic cleavage into a compound of formula G-Z3 (IV), wherein G denotes the part of the formula in the brackets designated G in formula (II), Z3 is YH, and Y is as defined for formula (I) under (1 ); or (c) a compound of formula G-Z4 (V), wherein Z4 is Y-CH2-phenyl, wherein the phenyl radical is unsubstituted or substituted by from one to three identical or different substituents selected from halogen, CN, nitro, d-C-ealkyl, CrCehaloalkyl, CrC6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C3-C6alkynyl, CrC6alkoxy, CrC6haloalkoxy, CrC6alkoxycarbonyl and C2-C6haloalkenyloxy, G denotes the part of the formula in the brackets designated G in formula (II), and Y is as defined for formula (I), is converted by removal of the benzyl group into a compound of formula (IV), as defined above; (d) the compound of formula (IV) so obtained is reacted in the presence of a base with a compound of formula -alkyl O' Hal o- - alkyl wherein Hal is halogen, preferably bromine or chlorine, and alkyl is CrC6alkyl, or the two alkyl radicals together form a C3-C8alkylene bridge, to form a compound of formula G-Z5 (VI), wherein G denotes the part of the formula in the brackets designated G in formula (II) and Z5 is
Figure imgf000011_0001
wherein alkyl and Y are as defined above; (e) the compound of formula (VI) so obtained is converted by deprotection of the acetal function in the presence of an acid into a compound of formula G-Z6 (VII), wherein Z6 is a group -Y-CH2-C(=O)H, G is as defined above for the compound of formula (II), and Y is as defined for formula (I) under (1), either (f-i) for the preparation of a compound of formula (I) wherein X- and X2 are chlorine or bromine, a compound of formula (VII) is reacted in the presence of a phosphine with a compound of formula C(X) wherein X is chlorine or bromine; or (f2) for the preparation of a compound of formula (I) wherein X^ and X2 are chlorine, a compound of formula (VII) is reacted first with CCI3-COOH or with chloroform in the presence of a strong base, then with acetic anhydride and subsequently with powdered zinc in acetic acid; or (f3) for the preparation of a compound of formula (I) wherein X^ is fluorine and X2 is chlorine or bromine, a compound of formula (VII) is reacted first with a compound of the formula CF2X2, of the formula CFX3, of the formula CF2XC(=O)ONa or of the formula CFX2C(=O)ONa, in the presence of a phosphine; or (g for the preparation of a compound of formula (I) wherein X^ and X2 are chlorine or bromine, a compound of formula (IV) is reacted in the presence of a base with a compound of formula
Figure imgf000012_0001
wherein L3 is a leaving group, preferably chlorine or bromine, and Hal is chlorine or bromine; or (g2) for the preparation of a compound of formula (I) wherein X^ and X2 are chlorine or bromine, a compound of formula (IV) is reacted in the presence of a base with a compound of formula
Figure imgf000012_0002
wherein Hal is halogen and X is chlorine or bromine. The invention relates also to (h) a process for the preparation of a compound of formula (I), as defined under (1), and wherein Q is O, NR7 or S, and R7 is as defined for formula (I) under (1 ), wherein a compound of formula
Figure imgf000012_0003
wherein A^ A2, A3, T, W, R4 and R5 are as defined for formula (I) under (1), and L is a leaving group, is reacted in the presence of a base with a compound of formula
Figure imgf000012_0004
wherein R^ R2, R3 and m are as defined for formula (I) under (1), Q is O, NR7 or S and Z is one of the radicals Z to Z6 as defined for formulae (II) to (VII) above, and R7 is as defined for formula (I) under (1), and the resulting compound of formula
Figure imgf000013_0001
wherein E, T, W, Q, A-,, A2, A3, R1 t R2, R3, R4, R5 and m are as defined for formula (I) under (1) and Z is one of the radicals Zi to Z6 as defined for formulae (II) to (VII) above, is, as necessary, that is to say according to the meaning of the radical Z, reacted further analogously to one or more of process steps (a) to (g).
In the compounds of formulae X/a to X/f, Z in compound X/a has the same meanings as Zi in the compound of formula (II), Z in compound X/b has the same meanings as Z2 in formula (III), and so on. The invention relates also to (i) a process for the preparation of a compound of formula (I) as defined under (1 ) above, wherein a compound of formula (VIII) as defined above, is reacted analogously to process step (h) with a compound of formula
Figure imgf000013_0002
wherein R^ R2, R3, Q, Xi, X2, Y and m are as defined for formula (I) under (1). The invention relates also to (k) a process for the preparation of a compound of (I) as defined above, wherein W is -C(=O)-0- or -C(=0)-NR9- and R9 is as defined for formula (I) under (1), wherein a compound of formula
Figure imgf000013_0003
wherein E, T, Aι, A2, R and R5 are as defined for formula (I) under (1) and D is a halogen atom, especially chlorine or bromine, or is OH, is reacted with a compound of formula
Figure imgf000014_0001
wherein W2 is O or NR9, and Q, A3, R-,, R2, R3, R9 and m are as defined for formula (I) under (1 ), and Z is one of the radicals Zi to Z6 as defined in formulae (II) to (VII) above, and a resulting compound of formula (Xa) to (Xf), wherein W is -C(=O)-O-, as defined above, is, as necessary, that is to say according to the meaning of the radical Z, reacted further analogously to one or more of process steps (a) to (g); or a compound of formula (XII) is reacted with a compound of formula (XI) analogously to process step (i). In the compounds of formulae X/a to X/f and XIII/a to Xlll/f, the radicals Z are as defined above for the compounds X/a to X/f; that is to say, Z in the compound of formula XIII/a has the same meanings as Z-i in the compound of formula (II), and Z in compound Xlll/b has the same meanings as Z2 in formula (III), and so on. The invention relates also to (l-i) a process for the preparation of a compound of formula
Figure imgf000014_0002
wherein E, T, A^ and A2 are as defined for formula (I) and R41 and R51 are CrC6alkyl, C C3haloalkyl, CrC6alkoxy-CrC6alkyl, C3-C8cycloalkyl, or C3-Cscycloalkyl-CrC6alkyl, wherein a compound of formula
Figure imgf000014_0003
which is known or can be prepared according to methods known per se, is reacted in the presence of a base with a compound of formula R41-C(=0)-R51, wherein R41 and R51 are as defined for formula (Xlla), and the resulting compound of formula
Figure imgf000015_0001
wherein E, T, A-,, A2, R41 and R51 are as defined for formula (Xlla), is converted according to methods known perse into the acid halide of formula (Xlla); and (l2) a process for the preparation of a compound of formula
Figure imgf000015_0002
wherein E, T, A^ and A2 are as defined for formula (I) and R is d-C6alkyl, wherein a compound of formula
Figure imgf000015_0003
wherein E, T, A1 and A2 are as defined for formula (I) and R is CrC6alkyl, is reacted with formaldehyde or paraformaldehyde in the presence of a base, and where appropriate, if desired, the resulting compound of formula (Xllc) may be converted into the corresponding acid halide; and (l3) a process for the preparation of a compound of formula
Figure imgf000015_0004
wherein E, T, AT and A2 are as defined for formula (I), R41 and R42 are as defined above for formula (XII) or are halogen, and R is C C6alkyl, wherein a compound of formula
Figure imgf000016_0001
wherein E, T, A-,, A2 and R are as defined for formula (Xlld), is reacted with a tetrahalomethane in the presence of triphenylphosphine or with an alkyltriphenyl- phosphonium salt in the presence of a base. The invention relates also to (m-i) a process for the preparation of a compound of formula
Figure imgf000016_0002
wherein E, T, Q, A^ A2, A3, R-,, R2, R3> X^ X2, Y and m are as defined for formula (I), wherein either a compound of formula
Figure imgf000016_0003
is reacted in the presence of a base with a compound of formula (XI) above, and the resulting compound of formula
(XVIII),
Figure imgf000016_0004
wherein E, T, Q, Aι, A2, A3, R-,, R2, R3 and m are as defined for formula (I), and Z is one of the radicals Z-, to Z6 as defined in formulae (II) to (VII) above, is oxidised, and then reacted further analogously to one or more of process steps (a) to (g); or (m2) a compound of formula (XVII) above is reacted with a compound of formula (IX) above, and the resulting compound (compound XVIII) is oxidised analogously to process steps (a) to (g) and analogously to process step (nrn). The invention relates also to a process for the preparation of a compound of formula (I), wherein W is a bond and A3 is CH2, wherein a compound of formula (XVIII) is processed further analogously to one of process steps (I-,) to (l3) and steps (a) to (g). It will be understood that the process steps (a) to (g) and (I-,) to (l3) may be carried out in any desired order, that is to say, for example, there are carried out first two steps analogously to steps (a) and (b), then, for example, step (l2), and subsequently the steps analogously to steps (c) to (g). The invention relates also to (n) a process for the preparation of a compound of formula
Figure imgf000017_0001
wherein E, T, AL A2, A3, R4 and R5 are as defined for formula (I) and L is a leaving group, wherein a compound of formula
Figure imgf000017_0002
wherein E, T, Ai, A2 and A3 are as defined for formula (I) and L is a leaving group, is treated with an acid, and the resulting compound of formula
Figure imgf000017_0003
wherein E, T, A-,, A2 and A3 are as defined for formula (I) and L is a leaving group, is reacted further analogously to process step (l3). It will be understood that a compound of formula (XXa) may also first be reacted with a compound of formula (IX) or (XI) analogously to process step (h), and the resulting compound of formula
Figure imgf000018_0001
wherein Z has the meanings given above for Z-i to Z6 or is the radical -Y-CH=CX1X2 defined in formula (I), and E, T, A-i, A2 and A3 are as defined for formula (I), and the resulting compound of formula (XXb) may be reacted further, if desired, according to processes (a) to (g) and (n). The invention relates also to (o-,) a process for the preparation of a compound of formula
Figure imgf000018_0002
wherein Q, A2, A3, R-,, R2, R3, X1 f X2, Y and m are as defined for formula (I) and L is a leaving group, wherein a compound of formula
(XXIII),
Figure imgf000018_0003
wherein A2, A3, R4 and R5 are as defined for formula (I) and the two L groups are leaving groups, is reacted with a compound of formula (IX) or (XI); and (o2) a process for the preparation of a compound of formula
Figure imgf000018_0004
wherein E, T, A^ A2 and A3 are as defined for formula (I) and L is a leaving group, wherein a compound of formula (XXIII) above is reacted with a compound of formula E-ArT-H, wherein E, Ai and T are as defined for formula (I). It will be understood that the processes (n) to (o) according to the invention can also be carried out on any precursor and such a precursor can then be processed in accordance with processes (a) to (m) to form compounds of formula (I). The invention relates also to corresponding intermediates, which are, where novel, the compounds of formulae (II) to (XXIV), in free form or in salt form. It will also be understood that compounds of formula (I) wherein the bridging members Q, T and W are O, NR7 or S can be obtained by reacting a starting compound that contains a leaving group at the appropriate position with another starting compound that contains OH, SH or NHR7at the position to be bridged. Such starting compounds are, for example, the compounds of formulae (VIII), (XIX), (XXI), (XXII), (XXIII) and (XXIV), some of which are known and some of which are novel. Where novel, the invention relates also to such compounds. Further suitable compounds that are also novel, to which the invention also relates, are, for example, the compounds of formulae
Figure imgf000019_0001
(XXVII),
Figure imgf000019_0002
(XXVIII) and
Figure imgf000019_0003
Figure imgf000019_0004
wherein E, T, Q, A1 ( A2, A3, R-,, R2, R3, R4, R5, R7, X^ X2, Y and m are as defined for formula (I). It will also be understood that compounds of formula (I) wherein the bridging members T and W are -C(=O)-O-, -O-C(=O)-, -C(=O)-NR6- or -NR6-C(=O)- or -C(R8)=N-O- can be prepared from two or more suitable precursors, in which, as, for example, in formula (XII) above, one of the starting materials contains an acid halide or an ester function and the other starting material contains a free OH group to form a bridging function -C(=O)-O- or -0-C(=0)- or contains an -NR6- group to form an acid amide. Similarly, in order to form a bridging member -C(R8)=N-0-, a starting material that carries an aldehyde or a keto function can be combined with a starting material that carries a hydroxylamine function at the appropriate position. Such preparation processes require, in addition to the above-mentioned compounds of formula (XII), for example, intermediates of the following formulae:
Figure imgf000020_0001
(XXXII) and
(XXXIII),
Figure imgf000020_0002
wherein E, T, Q, A-,, A2, A3, Rι, R2, R3, R4, R5, R7, X-t, X2, Y and m are as defined for formula (I) and R is alkoxy or halogen. Similarly, for the preparation of compounds of formula (I) there can also be used intermediates such as those of formulae (XXVIII) to (XXXIIIl) above, in which, however, the radical -Y-CH2-CH=CX1X2 has been replaced by a radical Z^ to Z6. The invention relates also to such compounds. For intermediates of formulae (II) to (XXXIII) the same preferred meanings apply as those defined for the compounds of formula (I) under (2) to (11). The reactions described hereinabove and hereinbelow are carried out in a manner known per se, for example in the absence or, if necessary, in the presence of a suitable solvent or diluent or of a mixture thereof, the reactions being carried out, as required, with cooling, at room temperature or with heating, for example in a temperature range of approximately from -80°C to the boiling temperature of the reaction mixture, preferably from approximately -20°C to approximately +150°C, and, if necessary, in a closed vessel, under pressure, under an inert gas atmosphere and/or under anhydrous conditions. Especially advantageous reaction conditions can be found in the Examples. A leaving group, for example the leaving groups L defined above, or a counter-ion is to be understood hereinbefore and hereinbelow as being any removable group that customarily comes into consideration for chemical reactions, such as are known to the person skilled in the art; especially OH, halogens, such as fluorine, chlorine, bromine, iodine, -0-Si(CrC8alkyl)3, -O-aryl, -S-(CrC8alkyl), -S-aryl, -O-S(=O)2U, -S(=O)U or -S(=O)2U, wherein U is unsubstituted or substituted CrC8alkyl, C2-C8alkenyl, C2-C8alkynyl, unsubstituted or substituted aryl or unsubstituted or substituted benzyl. Especially preferred as a leaving group are chlorine or bromine, mesylate, triflate, tosylate, especially chlorine; or chloride or bromide, especially chloride. Process (a): The reaction is carried out in acetic acid or a halogenated hydrocarbon, such as dichloromethane, at temperatures of from -20°C to 100°C, preferably at from 20°C to 50°C. As oxidising agents there are used, for example, hydrogen peroxide, a peracid, such as peracetic acid, trifluoroperacetic acid, 3-chloroperbenzoic acid or a mixture, such as sodium perborate in acetic acid. Process (b): The reaction is preferably carried out in an alcohol, such as methanol, ethanol or an alcohol/water mixture, in the presence of an inorganic base, such as NaOH or KOH, and at temperatures of from 0°C to 150°C, preferably from 20°C to 80°C. Alternatively aminolysis with a primary amine, such as n-butylamine, can be carried out in a hydrocarbon, such as toluene or benzene, at temperatures of from 0°C to 150°C, preferably at from 20°C to 80°C. Process (c): Depending upon the nature of the benzyl substituent to be removed, the reaction can be carried out, for example, under a hydrogen atmosphere, at from 1 to 150 bar, especially at from 1 to 20 bar, and with the addition of a catalyst, such as palladium- on-carbon, in an alcohol or ether. The preferred reaction temperature is from 0°C to 120°C, especially from 20°C to 80°C. Processes (d) and (a): The reaction is preferably carried out in the presence of a base, such as potassium or sodium carbonate, in acetone or dimethylformamide, at temperatures of from 0°C to 150°C, preferably from 20°C to 80°C. If necessary, catalytic amounts of potassium iodide or sodium iodide, or phase transfer catalysts, such as crown ethers or quaternary ammonium salts, are added. Process (e): The reaction is preferably carried out in acetone, dichloromethane, acetic acid, or especially in water, optionally with the addition of a mineral acid, at temperatures of from 0°C to 120°C, preferably at from 20°C to 50°C. For complete cleavage of the acetai it is preferable to add a strong mineral acid, for example hydrochloric acid, sulfuric acid or 4- toluenesulfonic acid. Process (f): For the preparation of the difluoro-, dichloro-, dibromo-, chlorofluoro- and bromofluoro-vinyl compounds, reaction with CCI4, CBr4, CF2X2, CFX3, CF2XC(=O)ONa or CFX2C(=0)ONa wherein X is bromine or chlorine is carried out in the presence of a trialkyl- or triaryl-phosphine, optionally with the addition of powdered zinc. The reaction is carried out in an inert solvent such as, for example, benzene or toluene, or an ether, such as diethyl ether, diisopropyl ether, dioxane or tetrahydrofuran, at temperatures of from 0°C to 150°C, preferably at from 20°C to 80°C. For the preparation of the dichlorovinyl compounds it is also possible for the process to be carried out in dimethylformamide, benzene, toluene, or in an ether, at temperatures of from 0°C to 120°C, preferably from 20°C to 80°C, and in the presence of trichloroacetic acid/ sodium trichloroacetate, then by addition of acetic anhydride, optionally with the addition of base, for example triethylamine, and finally by addition of zinc and acetic acid. Processes (h) and (i): The reaction is preferably carried out in an ether or an amide, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, at temperatures of from 0°C to 150°C, preferably at from 20°C to 80°C, with the addition of a base, such as potassium or sodium carbonate. Alternatively a coupling reagent, for example azodicar- boxylic acid diethyl or diisopropyl ester and triphenylphospine, can be used. Process (k):The reaction is preferably carried out in a halogenated hydrocarbon, such as methylene chloride, or in an ether, such as dioxane or tetrahydrofuran, at temperatures of from 0°C to 120°C, especially at from 20°C to 80°C, with the addition of a base, for example triethylamine or ethyldiisopropylamine. Processes ( ), (I?); The reaction may be carried out, on the one hand, in an alcohol, such as methanol or ethanol, in dimethylformamide, N-methylpyrrolidone or tetrahydrofuran as solvent, in the presence of a base, such as diethylamine, diisopropylamine, piperidine, KOH, NaOH or sodium methylate, at a temperature of from -70°C to the boiling temperature of the solvent; or, on the other hand, for example, the reaction may be carried out in acetic acid at from 20°C to 120°C in the presence of ammonium acetate. Process (l3):The reaction is preferably carried out in an ether, such as dioxane, tetrahydrofuran or dimethoxyethane, or in an aromatic solvent, such as toluene or xylene, at temperatures of from 0°C to 150°C, especially at from 20°C to 100°C, with the addition of a base, such as potassium or sodium carbonate, potassium tert-butylate or butyllithium. Process (m): The reaction is preferably carried out in an ether, such as dioxane, tetrahydrofuran or dimethoxyethane, in an amide, such as dimethylformamide, dimethylacet- amide or N-methylpyrrolidone, in an aromatic solvent, such as toluene or xylene, or in a nitrile, such as acetonitrile, at temperatures of from 0°C to 150°C, preferably from 20°C to 100°C, with the addition of a base, such as triethylamine or ethyldiisopropylamine. Processes (n) and (o): The reaction is preferably carried out in an ether, such as dioxane, tetrahydrofuran or dimethoxyethane, in an amide, such as dimethylformamide, dimethylacetamide or N-methylpyrrolidone, or in a nitrile, such as acetonitrile, at temperatures of from 0°C to 150°C, preferably from 20°C to 100°C, with the addition of a base, such as potassium or sodium carbonate. Especially preferred process conditions can be found in the Examples. The invention relates especially to the preparation processes described in Examples P1 to P11. Compounds of formula (I) obtainable in accordance with the process or by other means can be converted into other compounds of formula (I) in a manner known per se by replacement of one or more substituents in the starting compound of formula (I) in customary manner by another (other) substituent(s) according to the invention. In the case of such replacement, depending upon the choice of reaction conditions and starting materials suitable therefor, it is possible for only one substituent to be replaced by another substituent according to the invention in a reaction step or for a plurality of substit- uents to be replaced by other substituents according to the invention in the same reaction step. Salts of compounds of formula (I) can be prepared in a manner known per se. For example, salts of compounds of formula (I) with bases are obtained by treatment of the free compounds with a suitable base or with a suitable ion exchange reagent. Salts of compounds of formula (I) can be converted into the free compounds of formula (I) in customary manner, for example by treatment with a suitable acid or with a suitable ion exchange reagent. Salts of compounds of formula (I) can be converted in a manner known per se into other salts of a compound of formula (I). The compounds of formula (I), in free form or in salt form, may be in the form of one of the possible isomers or in the form of a mixture thereof, for example, depending upon the number of asymmetric carbon atoms occurring in the molecule and their absolute and relative configuration, and/or depending upon the configuration of non-aromatic double bonds occurring in the molecule, in the form of pure isomers, such as enantiomers 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 is to be interpreted as such hereinbefore and hereinafter, even if stereochemical details are not mentioned specifically in every case. Mixtures of diastereoisomers, mixtures of racemates and mixtures of double bond isomers of compounds of formula (I), in free form or in salt form, that are obtainable by the process according to the invention - depending upon the starting materials and procedures chosen - or by some other method, can be separated into the pure diastereoisomers or racemates in known manner on the basis of the physico-chemical differences between the constituents, for example by means of fractional crystallisation, distillation and/or chromato- graphy. Mixtures of enantiomers, such as racemates, that are obtainable in a corresponding manner can be resolved into the enantiomers by known methods, for example by recrystal- lisation from an optically active solvent, by chromatography on chiral adsorbents, for example high pressure liquid chromatography (HPLC) on acetylcellulose, with the aid of suitable microorganisms, by cleavage with specific, immobilised enzymes, via the formation of inclusion compounds, for example using chiral crown ethers, only one enantiomer being complexed, or by conversion into diastereoisomeric salts and separation of the mixture of diastereoisomers so obtained, for example on the basis of their different solubilities by fractional crystallisation, into the diastereoisomers, from which the desired enantiomer can be freed by the action of suitable agents. Apart from by separation of corresponding mixtures of isomers, it is also possible for pure diastereoisomers or enantiomers to be obtained according to the invention by generally known methods of diastereoselective or enantioselective synthesis, for example by carrying out the process according to the invention using starting materials having correspondingly suitable stereochemistry. In each case it is advantageous to isolate or synthesize the biologically more active isomer, e.g. enantiomer or diastereoisomer, or mixture of isomers, e.g. mixture of enantiomers or mixture of diastereoisomers, where the individual components have different biological activity. The compounds of formula (I), in free form or salt form, can also be obtained in the form of their hydrates and/or may include other solvents, for example solvents which may have been used for the crystallisation of compounds present in solid form. The invention relates to all those embodiments 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 some or all of the remaining steps are carried out or a starting material is used in the form of a derivative or salt and/or its racemates or enantiomers or, especially, is formed under the reaction conditions. In the process of the present invention it is preferable to use those starting materials and intermediates, in each case in free form or in salt form, which result in the compounds of formula (I) and their salts described at the beginning as being especially valuable. In the area of pest control, the compounds of formula (1) according to the invention are active ingredients exhibiting valuable preventive and/or curative activity with a very advantageous biocidal spectrum even at low rates of concentration, while being well tolerated by warm-blooded animals, fish and plants. The active ingredients according to 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 members of the order Acarina. The insecticidal or acaricidal activity of the active ingredients according to 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 ovi- position and/or hatching rate, good activity corresponding to a mortality of at least 50 to 60 %. Successful control within the scope of the subject of the invention is possible, in particular, of pests from the orders Lepidoptera, Coleoptera, Orthoptera, Isoptera, Psocoptera, Anoplura, Mallophaga, Thysanoptera, Heteroptera, Homoptera, Hymenoptera, Diptera, Siphonaptera, Thysanura and Acarina, mainly Lepidoptera and Coleoptera. Very especially good control is possible of the following pests: Abagrotis spp., Abraxas spp., Acantholeucania spp., Acanthoplusia spp., Acarus spp., Acarus siro, Aceria spp., Aceria sheldoni, Acleris spp., Acoloithus spp., Acompsia spp., Acossus spp., Acria spp., Acrobasis spp., Acrocercops spp., Acrolepia spp., Acrolepiopsis spp., Acronicta spp., Acropolitis spp., Actebia spp., Aculus spp., Aculus schlechtendali, Adoxophyes spp., Adoxophyes reticulana, Aedes spp., Aegeria spp., Aethes spp., Agapeta spp., Agonopterix spp., Agriopis spp., Agriotes spp., Agriphila spp., Agrochola spp., Agroperina spp., Alabama ssp., Alabama argillaceae, Agrotis spp., Albuna spp., Alcathoe spp., Alcis spp., Aleimma spp., Aletia spp., Aleurothrixus spp., Aleurothrixus floccosus, Aleyrodes spp., Aleyrodes brassicae, Allophyes spp., Alsophila spp., Amata spp., Amathes spp., Amblyomma spp., Amblyptilia spp., Ammoconia spp., Amorbia spp., Amphion spp., Amphipoea spp., Amphipyra spp., Amyelois spp., Anacamptodes spp., Anagrapha spp., Anarsia spp., Anatrychyntis spp., Anavitrinella spp., Ancylis spp., Andropolia spp., Anhimella spp., Antheraea spp., Antherigona spp., Antherigona soccata, Anthonomus ssp., Anthonomus grandis, Anticarsia spp., Anticarsia gemmatalis, Aonidiella spp., Apamea spp., Aphania spp., Aphelia spp., Aphididae, Aphis spp., Apotomis spp., Aproaerema spp., Archippus spp., Archips spp., Acromyrmex, Arctia spp., Argas spp., Argolamprotes spp., Argyresthia spp., Argyrogramma spp., Argyroploce spp., Argyrotaenia spp., Arotrophora spp., Ascotis spp., Aspidiotus spp., Aspilapteryx spp., Asthenoptycha spp., Aterpia spp., Athetis spp., Atomaria spp., Atomaria linearis, Atta spp., Atypha spp., Autographa spp., Axylia spp., Bactra spp., Barbara spp., Batrachedra spp., Battaristis spp., Bembecia spp., Bemisia spp., Bemisia tabaci, Bibio spp., Bibio hortulanis, Bisigna spp., Blastesthia spp., Blatta spp., Blatella spp., Blepharosis spp., Bleptina spp., Boarmia spp., Bombyx spp., Bomolocha spp., Boophilus spp., Brachmia spp., Bradina spp., Brevipalpus spp., Brithys spp., Bryobia spp., Bryobia praetiosa, Bryotropha spp., Bupalus spp., Busseola spp., Busseola fusca, Cabera spp., Cacoecimorpha spp., Cadra spp., Cadra cautella, Caenurgina spp., Calipitrimerus spp., Callierges spp., Callophpora spp., Callophpora erythrocephala, Calophasia spp., Caloptiiia spp., Calybites spp., Capnoptycha spp., Capua spp., Caradrina spp., Caripeta spp., Carmenta spp., Carposina spp., Carposina nipponensis, Catamacta spp., Catelaphris spp., Catoptria spp., Caustoloma spp., Celaena spp., Celypha spp., Cenopis spp., Cephus spp., Ceramica spp., Cerapteryx spp., Ceratitis spp, Ceratophyllus spp., Ceroplaster spp., Chaetocnema spp., Chaetocnema tibialis, Chamaesphecia spp., Charanvca spp., Cheimophila spp., Chersotis spp., Chiasmia spp., Chilo spp., Chionodes spp., Chorioptes spp., Choristoneura spp., Chrysaspidia spp., Chrysodeixis spp., Chrysomya spp., Chrysomphalus spp., Chrysomphalus dictyospermi, Chrysomphaius aonidium, Chrysoteuchia spp., Cilix spp., Cimex spp., Clysia spp., Clysia ambiguella, Clepsis spp., Cnaemidophorus spp., Cnaphalocrocis spp., Cnephasia spp., Coccus spp., Coccus hesperidum, Cochylis spp., Coleophora spp., Colotois spp., Commophila spp., Conistra spp., Conopomorpha spp., Corcyra spp., Comutiplusia spp., Cosmia spp., Cosmopolites spp., Cosmopterix spp., Cossus spp., Costaeonvexa spp., Crambus spp., Creatonotos spp., Crocidolomia spp., Crocidolomia binotalis, Croesia spp., Crymodes spp., Cryptaspasma spp., Cryptoblabes spp., Cryptocala spp., Cryptophlebia spp., Cryptophlebia leucotreta, Cryptoptila spp., Ctenopseustis spp., Cucullia spp., Curculio spp., Culex spp., Cuterebra spp., Cydia spp., Cydia pomonella, Cymbalophora spp., Dactylethra spp., Dacus spp., Dadica spp., Damalinea spp., Dasychira spp., Decadarchis spp., Decodes spp., Deilephila spp., Deltodes spp., Dendrolimus spp., Depressaria spp., Dermestes spp., Dermanyssus spp., Dermanyssus gallinae, Diabrotica spp., Diachrysia spp., Diaphania spp., Diarsia spp., Diasemia spp., Diatraea spp., Diceratura spp., Dicho- meris spp., Dichrocrocis spp., Dichrorampha spp., Dicycla spp., Dioryctria spp., Diparopsis spp., Diparopsis castanea, Dipleurina spp., Diprion spp., Diprionidae, Discestra spp., Distan- tiella spp., Distantiella theobroma, Ditula spp., Diurnea spp., Doratopteryx spp., Drepana spp., Drosphila spp., Drosphila melanogaster, Dysauxes spp., Dysdercus spp., Dysstroma spp., Eana spp., Earias spp., Ecclitica spp., Ecdytolopha spp., Ecpyrrhorrhoe spp., Ecto- myelois spp., Eetropis spp., Egira spp., Elasmopalpus spp., Emmelia spp., mpoasca spp., Empyreuma spp., Enargia spp., Enarmonia spp., Endopiza spp., Endothenia spp., Endo- tricha spp., Eoreuma spp., Eotetranychus spp., Eotetranychus carpini, Epagoge spp., Epelis spp., Ephestia spp., Ephestiodes spp., Epiblema spp., Epiehoristodes spp., Epinotia spp., Epiphyas spp., Epiplema spp., Epipsestis spp., Epirrhoe spp., Episimus spp., Epitymbia spp., Epllachna spp., Erannis spp., Erastria spp., Eremnus spp., Ereunetis spp., Eriophyes spp., Eriosoma spp., Eriosoma lanigerum, Erythroneura spp., Estigmene spp., Ethmia spp., Etiella spp., Euagrotis spp., Eucosma spp., Euehlaena spp., Euelidia spp., Eueosma spp., Euchistus spp., Eucosmomorpha spp., Eudonia spp., Eufidonia spp., Euhyponomeutoides spp., Euiepitodes spp., Eulia spp., Eulithis spp., Eupithecia spp., Euplexia spp., Eupoecilia spp., Eupoecilia ambiguella, Euproctis spp., Eupsilia spp., Eurhodope spp., Eurois spp., Eurygaster spp., Eurythmia spp., Eustrotia spp., Euxoa spp., Euzophera spp., Evergestis spp., Evippe spp., Exartema spp., Fannia spp., Faronta spp., Feltia spp., Filatima spp., Fishia spp., Frankliniella spp., Fumibotys spp., Gaesa spp., Gasgardia spp., Gastrophilus spp., Gelechia spp., Gilpinia spp., Gilpinia polytoma, Glossina spp., Glyphipterix spp., Glyphodes spp., Gnorimoschemini spp., Gonodonta spp., Gortyna spp., Gracillaria spp., Graphania spp., Grapholita spp., Grapholitha spp., Gravitarmata spp., Gretchena spp., Griselda spp., Gryllotalpa spp., Gynaephora spp., Gypsonoma spp., Hada spp., Haema- topinus spp., Halisidota spp., Harpipteryx spp., Harrisina spp., Hedya spp., Helicoverpa spp., Heliophobus spp., Heliothis spp., Hellula spp., Helotropa spp., Hemaris spp., Hercinothrips spp., Herculia spp., Hermonassa spp., Heterogenea spp., Holomelina spp., Homadaula spp., Homoeosoma spp., Homoglaea spp., Homohadena spp., Homona spp., Homonopsis spp., Hoplocampa spp., Hoplodrina spp., Hoshinoa spp., Hxalomma spp., Hydraecia spp., Hydriomena spp., Hyles spp., Hyloicus spp., Hypagyrtis spp., Hypatima spp., Hyphantria spp., Hyphantria cunea, Hypocala spp., Hypocoena spp., Hypodema spp., Hyppobosca spp., Hypsipyla spp., Hyssia spp., Hysterosia spp., Idaea spp., Idia spp., Ipimorpha spp., Isia spp., Isochorista spp., Isophrictis spp., Isopolia spp., Isotrias spp., Ixodes spp., Itame spp., Jodia spp., Jodis spp., Kawabea spp., Keiferia spp., Keiferia lycopersicella, Labdia spp., Lacini- polia spp., Lambdina spp., Lamprothritpa spp., Laodelphax spp., Lasius spp., Laspeyresia spp., Leptinotarsa spp., Leptinotarsa decemlineata, Leptocorisa spp., Leptostales spp., Lecanium spp., Lecanium comi, Lepidosaphes spp., Lepisma spp., Lepisma saccharina , Lesmone spp., Leucania spp., Leucinodes spp., Leucophaea spp., Leucophaea maderae, Leucoptera spp., Leucoptera scitella, Linognathus spp., Liposcelis spp., Lissorhoptrus spp., Lithacodia spp., Lithocolletis spp., Lithomoia spp., Lithophane spp., Lixodessa spp., Lobesia spp., Lobesia botrana, Lobophora spp., Locusta spp., Lomanaltes spp., Lomographa spp., Loxagrotis spp., Loxostege spp., Lucilia spp., Lymantria spp., Lymnaecia spp., Lyonetia spp., Lyriomyza spp., Macdonnoughia spp., Macrauzata spp., Macronoctua spp., Macro- siphus spp., Malacosoma spp., Maliarpha spp., Mamestra spp., Mamestra brassicae, Manduca spp., Manduca sexta, Marasmia spp., Margaritia spp., Matratinea spp., Matsumu- raeses spp., Melanagromyza spp., Melipotes spp., Melissopus spp., Melittia spp., Melolontha spp., Meristis spp., Meritastis spp., Merophyas spp., Mesapamea spp., Mesogona spp., Mesoleuca spp., Metanema spp., Metendothenia spp., Metzneria spp., Micardia spp., Micro- corses spp., Microleon spp., Mnesictena spp., Mocis spp., Monima spp., Monochroa spp., Monomorium spp., Monomorium pharaonis, Monopsis spp., Morrisonia spp., Musca spp., Mutuuraia spp., Myelois spp., Mythimna spp., Myzus spp., Naranga spp., Nedra spp., Nema- pogon spp., Neodiprion spp., Neosphaleroptera spp., Nephelodes spp., Nephotettix spp., Nezara spp., Nilaparvata spp., Niphonympha spp., Nippoptilia spp., Noctua spp., Nola spp., Notocelia spp., Notodonta spp., Nudaurelia spp., Ochropleura spp., Ocnerostoma spp., Oestrus spp., Olethreutes spp., Oligia spp., Olindia spp., Olygonychus spp., Olygonychus gallinae, Oncocnemis spp., Operophtera spp., Ophisma spp., Opogona spp., Oraesia spp., Omiodoros spp., Orgyia spp., Oria spp., Orseoiia spp., Orthodes spp., Orthogonia spp., Orthosia spp., Oryzaephilus spp., Oscinella spp., Oscinella frit, Osminia spp., Ostrinia spp., Ostrinia nubilalis, Otiorhynchus spp., Ourapteryx spp., Pachetra spp., Pachysphinx spp., Pagyda spp., Paleacrita spp., Paliga spp., Palthis spp., Pammene spp., Pandemis spp., Panemeria spp., Panolis spp., Panolis flammea, Panonychus spp., Parargyresthia spp., Paradiarsia spp., Paralobesia spp., Paranthrene spp., Parapandemis spp., Parapediasia spp., Parastichtis spp., Parasyndemis spp., Paratoria spp., Pareromeme spp., Pectinophora spp., Pectinophora gossypiella, Pediculus spp., Pegomyia spp., Pegomyia hyoscyami, Pelochrista spp., Pennisetia spp., Penstemonia spp., Pemphigus spp., Peribatodes spp., Peridroma spp., Perileucoptera spp., Periplaneta spp., Perizoma spp., Petrova spp., Pexi- copia spp., Phalonia spp., Phalonidia spp., Phaneta spp., Phlyctaenia spp., Phlyctinus spp., Phorbia spp., Phragmatobia spp., Phricanthes spp., Phthorimaea spp., Phthorimaea oper- culella, Phyllocnistis spp., Phyllocoptruta spp., Phyllocoptruta oleivora, Phyllonorycter spp., Phyllophila spp., Phylloxera spp., Pieris spp., Pieris rapae, Piesma spp., Planococus spp., Planotortrix spp., Platyedra spp., Platynota spp., Platyptilia spp., Platysenta spp., Plodia spp., Plusia spp., Plutella spp., Plutella xylostella, Podosesia spp., Polia spp., Popillia spp., Polymixis spp., Polyphagotarsonemus spp., Polyphagotarsonemus latus, Prays spp., Prionoxystus spp., Probole spp., Proceras spp., Prochoerodes spp., Proeulia spp., Pros- chistis spp., Proselena spp., Proserpinus spp., Protagrotis spp., Proteoteras spp., Proto- bathra spp., Protoschinia spp., Pselnophorus spp., Pseudaletia spp., Pseudanthonomus spp., Pseudatemelia spp., Pseudaulacaspis spp., Pseudexentera spp., Pseudococus spp., Pseudohermenias spp., Pseudoplusia spp., Psoroptes spp., Psylla spp., Psylliodes spp., Pterophorus spp., Ptycholoma spp., Pulvinaria spp., Pulvinaria aethiopica, Pyralis spp., Pyrausta spp., Pyrgotis spp., Pyrreferra spp., Pyrrharctia spp., Quadraspidiotus spp., Ran- cora spp., Raphia spp., Reticultermes spp., Retinia spp., Rhagoletis spp, Rhagoletis pomo- nella, Rhipicephalus spp., Rhizoglyphus spp., Rhizopertha spp., Rhodnius spp., Rhopha- losiphum spp., Rhopobota spp., Rhyacia spp., Rhyacionia spp., Rhynchopacha spp., Rhyzo- sthenes spp., Rivula spp., Rondotia spp., Rusidrina spp., Rynchaglaea spp., Sabulodes spp., Sahlbergella spp., Sahlbergella singularis, Saissetia spp., Samia spp., Sannina spp., Sanninoidea spp., Saphoideus spp., Sarcoptes spp., Sathrobrota spp., Scarabeidae, Sceli- odes spp., Schinia spp., Schistocerca spp., Schizaphis spp., Schizura spp., Schrecken- steinia spp., Sciara spp., Scirpophaga spp., Scirthrips auranti, Scoparia spp., Scopula spp., Scotia spp., Scotinophara spp., Scotogramma spp., Scrobipalpa spp., Scrobipalpopsis spp., Semiothisa spp., Sereda spp., Sesamia spp., Sesia spp., Sicya spp., Sideridis spp., Simyra spp., Sineugraphe spp., Sitochroa spp., Sitobion spp., Sitophilus spp., Sitotroga spp., Solen- opsis spp., Smerinthus spp., Sophronia spp., Spaelotis spp., Spargaloma spp., Sparganothis spp., Spatalistis spp., Sperchia spp., Sphecia spp., Sphinx spp., Spilonota spp., Spodoptera spp., Spodoptera littoralis, Stagmatophora spp., Staphylinochrous spp., Stathmopoda spp., Stenodes spp., Sterrha spp., Stomoxys spp., Strophedra spp., Sunira spp., Sutyna spp., Swammerdamia spp., Syllomatia spp., Sympistis spp., Synanthedon spp:, Synaxis spp., Syncopacma spp., Syndemis spp., Syngrapha spp., Synthomeida spp., Tabanus spp., Taeniarchis spp., Taeniothrips spp., Tannia spp., Tarsonemus spp., Tegulifera spp., Teha- ma spp., Teleiodes spp., Telorta spp., Tenebrio spp., Tephrina spp., Teratoglaea spp., Terri- cula spp., Tethea spp., Tetranychus spp., Thalpophila spp., Thaumetopoea spp., Thiodia spp., Thrips spp., Thrips palmi, Thrips tabaci, Thyridopteryx spp., Thyris spp., Tineola spp., Tipula spp., Tortricidia spp., Tortrix spp., Trachea spp., Trialeurodes spp., Trialeurodes va- porariorum, Triatoma spp., Triaxomera spp., Tribolium spp., Tricodectes spp., Trichoplusia spp., Trichoplusia ni, Trichoptilus spp., Trioza spp., Trioza erytreae, Triphaenia spp., Tripho- sa spp., Trogoderma spp., Tyria spp., Udea spp., Unaspis spp., Unaspis citri, Utetheisa spp., Valeriodes spp., Vespa spp., Vespamima spp., Vitacea spp., Vitula spp., Witlesia spp., Xan- thia spp., Xanthorhoe spp., Xanthotype spp., Xenomicta spp., Xenopsylla spp., Xenopsylla cheopsis, Xestia spp., Xylena spp., Xylomyges spp., Xyrosaris spp., Yponomeuta spp., Yp- solopha spp., Zale spp., Zanclognathus spp., Zeiraphera spp., Zenodoxus spp., Zeuzera spp., Zygaena spp., It is also possible to control pests of the class Nematoda using the compounds according to the invention. Such pests include, for example, root knot nematodes, cyst- forming nematodes and also stem and leaf nematodes; especially of Heterodera spp., e.g. Heterodera schachtii, Heterodora avenae and Heterodora trifolii; Globodera spp., e.g. Globodera rostochiensis; Meloidogyne spp., e.g. Meloidogyne incognita and Meloidogyne javanica; Radopholus spp., e.g. Radopholus similis; Pratylenchus, e.g. Pratylenchus neglectans and Pratylenchus penetrans; Tylenchulus, e.g. Tylenchulus semipenetrans; Longidorus, Trichodorus, Xiphinema, Ditylenchus, Apheen- choides and Anguina; especially Meloidogyne, e.g. Meloidogyne incognita, and Heterodera, e.g. Heterodera glycines. An especially important aspect of the present invention is the use of the compounds of formula (I) according to the invention in the protection of plants against parasitic feeding pests. The action of the compounds according to the invention and the compositions comprising them against animal pests can be significantly broadened and adapted to the given circumstances by the addition of other insecticides, acaricides or nematicides. Suitable additives include, for example, representatives of the following classes of active ingredient: organophosphorus compounds, nitrophenols and derivatives, formamidines, ureas, carba- mates, pyrethroids, chlorinated hydrocarbons, neonicotinoids and Bacillus thuringiensis preparations. Examples of especially suitable mixing partners include: azamethiphos; chlorfenvin- phos; cypermethrin, cypermethrin high-cis; cyromazine; diafenthiuron; diazinon; dichlorvos; dicrotophos; dicyclanil; fenoxycarb; fluazuron; furathiocarb; isazofos; iodfenphos; kinoprene; lufenuron; methacriphos; methidathion; monocrotophos; phosphamidon; profenofos; dio- fenolan; a compound obtainable from the Bacillus thuringiensis strain GC91 or from strain NCTC11821 ; pymetrozine; bromopropylate; methoprene; disulfoton; quinalphos; tau- fluvalinate; thiocyclam; thiometon; aldicarb; azinphos-methyl; benfuracarb; bifenthrin; buprofezin; carbofuran; dibutylaminothio; cartap; chlorfluazuron; chlorpyrifos; cyfluthrin; lambda-cyhaiothrin; alpha-cypermethrin; zeta-cypermethrin; deltamethrin; diflubenzuron; endosulfan; ethiofencarb; fenitrothion; fenobucarb; fenvalerate; formothion; methiocarb; hep- tenophos; imidacloprid; thiamethoxam; clothianidin; isoprocarb; methamidophos; methomyl; mevinphos; parathion; parathion-methyl; phosalone; pirimicarb; propoxur; teflubenzuron; terbufos; triazamate; fenobucarb; tebufenozide; fipronil; beta-cyfluthrin; silafluofen; fenpyroximate; pyridaben; fenazaquin; pyriproxyfen; pyrimidifen; nitenpyram; acetamiprid; emamectin; emamectin-benzoate; spinosad; a plant extract that is active against insects; a preparation that comprises nematodes and is active against insects; a preparation obtainable from Bacillus subtilis; a preparation that comprises fungi and is active against insects; a preparation that comprises viruses and is active against insects; chlorfenapyr; acephate; acrinathrin; alanycarb; alphamethrin; amitraz; AZ 60541 ; azinphos A; azinphos M; azocyclotin; bendiocarb; bensultap; beta-cyfluthrin; BPMC; brofenprox; bromophos A; bufencarb; butocarboxin; butylpyridaben; cadusafos; carbaryl; carbophenothion; chloetho- carb; chlorethoxyfos; chlormephos; cis-resmethrin; clocythrin; clofentezine; cyanophos; cycloprothrin; cyhexatin; demeton M; demeton S; demeton-S-methyl; dichlofenthion; dicliphos; diethion; dimethoate; dimethylvinphos; dioxathion; edifenphos; esfenvalerate; ethion; ethofenprox; ethoprophos; etrimphos; fenamiphos; fenbutatin oxide; fenothiocarb; fenpropathrin; fenpyrad; fenthion; fluazinam; flucycloxuron; flucythrinate; flufenoxuron; flufenprox; fonophos; fosthiazate; fubfenprox; HCH; hexaflumuron; hexythiazox; IKI-220; iprobenfos; isofenphos; isoxathion; ivermectin; malathion; mecarbam; mesulfenphos; metaldehyde; metolcarb; milbemectin; moxidectin; naled; NC 184; omethoate; oxamyl; oxydemethon M; oxydeprofos; permethrin; phenthoate; phorate; phosmet; phoxim; pirimiphos M; pirimiphos E; promecarb; propaphos; prothiofos; prothoate; pyrachlophos; pyradaphenthion; pyresmethrin; pyrethrum; tebufenozide; salithion; sebufos; sulfotep; sul- profos; tebufenpyrad; tebupirimphos; tefluthrin; temephos; terbam; tetrachlorvinphos; thiaclo- prid; thiafenox; thiodicarb; thiofanox; thionazin; thuringiensin; tralomethrin; triarathene; triazophos; triazuron; trichlorfon; triflumuron; trimethacarb; vamidothion; xylylcarb; Yl 5301/5302; zetamethrin; DPX-MP062 — indoxacarb; methoxyfenozide; bifenazate; XMC (3,5-xylyl methylcarbamate); or the fungus pathogen Metarhizium anisopliae. The compounds according to the invention can be used to control, i.e. to inhibit or destroy, pests of the mentioned type occurring on plants, especially on useful plants and ornamentals in agriculture, in horticulture and in forestry, or on parts of such plants, such as the fruits, blossoms, leaves, stems, tubers or roots, while in some cases plant parts that grow later are still protected against those pests. Target crops include especially cereals, such as wheat, barley, rye, oats, rice, maize and sorghum; beet, such as sugar beet and fodder beet; fruit, e.g. pomes, stone fruit and soft fruit, such as apples, pears, plums, peaches, almonds, cherries and berries, e.g. strawberries, raspberries and blackberries; leguminous plants, such as beans, lentils, peas and soybeans; oil plants, such as rape, mustard, poppy, olives, sunflowers, coconut, castor oil, cocoa and groundnuts; cucurbitaceae, such as marrows, cucumbers and melons; fibre plants, such as cotton, flax, hemp and jute; citrus fruits, such as oranges, lemons, grapefruit and mandarins; vegetables, such as spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes and paprika; lauraceae, such as avocado, cinnamon and camphor; and tobacco, nuts, coffee, aubergines, sugar cane, tea, pepper, vines, hops, bananas, natural rubber plants and ornamentals. Further areas of use of the compounds according to the invention are the protection of stored goods and storerooms and the protection of raw materials, and also in the hygiene sector, especially the protection of domestic animals and productive livestock against pests of the mentioned type, more especially the protection of domestic animals, especially cats and dogs, from infestation by fleas, ticks and nematodes. The invention therefore relates also to pesticidal compositions, such as emulsifiable concentrates, suspension concentrates, directly sprayable or dilutable solutions, spreadable pastes, dilute emulsions, wettable powders, soluble powders, dispersible powders, wettable powders, dusts, granules and encapsulations of polymer substances, that comprise at least one of the compounds according to the invention, the choice of formulation being made in accordance with the intended objectives and the 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, e.g. solvents or solid carriers, or surface-active compounds (surfactants). In the area of parasite control in humans, domestic animals, productive livestock and pets it will be self-evident that only physiologically tolerable additives are used. Solvents are, for example: non-hydrogenated or partly hydrogenated aromatic hydrocarbons, preferably fractions C8 to C12 of alkylbenzenes, 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 ethers and esters thereof, such as propylene glycol, dipropyiene glycol ether, ethylene glycol or ethylene glycol monomethyl or -ethyl 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, non-epoxidized or epoxidized plant oils, such as non-epoxidized or epoxidized rapeseed, castor, coconut or soya oil, and silicone oils. Suitable carriers and adjuvants include all substances customarily used in crop protection products, especially products for the control of slugs and snails.
The solid carriers used, for example for dusts and dispersible powders, are as a rule natural rock powders, such as calcite, talc, kaolin, montmorillonite or attapulgite. Highly disperse silicic acids or highly disperse absorbent polymers can also be added to improve the physical properties. Granular adsorptive granule carriers are porous types, such as pumice, crushed brick, sepiolite or bentonite, and non-sorbent carrier materials are calcite or sand. A large number of granular materials of inorganic or organic nature can furthermore be used, in particular dolomite or comminuted plant residues. Surface-active compounds are, depending on the nature of the active compound to be formulated, nonionic, cationic and/or anionic surfactants or surfactant mixtures with good emulsifying, dispersing and wetting properties. The surfactants listed below are to be regarded only as examples; many other surfactants which are customary in formulation technology and are suitable according to the invention are described in the relevant literature. Nonionic surfactants are, in particular, polyglycol ether derivatives of aliphatic or cyclo- aliphatic alcohols, saturated or unsaturated fatty acids and alkylphenols, which can contain 3 to 30 glycol ether groups and 8 to 20 carbon atoms in the (aliphatic) hydrocarbon radical and 6 to 18 carbon atoms in the alkyl radical of the alkylphenols. Substances which are furthermore suitable are water-soluble polyethylene oxide adducts, containing 20 to 250 ethylene glycol ether and 10 to 100 propylene glycol ether groups, on propylene glycol, ethylene diaminopolypropylene glycol and alkyl polypropylene glycol having 1 to 10 carbon atoms in the alkyl chain. The compounds mentioned usually contain 1 to 5 ethylene glycol units per propylene glycol unit. Examples are nonylphenol-polyethoxyethanols, castor oil polyglycol ethers, polypropylene-polyethylene oxide adducts, tributylphenoxypoly- ethoxyethanol, polyethylene glycol and octylphenoxypolyethoxyethanol. Other substances are fatty acid esters of polyoxyethylene sorbitan, such as polyoxyethylene sorbitan trioleate. The cationic surfactants are, in particular, quaternary ammonium salts which contain, as substituents, at least one alkyl radical having 8 to 22 C atoms and, as further substituents, lower, non-halogenated or halogenated alkyl, benzyl or lower hydroxyalkyl radicals. The salts are preferably in the form of halides, methyl-sulfates or ethyl-sulfates. Examples are stearyl-trimethyl-ammoniurn chloride and benzyl-di-(2-chloroethyl)-ethyl- ammonium bromide. Suitable anionic surfactants can be both water-soluble soaps and water-soluble synthetic surface-active compounds. Suitable soaps are the alkali metal, alkaline earth metal and substituted or unsubstituted ammonium salts of higher fatty acids (C10-C22), such as the sodium or potassium salts of oleic or stearic acid, or of naturally occurring fatty acid mixtures, which can be obtained, for example, from coconut oil or tall oil; and furthermore also the fatty acid methyl-taurine salts. However, synthetic surfactants are more frequently used, in particular fatty sulfonates, fatty sulfates, sulfonated benzimidazole derivatives or alkylarylsulfonates. The fatty sulfonates and sulfates are as a rule in the form of alkali metal, alkaline earth metal or substituted or unsubstituted ammonium salts and in general have an alkyl radical of 8 to 22 C atoms, alkyl also including the alkyl moiety of acyl radicals; examples are the sodium or calcium salt of ligninsulfonic acid, of dodecylsulfuric acid ester or of a fatty alcohol sulfate mixture prepared from naturally occurring fatty acids. These also include the salts of sulfuric acid esters and sulfonic acids of fatty alcohol-ethylene oxide adducts. The sulfonated benzimidazole derivatives preferably contain 2 sulfonic acid groups and a fatty acid radical having about 8 to 22 C atoms. Alkylarylsulfonates are, for example, the sodium, calcium or triethanolammonium salts of dodecylbenzenesulfonic acid, of dibutylnaphthalenesulfonic acid or of a naphthalenesulfonic acid-formaldehyde condensation product. Corresponding phosphates, such as salts of the phosphoric acid ester of a p-nonylphenol-(4-14)-ethylene oxide adduct or phospholipids, can further also be used. The compositions as a rule comprise 0.1 to 99 %, in particular 0.1 to 95 %, of active compound and 1 to 99.9 %, in particular 5 to 99.9 %, of - at least - one solid or liquid auxiliary, it being possible as a rule for 0 to 25 %, in particular 0.1 to 20 %, of the composition to be surfactants (% is in each case per cent by weight). While concentrated compositions are more preferred as commercial goods, the end user as a rule uses dilute compositions which comprise considerably lower concentrations of active compound. Preferred compositions are composed, in particular, as follows (% = per cent by weight):
Emulsifiable concentrates: 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%
Dusts: active ingredient: 0.1 to 10%, preferably 0.1 to 1% solid carrier: 99.9 to 90%, preferably 99.9 to 99%
Suspension concentrates: active ingredient: 5 to 75%, preferably 10 to 50% water: 94 to 24%, preferably 88 to 30% surfactant: 1 to 40%, preferably 2 to 30% Wettable powders: 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%
Granules: active ingredient: 0.5 to 30%, preferably 3 to 15% solid carrier: 99.5 to 70%, preferably 97 to 85%
The compositions according to the invention may also comprise further solid or liquid adjuvants, such as stabilisers, e.g. vegetable oils or epoxidised vegetable oils (e.g. epoxi- dised coconut oil, rapeseed oil or soybean oil), antifoams, e.g. silicone oil, preservatives, viscosity regulators, binders and/or tackifiers as well as fertilisers or other active ingredients for obtaining special effects, e.g. acaricides, bactericides, fungicides, nematicides, mollus- cicides or selective herbicides. The crop protection products according to the invention are prepared in known manner, in the absence of adjuvants, e.g. by grinding, sieving and/or compressing a solid active ingredient or mixture of active ingredients, for example to a certain 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 adjuvant(s). The invention relates likewise to those processes for the preparation of the compositions according to the invention and to the use of the compounds of formula (I) in the preparation of those compositions. The invention relates also to the methods of application of the crop protection products, 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 the 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 crop protection is application to the foliage of the plants (foliar application), the frequency and the rate of application being dependent upon the risk of infestation by the pest in question. However, the active ingredient can also penetrate the plants through the roots (systemic action) when the locus of the plants is impregnated with a liquid formulation or when 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 the case of paddy rice crops, such granules may be applied in metered amounts to the flooded rice field. The crop protection products according to the invention are also suitable for protecting plant propagation material, e.g. seed, such as fruits, tubers or grains, or plant cuttings, against animal pests. The propagation material can be treated with the composition before planting: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition can also be applied to the planting site when the propagation material is being planted, for example to the seed furrow during sowing.
The compositions according to the invention are also suitable for protecting plant propagation material, including genetically modified propagation material, e.g. seed, such as fruits, tubers or grains, or plant seedlings, against animal pests. The propagation material can be treated with the composition before being planted: seed, for example, can be dressed before being sown. The active ingredients according to the invention can also be applied to grains (coating), either by impregnating the seeds in a liquid formulation or by coating them with a solid formulation. The composition 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 such methods of treating plant propagation material and to the plant propagation material so treated. The following Examples serve to illustrate the invention. They do not limit the invention. Temperatures are given in degrees Celsius; mixing ratios of solvents are given in parts by volume. Preparation Examples: Example P1 ): Preparation of 3,3-dichloro-N-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)- phenoxy]-propyl}-2-(4-trifluoromethyl-phenyl)-acrylamide
Figure imgf000038_0001
P1.1 ): 680 mg of oxo-(4-trifluoromethyl-phenyl)-acetic acid ethyl ester and 2.2 g of tri- phenylphosphine are introduced into 8 ml of acetonitrile. 0.8 ml of carbon tetrachloride is then added and the mixture is heated at reflux for 4 hours. The reaction mixture is concentrated completely and the crude product is purified over silica gel. 3,3-Dichloro-2-(4- trifluoromethyi-phenyl)-acrylic acid ethyl ester is obtained. 1H-NMR (CDCI3) 300 MHz: 1.30 (t,3H), 4.30 (q,2H), 7.52 (d,2H), 7.68 (d,2H). P1.2): 650 mg of 3,3-dichloro-2-(4-trifluoromethyl-phenyl)-acrylic acid ethyl ester are introduced into 4 ml of tetrahydrofuran. 100 mg of lithium hydroxide in 1.5 ml of water are then added and the mixture is stirred at room temperature for 16 hours. After a further 4 hours at 40°C, the reaction mixture is poured into water, rendered acidic with concentrated hydrochloric acid and extracted with ethyl acetate. The organic phases are washed twice with water and concentrated. 3,3-Dichloro-2-(4-trifluoromethyl-phenyl)-acryIic acid is obtained. P1.3): 74 mg of 3,3-dichloro-2-(4-trifluoromethyl-phenyl)-acrylic acid, 67 mg of bis(2- oxo-3-oxazolidinyl)-phosphinic acid chloride, 53 mg of triethylamine and 100 mg of 3-[2,6- dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propylamine are stirred in 2 ml of dichloromethane for 48 hours at 40°C. The reaction mixture is diluted with 16 ml of ethyl acetate and washed twice with aqueous potassium carbonate solution. After concentration of the organic phase and purification over silica gel, the title compound is obtained. Example P2): Preparation of 1 ,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[2-(4- trifluoromethyl-phenoxymethyl)-allyloxy]-benzene
Figure imgf000038_0002
P2.1 ): 5 g of 4-hydroxybenzotrifluoride, 12.8 g of potassium carbonate, 500 mg of potassium iodide and 18 g of epichlorohydrin are stirred in 75 ml of acetone for 15 hours at 60°C. The reaction mixture is filtered and the filtrate is concentrated. The residue is taken up in ethyl acetate and washed with water. After concentration of the organic phase and Kugelrohr distillation, 2-(4-trifluoromethyl-phenoxymethyl)-oxirane is obtained. (b.p.20 145- 150°C) P2.2): 8 g of 2-(4-trifluoromethyI-phenoxymethyl)-oxirane and 3.8 g of 2,6-dichloro-4- (3,3-dichloro-ailyloxy)-phenol are stirred in 80 mi of N-ethyl-diisopropylamine and 50 ml of toluene for 14 days at 100°C. The reaction mixture is concentrated, and the residue is taken up in ethyl acetate and washed with hydrochloric acid and water. After concentration of the organic phase and purification over silica gel, 1-[2,6-dichloro-4-(3,3-dichloro-allyloxy)- phenoxy]-3-(4-trifluoromethyl-phenoxy)-propan-2-ol is obtained. 1H-NMR (CDCI3) 300 MHz: 2.81 (d,1 H), 4.15-4.48 (m,5H), 4.59 (d,2H), 6.11 (t,1 H), 6.86 (s,2H), 7.01 (d,2H), 7.58 (d,2H) P2.3): 1.15 ml of dimethyl sulfoxide are added at -60°C in the course of 5 minutes to 0.63 ml of oxalyl chloride in 50 ml of dichloromethane. After 40 minutes, a solution of 3.4 g of 1-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-3-(4-trifluoromethyl-phenoxy)-propan-2-ol in 30 ml of dichloromethane is added dropwise in the course of 10 minutes. After 40 minutes, 4.5 ml of triethylamine are added and the reaction mixture is slowly heated to room temperature. The reaction mixture is then poured into water and extracted with dichloromethane. After concentration of the organic phase and crystallisation from diethyl ether/hexane, 1-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-3-(4-trifluoromethyl- phenoxy)-propan-2-one is obtained. 1H-NMR (CDCI3) 300 MHz: 4.61 (d,2H), 4.74 (s,2H), 5.21 (s,2H), 6.12 (t,1 H), 6.90 (s,2H), 7.11 (d,2H), 7.59 (d,2H) P2.4): 189 mg of potassium tert-butylate and 532 mg of methyltriphenylphosphonium bromide are heated in 8 ml of toluene for 3 hours at 80°C. The reaction mixture is cooled to 50°C and a solution of 500 mg of 1-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-3-(4-tri- fluoromethyl-phenoxy)-propan-2-one in 5 ml of toluene is added in the course of 5 minutes. After 2 hours at 80°C, the reaction mixture is filtered, diluted with ethyl acetate and washed with water. After concentration of the organic phase and purification over silica gel, the title compound is obtained. Example P3): Preparation of 1-(4-{2-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy- methyl]-allyloxy}-phenyl)-ethanone O-methyl-oxime
Figure imgf000039_0001
P3.1) 20 g of 2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenol and 28.8 g of potassium carbonate are introduced into 150 ml of acetonitrile. 26 g of 3-chloro-2-chloromethyl-propene are then added and the mixture is stirred for 2.5 hours at 80°C. The reaction mixture is cooled to room temperature and filtered, and the filtrate is concentrated. After purification over silica gel, 1 ,3-dichloro-2-(2-chloromethyl-allyloxy)-5-(3,3-dichloro-allyloxy)-benzene is obtained. P3.2) 1.6 g of 1 ,3-dichloro-2-(2-chloromethyl-allyloxy)-5-(3,3-dichloro-allyloxy)-benzene and 686 mg of 4-hydroxyacetophenone are introduced into 25 ml of acetonitrile. 1.7 g of potassium carbonate and 50 mg of potassium iodide are then added and the mixture is stirred for 3 hours at 80°C. The reaction mixture is filtered and the filtrate is concentrated. After purification over silica gel, 1-(4-{2-[2,6-dichloro-4-(3,3-dichioro-allyloxy)- phenoxymethyl]-allyloxy}-phenyl)-ethanone is obtained. P3.3) 286 mg of 1-(4-{2-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxymethyl]-allyloxy}- phenyl)-ethanone and 56 mg of O-methyl-hydroxylamine hydrochloride are introduced into 4 ml of methanol. 55 mg of sodium acetate are then added and the mixture is stirred for 24 hours at 25°C. The reaction mixture is diluted with 12 ml of ethyl acetate and washed twice with water. After concentration of the organic phase and purification over silica gel, the title compound is obtained. Example P4): Preparation of 1 ,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[3,3-dichloro-2- (4-trifiuoromethyl-phenoxymethyl)-allyloxy]-benzene
Figure imgf000040_0001
312 mg of triphenylphosphine, 183 mg of carbon tetrachloride and 200 mg of 1-[2,6- dichloro-4-(3,3-dichloro-aIlyloxy)-phenoxy]-3-(4-trifluoromethyl-phenoxy)-propan-2-one are stirred in 3 ml of acetonitrile for 24 hours at 55°C. The reaction mixture is concentrated and the residue is purified over silica gel. The title compound is obtained. Example P5): Preparation of 1 ,3-dichloro-5-(3,3-dichloro-allyloxy)-2-[4-(4-fluoro- phenyl)-pent-4-enyloxy]-benzene
Figure imgf000041_0001
P5.1) 2.0 g of 2-(3-chloro-propyl)-2-(4-fluoro-phenyl)-[1 ,3]dioxolane are added to a suspension of 2.36 g of 2,6-dichioro-4-(3,3-dichloro-allyloxy)-phenol, 1.7 g of potassium carbonate and 120 mg of potassium iodide in 50 ml of acetone. The mixture is then stirred for 48 hours at 60°C. The reaction mixture is concentrated and the residue is taken up in water and extracted with ethyl acetate. After concentration of the organic phase and purification over silica gel, 2-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl}-2-(4- fluoro-phenyl)-[1 ,3]dioxolane is obtained. P5.2) 2.0 g of 2-{3-[2,6-dichloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl}-2-(4-fluoro- phenyl)-[1 ,3]dioxolane are dissolved in 20 ml of ethanol, and 1.95 g of 10% aqueous hydrochloric acid are added thereto. After stirring for 16 hours at 80°C, the reaction mixture is concentrated. After purification over silica gel, 4-[2,6-dichloro-4-(3,3-dichloro-allyloxy)- phenoxy]-1-(4-fluoro-phenyl)-butan-1-one is obtained. P5.3) 84 mg of potassium tert-butylate and 236 mg of methyltriphenylphosphonium bromide are stirred in 6 ml of toluene for 3 hours at 80°C. 200 mg of 4-[2,6-dichloro-4-(3,3- dichloro-allyloxy)-phenoxy]-1-(4-fluoro-phenyl)-butan-1-one in 2 ml of toluene are then added and the mixture is stirred for a further 2 hours at 80°C. The reaction mixture is cooled and filtered and the filtrate is concentrated. After purification over silica gel, the title compound is obtained. Example P6): Preparation of 2-(4-fluoro-phenyl)-3-methyl-but-2-enoic acid {3-[2,6-di- chloro-4-(3,3-dichloro-allyloxy)-phenoxy]-propyl}-amide
Figure imgf000041_0002
233 mg of 2-(4-fluoro-phenyl)-3-methyl-but-2-enoic acid are introduced into 10 ml of toluene. 10 mg of dimethylformamide and 0.17 ml of thionyl chloride are then added and the mixture is stirred for 2 hours at 110°C. The reaction mixture is concentrated and the residue is added to a solution of 343 mg of 2-[2,6-dichloro-4-(3,3-dichIoroallyloxy)-phen- oxy]-propylamine hydrochloride, 0.23 ml of pyridine and 0.13 ml of triethylamine in 20 ml of dichloromethane. After stirring for 2 hours at room temperature, the reaction mixture is poured into water and extracted with dichloromethane. After concentration of the organic phase and purification over silica gel, the title compound is obtained. Example P7: The further Examples in the following Tables can also be prepared in a manner analogous to that described above. Table 1 : Compounds of formula
Figure imgf000042_0001
wherein the symbol indicates the bond to the basic structure
Figure imgf000042_0002
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
No. R 1H-NMR (CDCI3) 300 MHz; m p. or 20 'D
1.67 Resin
1.68 Resin
1.69 Resin
Figure imgf000052_0001
1.70 Resin
1.71 Resin
1.72 Resin
Figure imgf000052_0002
1.73 Resin
Figure imgf000052_0003
Figure imgf000053_0001
Figure imgf000054_0001
No. R 1H-NMR (CDCI3) 300 MHz; m.p. or 20
1 .90 Resin
1.91 Resin
1.92 Resin
Figure imgf000055_0001
1.93 Br Resin
1.94 Resin
Figure imgf000055_0002
1.95 Resin
Figure imgf000055_0003
1.96 Resin
Figure imgf000055_0004
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0002
Table A: Compounds of formulae
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000059_0002
Figure imgf000060_0001
- 60
No. R
A.57 4-C(=0)C2H5
A.58 4-C(=0)-n-C3H7
A.59 4-C(=0)-n-C4H9
A.60 4-C(=O)-n-C5H11
A.61 4-C(=0)-n-C6H13
A.62 4-C(=0)-iso-C3H7
A.63 4-C(=0)-iso-C4H9
A.64 4-C(=O)-iso-C5H11
A.65 4-C(=0)-tert-C4H9
A.66 4-C(=0)-cyclopropyl
A.67 4-C(=N-OCH3)CH3
A.68 4-C(=N-OCH3)C2H5
A.69 4-C(=N-OCH3)-n-C3H7
A.70 4-C(=N-OCH3)-n-C4H9
A.71 4-C(=N-OCH3)-n-C5H11
A.72 4-C(=N-OCH3)-n-C6H13
A.73 4-C(=N-OCH3)-iso-C3H7
A.74 4-C(=N-OCH3)-iso-C4H9
A.75 4-C(=N-OCH3)-iso-C5H11
A.76 4-C(=N-OCH3)-tert-C4H9
A.77 4-C(=N-OCH3)-cyclopropyl
A.78 4-C(=N-OCH2CH3)CH3
A.79 4-C(=N-OCH2CH3)C2H5
A.80 4-C(=N-OCH2CH3)-n-C3H7
A.81 4-C(=N-OCH2CH3)-n-C4H9
A.82 4-C(=N-OCH2CH3)-n-C5H11 A.83 4-C(=N-OCH2CH3)-n-C6H13 A.84 4-C(=N-OCH2CH3)-iso-C3H7 A.85 4-C(=N-OCH2CH3)-iso-C4H9 A.86 4.C(=N-OCH2CH3)-iso-C5H11 A.87 4-C(=N-OCH2CH3)-tert-C4H9 A.88 4-C(=N-OCH2CH3)-cyclopropyl A.89 4-C(=N-OCH2CH=CH2)CH3 A.90 4-C(=N-OCH2CH=CH2)C2H5 A.91 • 4-C(=N-OCH2CH=CH2)-n-C3H7 A.92 4-C(=N-OCH2CH=CH2)-n-C4H9 A.93 4-C(=N-OCH2CH=CH2)-n-C5H11 No. R
A.94 4-C(=N-OCH2CH=CH2)-n-C6H13
A.95 4-C(=N-OCH2CH=CH2)-iso-C3H7
A.96 4-C(=N-OCH2CH=CH2)-iso-C4H9
A.97 4-C(=N-OCH2CH=CH2)-iso-C5H11
A.98 4-C(=N-OCH2CH=CH2)-tert-C4H9
A.99 4-C(=N-OCH2CH=CH2)-cyclopropyl
A.100 4-C(=N-OCH2c=CH)CH3
A.101 4-C(=N-OCH2C≡CH)C2H5
A.102 4-C(=N-OCH2C≡CH)-n-C3H7
A.103 4-C(=N-OCH2C≡CH)-n-C4H9
A.104 4-C(=N-OCH2C≡CH)-n-C5H11
A.105 4-C(=N-OCH2C≡CH)-n-C6H13
A.106 4-C(=N-OCH2C≡CH)-iso-C3H7
A.107 4-C(=N-OCH2C≡CH)-iso-C4H9
A.108 4-C(=N-OCH2CsCH)-iso-C5H11
A.109 4-C(=N-OCH2C≡CH)-tert-C4H9
A.110 4-C(=N-OCH2C≡CH)-cyclopropyl
A.111 4-NHC(=0)OCH3
A.112 4-NHC(=0)OC2H5
A.113 4-NHC(=0)0-n-C3H7
A.114 4-NHC(=0)0-n-C4H9
A.115 4-NHC(=0)OCH2CH=CH2
A.116 4-NHC(=0)OCH2C≡CCH3
A.117 4-CH2NHC(=O)OCH3 A.118 4-CH2NHC(=O)OC2H5 A.119 4-CH2NHC(=0)0-n-C3H7 A.120 4-CH2NHC(=0)0-n-C4H9 A.121 4-CH2NHC(=0)OCH2CH=CH2 A.122 4-CH2NHC(=0)OCH2C≡CCH3 A.123 4-N(CH3)C(=O)OCH3 A.124 4-N(CH3)C(=O)OC2H5 A.125 4-N(CH3)C(=O)0-n-C3H7 A.126 4-N(CH3)C(=0)0-n-C4H9 A.127 4-N(CH3)C(=0)OCH2CH=CH2 A.128 4-N(CH3)C(=0)OCH2C≡CCH3 A.129 4-CH2N(CH3)C(=0)OCH3 A.130 4-CH2N(CH3)C(=0)OC2H5 No. R A.131 4-CH2N(CH3)C(=0)0-n-C3H7 A.132 4-CH2N(CH3)C(=0)0-n-C4H9 A.133 4-CH2N(CH3)C(=0)OCH2CH=CH2 A.134 4-CH2N(CH3)C(=0)OCH2C≡CCH3 A.135 4-N(C2H5)C(=0)OCH3 A.136 4-N(C2H5)C(=0)OC2H5 A.137 4-N(C2H5)C(=0)0-n-C3H7 A.138 4-N(C2H5)C(=0)0-n-C4H9 A.139 4-N(C2H5)C(=0)OCH2CH=CH2 A.140 4-N(C2H5)C(=0)OCH2C--CCH3 A.141 4-CH2N(C2H5)C(=0)OCH3 A.142 4-CH2N(C2H5)C(=0)OC2H5 A.143 4-CH2N(C2H5)C(=0)0-n-C3H7 A.144 4-CH2N(C2H5)C(=0)0-n-C4H9 A.145 4-CH2N(C2H5)C(=0)OCH2CH=CH2 A.146 4-CH2N(C2H5)C(=0)OCH2C=CCH3
Table 2: A compound of general formula X-, and X2 are chlorine and the substituent R for each compound corresponds to A.146 of Table A. Table 3: A compound of general formula X-i and X2 are chlorine and the substituent R for each compound corresponds to A.146 of Table A. Table 4: A compound of general formula Xi and X2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A. Table 5: A compound of general formula X-i and X2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A. Table 6: A compound of general formula X and X2 are chlorine and the substituent R for each compound corresponds 1 to A.146 of Table A. Table 7: A compound of general formula X1 and X2 are bromine and the substituent R for each compound corresponds 1 to A.146 of Table A. Table 8: A compound of general formula XΪ and X2 are bromine and the substituent R for each compound corresponds 1 to A.146 of Table A. Table 9: A compound of general formula XT and X2 are bromine and the substituent R for each compound corresponds
Figure imgf000063_0001
1 to A.146 of Table A. Table 10: A compound of general formula (Id) wherein Xn and X2 are bromine and the substituent R for each compound corresponds to a line A.1 to A.146 of Table A. Table 11 : A compound of general formula (le) wherein X^ and X2 are bromine and the substituent R for each compound corresponds to a line A.1 to A.146 of Table A. Table B: Compounds of formulae
Figure imgf000064_0001
Figure imgf000064_0002
Table 12: A compound of general formula (If) wherein X-i and X2 are chlorine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B. Table 13: A compound of general formula (Ig) wherein
Figure imgf000065_0001
and X2 are chlorine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B. Table 14: A compound of general formula (If) wherein Xi and X2 are bromine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B. Table 15: A compound of general formula (Ig) wherein
Figure imgf000065_0002
and X2 are bromine and the substituent R for each compound corresponds to a line B.1 to B.16 of Table B.
Formulation Examples (% = percent by weight)
Example F1 : Emulsifiable concentrates a) b) c) active ingredient 25% 40% 50% calcium dodecylbenzenesulfonate 5% 8% 6% castor oil polyethylene glycol ether (36 mol EO) 5% - - tributylphenol polyethylene glycol ether (30 mol EO) - 12% 4% cyclohexanone - 15% 20% xylene mixture 65% 25% 20%
Mixing finely ground active ingredient and additives gives an emulsifiable concentrate which yields emulsions of the desired concentration on dilution with water.
Example F2: Solutions a) b) c) d) active ingredient 80% 10% 5% 95% ethylene glycol monomethyl ether 20% - - - polyethylene glycol (MW 400) - 70% - -
N-methylpyrrolid-2-one - 20% - - epoxidised coconut oil - - 1 % 5% benzine (boiling range: 160-190°) _ _ 94% _
Mixing finely ground active ingredient and additives gives a solution suitable for use in the form of microdrops.
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% The active ingredient is dissolved in dichloromethane, the solution is sprayed onto the carrier mixture and the solvent is evaporated off in vacuo.
Biological Examples
Example B1 : Action against Heliothis virescens caterpillars
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising
400 ppm of test compound. After the spray-coating has dried, the soybean plants are populated with 10 caterpillars of Heliothis virescens in the first stage and placed in a plastics container. Evaluation is made 6 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.
The compounds of the Tables exhibit good activity against Heliothis virescens in this test. In particular, the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to 1.37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.
Example B2: Action against Plutella xylostella caterpillars
Young cabbage plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound. After the spray-coating has dried, the cabbage plants are populated with 10 caterpillars of Plutella xylostella in the third stage and placed in a plastics container. Evaluation is made 3 days later. The percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on the untreated plants.
The compounds of the Tables exhibit good activity against Plutella xylostella in this test. In particular, the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to 1.37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.
Example B3: Action against Spodoptera littoralis
Young soybean plants are sprayed with an aqueous emulsion spray mixture comprising 400 ppm of test compound and, after the spray-coating has dried, the plants are populated with 10 caterpillars of Spodoptera littoralis in the first stage and then placed in a plastics container. 3 days later, the percentage reduction in population and the percentage reduction in feeding damage (% activity) are determined by comparing the number of dead caterpillars and the feeding damage on the treated plants with that on untreated plants.
The compounds of the Tables exhibit good activity against Spodoptera littoralis in this test. In particular, the compounds 1.2 to 1.6, 1.8 to 1.9, 1.11 , 1.13 to 1.14, 1.18 to 1.19, 1.32 to .37, 1.41 to 1.44 and 1.46 to 1.115 are more than 80 % effective.

Claims

What is claimed is:
1. A compound of formula
Figure imgf000068_0001
wherein Xi and X2 are each independently of the other fluorine, chlorine or bromine; Ai and A2 are each independently of the other a bond or a d-C6alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C3-C8cycloalkyl; A3 is a d-C6alkylene bridge which is unsubstituted or substituted by from one to six identical or different substituents selected from halogen and C3-C8cycloalkyl; R and R2 are each independently of the other halogen, OH, SH, CN, nitro, d-C6alkyl, CrCehaloalkyl, d-C6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, d-C6alkoxy, d-C6haloalkoxy, C2-C6alkenyloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, C2-C6haloalkynyloxy, -(S=0)CrC6alkyl, -S(=0)2-CrC6alkyl or d-C6alkoxycarbonyl; R3 is H, halogen, OH, SH, CN, nitro, d-C6alkyl, CrCehaloalkyl, d-C6alkyl-carbonyl, C2-C6alkenyl, C2-C6haloalkenyl, C2-C6alkynyl, d-C6alkoxy, d-C6haloalkoxy, C2-C6alken- yloxy, C2-C6haloalkenyloxy, C3-C6alkynyloxy, -(S=0)-C C6alkyl, -S(=0)2-CrC6alkyl, C C6alkoxycarbonyl or C2-C6haloalkynyloxy; the substituents R3 being independent of one another when m is 2; R4 and R5 are each independently of the other H, halogen, cyano, nitro, Crdalkyl, d-C3haloalkyl, d-C6alkoxy-CrC6alkyl, d-C3alkyl-carbonyl, d-C3haloalkylcarbonyl, CrC6alkoxycarbonyl, C3-C8cycloalkyl, C3-C8cycloalkyl-CrC6alkyl or C3-C8cycloalkylcarbonyl; m is 1 or 2; Y is O, NR6, S, SO or S02; Q is O, NR7, S, SO or S02; W is a bond, O, NR7, S, SO, S02, -C(=0)-0-, -0-C(=0)-, -C(R8)=N-0-, -C(=0)-NR9- or -NR9-C(=0)-; T is a bond, O, NR7, S, SO, S02, -C(=0)-0-, -0-C(=0)-, -C(=0)-NR9- or -NR9-C(=0)- or -C(R8)=N-0-; R6 and R7 are each independently of the other H, d-C6alkyI, d-C3haloalkyl, d-C6alkyl-carbonyl, CrC3haloalkylcarbonyl, CrC6alkoxy-CrC6alkyl, CrC6alkoxycarbonyl, C3-C8cycloalkyl, C3-C8cycloalkyl-CrC6alkyl or C3-C8cycloalkylcarbonyl; R8 is H, CrC6alkyl, d-C3haloalkyl, CrC6alkoxy-CrC6alkyl or C3-C8cycloalkyl; R9 is H, d-C6alkyl, CrC3haloalkyl, CrC6alkyl-carbonyl, d-dhaloalkylcarbonyl, CrC6alkoxy-CrC6alkyl, CrC6alkoxycarbonyl or C3-C8cycloalkyl; and E is aryl unsubstituted or substituted from one to five times or heterocyclyl unsubstituted or, depending upon the possibilities of substitution on the ring, substituted from one to four times; and, where applicable, their possible E/Z isomers, E/Z isomeric mixtures and/or tautomers, in each case in free form or in salt form.
2. A compound according to claim 1 in free form.
3. A compound according to any one of claims 1 to 2, wherein X^ and X2 are chlorine or bromine.
4. A compound according to any one of claims 1 to 3, wherein Q is oxygen.
5. A compound according to any one of claim 1 to 4, wherein A3 is methylene.
6. A compound according to any one of claim 1 to 5, wherein W is a bond.
7. A pesticidal composition which comprises as active ingredient at least one compound defined in any one of claims 1 to 6, in free form or in agrochemically acceptable salt form, and at least one adjuvant.
8. A method of controlling pests which comprises applying a pesticidal composition as defined in claim 7 to the pests or to the locus thereof.
PCT/EP2004/009500 2003-08-26 2004-08-25 Pesticidally active phenol derivatives Ceased WO2005019147A2 (en)

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