WO2015055497A1 - Substituted pesticidal pyrazole compounds - Google Patents

Substituted pesticidal pyrazole compounds Download PDF

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Publication number
WO2015055497A1
WO2015055497A1 PCT/EP2014/071642 EP2014071642W WO2015055497A1 WO 2015055497 A1 WO2015055497 A1 WO 2015055497A1 EP 2014071642 W EP2014071642 W EP 2014071642W WO 2015055497 A1 WO2015055497 A1 WO 2015055497A1
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methyl
chloro
compound
phenyl
compounds
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PCT/EP2014/071642
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French (fr)
Inventor
Birgit GOCKEL
Daniel SÄLINGER
Sebastian SÖRGEL
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Basf Se
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D403/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00
    • C07D403/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings
    • C07D403/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, not provided for by group C07D401/00 containing two hetero rings linked by a chain containing hetero atoms as chain links
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/58—1,2-Diazines; Hydrogenated 1,2-diazines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/14—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing three or more hetero rings

Definitions

  • the present invention relates to substituted pyrazoles of formula I
  • R 1 is H, Ci-C 2 -alkyl, or Ci-C 2 -alkoxy-Ci-C 2 -alkyl;
  • R 2 is CH3, or halomethyl
  • R 3 is H, F, CI, Br, CN, C C 2 -alkyl, or halomethyl
  • D is a 3- to 6-membered non-aromatic carbo- or heterocycle, which heterocycle may contain
  • R 4 is halogen, OH, CN, N0 2 , Ci-Cio-alkyl, Ci-Ce-haloalkyl, Ci-C 8 -alkoxy, d-C 8 -halo- alkoxy, or S(0) n R a , C3-C6-cycloalkyl, or 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N-R b , O, and S, wherein S may be oxidized,
  • R 4 groups are unsubstituted or partially or fully substituted by R c ;
  • R a is H, Ci-C4-alkyl, Ci-C 2 -haloalkyl, or C3-C6-cycloalkyl, which cycle may be par- tially or fully substituted by R b , wherein R a is not haloalkyl or unsubstituted cy- cloalkyl if D is a cycloalkyl or cycloalkenyl ring;
  • n 0, 1 , or 2;
  • R b is H, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, Ci-C 2 -alkylcarbonyl, or Ci-C 2 -alkoxy- carbonyl;
  • R c is halogen, OH, CN, N0 2 , Ci-C 4 -alkyl, Ci-C 2 -haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 2 - alkoxy, Ci-C 2 -haloalkoxy, or S(0) n R d ;
  • R d is H, Ci-C 4 -alkyl, Ci-C 2 -haloalkyl, or C3-C6-cycloalkyl, which cycle may be partially or fully substituted by R b ;
  • R 4 connected to the same or adjacent ring atoms may together form a 3- to 6-membered carbo- or heterocycle which heterocycle may contain 1 or 2 heteroatoms selected from N-R b , O, and S, wherein S may be oxidised, which cycles may be partially or fully substituted by R 4 radicals;
  • the invention relates to processes and intermediates for preparing the pyrazoles of formula I, and also to active compound combinations comprising them, to compositions comprising them and to their use for combating invertebrate pests. Furthermore, the invention relates to methods of applying such compounds.
  • WO 2010/034737, WO 2010/1 12177, and WO 2012/143317 describe derivatives of pyrid- azineamides derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests.
  • Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property.
  • There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.
  • the compounds according to the invention can be prepared analogously to the synthesis routes described in WO 2010/034737 and WO 2012/143317 according to standard processes of organic chemistry, for example according to the following synthesis route:
  • Compounds of formula I can be prepared e.g. by reacting activated pyrazole carboxylic acid derivative II with a 4-aminopyridazine of formula III (e.g. Houben-Weyl: "Methoden der organ. Chemie” [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 941 -1045).
  • a 4-aminopyridazine of formula III e.g. Houben-Weyl: "Methoden der organ. Chemie” [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 941 -1045.
  • Activated pyrazole carboxylic acid derivatives II are preferably halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluoro- phenyl esters, (2,5-dioxopyrrolidin-1 -yl) esters, benzotriazol-1 -yl esters, triazolo[4,5-b]pyridin-3- yl esters, or tripyrrolidin-1 -ylphosphaniumyl esters.
  • X is a suitable leaving group such as halogen, N3, p-nitrophenoxy or pentafluorophenoxy and the like.
  • Compounds of formula I wherein R 1 is different from hydrogen can also be prepared by alkylating the amides I, in which R 1 is hydrogen, using suitable alkylating agents in the presence of bases.
  • the alkylation can be effected under standard conditions known from literature.
  • Formula I compounds may be present in three isomeric forms, hence formula I encompasses tautomers and isomers T-A, T-B, and T-C:
  • Isomer T-C can be obtained by alkylation of compounds I wherein R 1 is hydrogen.
  • the reaction can be performed by analogy to known N-alkylation of pyridazines.
  • N-Alkylation of Pyri- dazines is known in literature and can be found in e.g.: J. Chem. Soc, Perkin Trans. Vol. 1 , p. 401 (1988), and J. Org. Chem. Vol. 46, p. 2467 (1981 ).
  • the compounds II and III are known in the art or are commercially available or can be prepared by methods known from the literature (cf. WO 05/040169; WO 08/074824; Journal of Fluorine chemistry 132(1 1 ), p.995 (201 1 )).
  • N-oxides of the compounds of formula I can be prepared by oxidation of compounds I according to standard methods of preparing heteroaromatic N-oxides, e.g. by the method described in Journal of Organometallic Chemistry 1989, 370, 17-31 .
  • reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel.
  • Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.
  • compound(s) according to the invention comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof.
  • compound(s) of the present invention is to be understood as equivalent to the term “compound(s) according to the invention”, therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
  • the radicals attached to the backbone of formula I may contain one or more centers of chirali- ty.
  • the formula I are present in the form of different enantiomers or diastereomers, depending on the substituents.
  • the present invention relates to every possible stereoisomer of the formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
  • the compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention relates to amor- phous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.
  • Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the pesticidal action of the compounds of formula I.
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • N-oxide includes any compound of formula I which has at least one tertiary nitro- gen atom that is oxidized to an N-oxide moiety.
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n - Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular flu- orine, chlorine or bromine.
  • alkyl as used herein and in the alkyl moieties of alkoxy, alkylcarbonyl, alkylthio, al- kylsulfinyl, alkylsulfonyl and alkoxyalkyi denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms.
  • Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di- methylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbut
  • haloalkyl as used herein and in the haloalkyl moieties of haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, frequently from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • Preferred haloalkyl moieties are selected from Ci-C2-haloalkyl, in particular from C1-C2- fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
  • alkoxy denotes in each case a straight-chain or branched alkyl group which is bound via an oxygen atom and has usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkoxy group examples are methoxy, ethoxy, n-propoxy, iso-prop- oxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylmethyl denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • alkenyl denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen-1 -yl), 1 - propen-1 -yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1 -yl, 3-buten-1 -yl, 2- penten-1 -yl, 3-penten-1 -yl, 4-penten-1 -yl, 1 -methylbut-2-en-1 -yl, 2-ethylprop-2-en-1 -yl and the like.
  • alkynyl denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1 - yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 - yl, 4-pentyn-1 -yl, 1 -methylbut-2-yn-1 -yl, 1 -ethylprop-2-yn-1 -yl and the like.
  • alkoxyalkyl refers to alkyl usually comprising 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
  • heterocyclyl includes in general 5-, or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals.
  • the heterocyclic non-aromatic radicals usually comprise 1 , 2, or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
  • Examples of 5-, or 6-membered heterocyclic radicals comprise saturated or unsaturated, non- aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothieta- nyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxo- dihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl,
  • the particularly preferred embodiments of the intermediates cor- respond to those of the groups of the formula I.
  • variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I:
  • R 1 is H.
  • R 1 is Ci-C2-alkyl, preferably CH3.
  • R 1 is CH2CH3.
  • R 1 is Ci-C2-alkoxy-Ci-C2-alkyl, preferably Ci-C2-alkoxy-methyl, particularly CH2OCH3.
  • R 2 is CH3.
  • R 2 is halomethyl, preferably fluoromethyl, particularly CHF2, or CF3.
  • R 3 is H.
  • R 3 is selected from F, CN, CH3, C2H5, CH2F, CHF2, and CF3.
  • D is substituted by one or two, particularly two groups R 4 .
  • D is a saturated ring.
  • D is a carbocycle
  • D is a cycloalkyl ring (formula I.A), preferably a cyclohexyl ring.
  • Such compounds correspond to formula I.A1 :
  • R 3 is H, halogen, CN, Ci-C 2 -alkyl, halomethyl, preferably H, CN, CH 3 , CH 2 F, CHF 2 , or CF 3 .
  • R 4 is as defined in the outset, preferably halogen, OH, CN, Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-
  • z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
  • formula I.A Another embodiment of formula I.A are compounds wherein D is a cyclopentyl ring; such compounds correspond to formula I.A2, wherein the variables have the meanings given above.
  • formula I.A Another embodiment of formula I.A are compounds wherein D is a cyclobutyl ring; such com pounds correspond to formula I.A3, wherein the variables have the meanings given above.
  • R 4 preferably is in ortho or para position to the connection to the py- razole, particularly in para position.
  • R 4 stands preferably in ortho posi- tion.
  • D is a saturated heterocyclic ring, preferably a six-membered ring (formula I.B), such as a tetrahydropyrane, particularly a 4-tetrahydropyrane.
  • a tetrahydropyrane particularly a 4-tetrahydropyrane.
  • R 3 , R 4 are each as defined and preferred above;
  • z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
  • R 4 preferably is in ortho position to the connection to the pyrazole. If z is an inte- ger greater than 1 , then two groups R 4 are preferably positioned at the same carbon atom.
  • D is a saturated five-membered heterocyclic ring, such as a tetrahydrofurane (formula I.C), particularly a 2-tetrahydrofurane.
  • a tetrahydrofurane formula I.C
  • 2-tetrahydrofurane Such compounds correspond to formula I.C1 :
  • R 3 , R 4 are each as defined and preferred above;
  • z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
  • R 4 preferably is in 3- or in 5-position. If z is an integer greater than 1 , then two groups R 4 are preferably positioned at the same carbon atom.
  • formula I.C Another embodiment of formula I.C are compounds wherein D is a 3-tetrahydrofurane; such compounds correspond to formula I.C2, wherein the variables have the meanings given above.
  • R 4 preferably is in 4-position. If z is an integer greater than 1 , then two groups R 4 are preferably positioned at the same carbon atom.
  • D is a saturated four-membered heterocyclic ring, such as an oxetane, particularly a 3-oxetane.
  • oxetane particularly a 3-oxetane.
  • Such compounds correspond to formula I.D1 :
  • R 3 , R 4 are each as defined and preferred above;
  • z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
  • D is a saturated four-membered heterocyclic ring, such as a thietane, thietane-1 -oxide, and thietane-1 ,1 -dioxide, particularly a 3-thietane.
  • thietane thietane-1 -oxide
  • thietane-1 ,1 -dioxide particularly a 3-thietane
  • R 3 , R 4 are each as defined and preferred above;
  • z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2 and
  • n 0, 1 , or 2.
  • R 4 preferably is in 2-position. If z is an integer greater than 1 , then two groups R 4 are preferably positioned at the same carbon atom.
  • R 4 is halogen, preferably F.
  • R 4 is CN
  • R 4 is alkyl, preferably CH3, C2H5, CH(CH3)2 or C(CH3)3, particularly CH 3 .
  • R 4 is haloalkylalkyl, preferably CHF3, CH2F, or CF3.
  • R 4 is alkoxy, preferably OCH3.
  • R 4 is haloalkylalkoxy, preferably OCHF3, OCH2F, or OCF3.
  • R 4 is cycloalkyi or cycloalkylalkyl, preferably C-C3H5 or CH2-C-C3H5.
  • the cycloalkyi moiety is unsubstituted or substituted by one or two groups R c , which are preferably selected from halogen, such as fluoro, alkyl, such as CH3, and CN.
  • R 4 is S(0) n R a , with n being 0, 1 , and 2, and R a being preferably CH3.
  • the compounds of the present invention may be used for controlling invertebrate pests.
  • the present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the present invention or a composition as defined above.
  • the present invention also relates to a method for protecting growing plants from attack or in- festation by invertebrate pests, preferably of the group of insects, which method comprises contacting a plant, or soil or water in which the plant is growing or may grow, with a pesticidally effective amount of at least one compound according to the invention including a stereoisomer, salt, tautomer or N-oxide thereof or a composition according to the invention.
  • the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from invertebrate pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below.
  • the method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
  • invertebrate pests are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes. In the sense of the present invention, “invertebrate pests” are most preferably insects.
  • the compounds of the present invention are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriape- des and insects as well as nematodes, especially insects.
  • the compounds of the formula I are especially suitable for efficiently combating the following pests:
  • insects from the order of the lepidopterans for example Acronicta major, Adox- ophyes orana, Aedia leucomelas, Agrotis spp. such as Agrotis fucosa, Agrotis segetum, Agrotis ypsilon; Alabama argillacea, Anticarsia gemmatalis, Anticarsia spp., Argyresthia conjugella, Au- tographa gamma, Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia murinana, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp.
  • Chilo suppressalis such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp.
  • Feltia subterranean such as Feltia subterranean; Galleria mellonella, Grapholitha fune- brana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp. such as Heliothis armigera, Heliothis virescens, Heliothis zea; Hellula undalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homona magnanima, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma spp.
  • Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkel- la, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mods repanda, Mythim- na separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp.
  • Pseudoplusia includens, Pyrausta nubilalis, Rhyacionia frustrana, Scrobipalpula absolutea, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp.
  • beetles (Coleoptera), for example Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus sinuatus, Agriotes spp. such as Agriotes fuscicollis, Agriotes lineatus, Agriotes obscurus; Amphimallus solstitialis, Anisandrus dispar, Anobium punctatum, Anomala rufocuprea, Ano- plophora spp. such as Anoplophora glabripennis; Anthonomus spp.
  • Anthonomus gran- dis such as Anthonomus pomorum; Anthrenus spp., Aphthona euphoridae, Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp.
  • Conoderus vespertinus such as Conoderus vespertinus; Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptorhynchus lapathi, Ctenicera ssp. such as Ctenicera destructor; Cur- culio spp., Dectes texanus, Dermestes spp., Diabrotica spp. such as Diabrotica 12-punctata Diabrotica speciosa, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica virgifera; Epi- lachna spp. such as Epilachna varivestis, Epilachna vigintioctomaculata; Epitrix spp.
  • Leptinotarsa decemlineata such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolon- tha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp.
  • Phyllotreta chrysocephala such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais; Sphenophorus spp. such as Sphenophorus levis; Sternechus spp.
  • Sternechus sub- signatus such as Sternechus sub- signatus; Symphyletes spp., Tenebrio molitor, Tribolium spp. such as Tribolium castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., and Zabrus spp. such as Zabrus tenebri- oides,
  • mosquitoes e.g. Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp.
  • Anopheles albimanus such as Anopheles albimanus, Anopheles crucians, Anopheles freeborni, Anopheles gambiae, Anopheles leucosphyrus, Anopheles maculi- pennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp.
  • Chrysomya bezziana such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochliomyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp.
  • Lucilia caprina such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetio- la destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabulans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pe- gomya hysocyami, Phlebotomus argentipes, Phorbia spp.
  • Phorbia antiqua Phorbia brassicae, Phorbia coarctata
  • Prosimulium mixtum Psila rosae, Psorophora columbiae, Psoro- phora discolor, Rhagoletis cerasi, Rhagoletis pomonella
  • Sarcophaga spp. such as Sarcophaga haemorrhoidalis
  • Simulium vittatum Stomoxys spp. such as Stomoxys calcitrans
  • thrips (Thysanoptera), e.g. Basothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp. such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp. such as Scirtothrips citri; Taeniothrips cardamoni, Thrips spp. such as Thrips oryzae, Thrips palmi, Thrips tabaci;
  • Isoptera e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis,
  • cockroaches (Blattaria - Blattodea), e.g. Acheta domesticus, Blatta orientalis, Blattella asa- hinae, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fulig- ginosa, Periplaneta japonica,
  • Acrosternum spp. such as Acrosternum hilare
  • Aphis fabae such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp.
  • Dysaphis plantaginea such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cin- gulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster in- tegriceps; Euscelis bilobatus, Euschistus spp.
  • Euschistuos heros such as Euschistuos heros, Euschistus impic- tiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hy- peromyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Leca- nium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp.
  • Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbi- ae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia cos- talis, Monelliopsis pecanis, Myzus spp.
  • Nezara spp. such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp.
  • Piezodo- rus guildinii Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Psallus seria- tus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as Pseudo- coccus comstocki; Psylla spp.
  • Psylla mail such as Psylla mail, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp.
  • Rhopalosiphum pseudobrassicas such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scaphoides titan us, Schi- zaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobi- on avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp.
  • Thyanta perditor such as Thyanta perditor; Tibraca spp., Tinocal- lis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii,
  • crickets grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Calliptamus italicus, Chortoicetes terminifera, Dociostaurus maroccanus, Gryllotalpa africana, Gryllotalpa gryllotalpa, Hieroglyphus daganensis, Kraussaria angulifera, Locusta migratoria, Locustana pardalina, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Oedaleus senegalensis, Schistocerca ameri- cana, Schistocerca gregaria, Tachycines asynamorus, and Zonozerus variegatus,
  • arachnids such as acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. Amblyomma americanum, Amblyomma variegatum, Amblyom- ma maculatum), Argas spp. (e.g. Argas persicus), Boophilus spp. (e.g. Boophilus annulatus, Boophilus decoloratus, Boophilus microplus), Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma spp. (e.g.
  • Ixodes spp. e.g. Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus
  • Ornithodo- rus spp. e.g. Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata
  • Ornithonys- sus bacoti Otobius megnini, Dermanyssus gallinae, Psoroptes spp. (e.g. Psoroptes ovis), Rhipicephalus spp. (e.g.
  • Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp.
  • Eotetranychus spp. Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae
  • Bryobia praetiosa Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligonychus pratensis), Vasates lycopersici
  • Araneida e.g. Latrodectus mactans, and Loxosceles reclusa.
  • fleas e.g. Ceratophyllus spp., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Geophilus spp., Scutigera spp. such as Scutigera coleoptrata; millipedes (Diplopoda), e.g. Blaniulus guttulatus, Narceus spp.,
  • Earwigs e.g. forficula auricularia
  • Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eu- rysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp., springtails (Collembola ), e.g. Onychiurus ssp. such as Onychiurus armatus,
  • nematodes plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiy
  • Xiphinema species and other plant parasitic nematode species.
  • Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancy- lostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., As- caris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp.
  • pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caeno- rhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalo- crosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cy- clocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furca- tus, Dicladispa armigera
  • Diloboderus abderus such as Diloboderus abderus; Edessa spp., Epino- tia spp., Formicidae, Geocoris spp., Globitermes sulfureus, Gryllotalpidae, Halotydeus destructor, Hipnodes bicolor, Hydrellia philippina, Julus spp., Laodelphax spp., Leptocorsia acuta , Leptocorsia oratorius , Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Ma lad era matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipter- us, Microtheca spp., Mods latipes, Murgantia spp., Mythe
  • Orseolia oryzae such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Ra- chiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp. such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinopha- ra coarctata; Sesamia spp.
  • Sesamia inferens such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis, Steneotarsonemus spinki, Sylepta derogata, Telehin licus, Trichostrongylus spp..
  • insects preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species: Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips cit- ri, Thrips oryzae, Thrips palmi and Thrips tabaci.
  • the compounds of the present invention are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera as outlined above.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
  • An agrochemical composition comprises a pesticidally effective amount of a compound I.
  • effective amount denotes an amount of the composition or of the compounds I, which is sufficient for controlling invertebrate pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
  • compositions e.g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof.
  • composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g.
  • compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6 th Ed. May 2008, CropLife International.
  • compositions are prepared in a known manner, such as described by Mollet and
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
  • Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g.
  • mineral oil fractions of medium to high boiling point e.g. kerosene, diesel oil
  • oils of vegetable or animal origin oils of vegetable or animal origin
  • aliphatic, cyclic and aromatic hydrocarbons e. g. toluene, paraffin, tetrahydronaphthalene, alkylated
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
  • Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
  • mineral earths e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide
  • polysaccharide powders e.g. cellulose, starch
  • Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
  • Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof.
  • sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox- ylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
  • Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof.
  • alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents.
  • Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines.
  • Suitable amphoteric surfactants are alkylbetains and imidazolines.
  • Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide.
  • Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
  • Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
  • Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
  • Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
  • Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
  • Suitable colorants are pigments of low water solubility and water- soluble dyes.
  • examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
  • Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
  • composition types and their preparation are:
  • a compound I according to the invention 10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%.
  • the active substance dissolves upon dilution with water.
  • a compound I according to the invention 5-25 wt% of a compound I according to the invention and 1 -10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvi- nylpyrrolidone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20-40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I according to the invention In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alco- hol ethoxylate
  • 0,1 -2 wt% thickener e.g. xanthan gum
  • 50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants and wetting agents e.g. sodium lignosulfonate and alcohol ethoxylate
  • wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -3 wt% wetting agents e.g. alcohol ethoxylate
  • solid carrier e.g. silica gel
  • a compound I according to the invention In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
  • dispersants e.g. sodium lignosulfonate
  • 1 -5 wt% thickener e.g. car- boxymethylcellulose
  • 5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
  • organic solvent blend e.g. fatty acid dimethylamide and cyclohexanone
  • surfactant blend e.g. alkohol ethoxylate and arylphenol ethoxylate
  • An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g.
  • methylmethacrylate, methacrylic acid and a di- or triacrylate are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi- cal initiator results in the formation of poly(meth)acrylate microcapsules.
  • a protective colloid e.g. polyvinyl alcohol.
  • Radical polymerization initiated by a radi- cal initiator results in the formation of poly(meth)acrylate microcapsules.
  • an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol).
  • a polyamine e.g. hexamethylenediamine
  • the monomers amount to 1 -10 wt%.
  • the wt% relate to the total CS composition.
  • Dustable powders (DP, DS)
  • 1 -10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
  • 0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
  • solid carrier e.g. silicate
  • Ultra-low volume liquids (UL) 1 -50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
  • auxiliaries such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
  • the agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance.
  • the active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
  • Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds.
  • the compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing.
  • Methods for applying or treating compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material.
  • compound I or the compositions thereof, respectively are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
  • the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
  • amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
  • the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
  • oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix).
  • pesticides e.g. herbicides, insecticides, fungicides, growth regulators, safeners
  • These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
  • the user applies the composition according to the invention usually from a predosage de- vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system.
  • the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained.
  • 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area.
  • individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
  • either individual components of the composition according to the invention or partially premixed components e. g. components comprising compounds I and/or active substances from the groups A) to O
  • the compounds according to the invention may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, e. g. endosulfan, or chlordane; or M.2B fiproles (phenylpyrazoles), e. g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
  • M.3 Sodium channel modulators from the class of M.3A pyrethroids e. g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta- cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox,
  • M.4 Nicotinic acetylcholine receptor agonists from the class of M.4A neonicotinoids, e. g. acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thia- methoxam; or the compounds M.4A.1 : 1 -[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8- hexahydro-9-nitro-(5S,8R)-5,8-Epoxy-1 H-imidazo[1 ,2-a]azepine; or M.4A.2: 1 -[(6-chloro- 3-pyridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; or M4.A.3: 1 -[(6-chloro-3- pyridyl)methyl
  • M.6 Chloride channel activators from the class of avermectins and milbemycins e. g.
  • abamectin emamectin benzoate, ivermectin, lepimectin, or milbemectin;
  • M.7 Juvenile hormone mimics such as M.7A juvenile hormone analogues as hydroprene, ki- noprene and methoprene; or others, as M.7B fenoxycarb, or M.7C pyriproxyfen;
  • M.8 miscellaneous non-specific (multi-site) inhibitors e. g. M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
  • M.9 Selective homopteran feeding blockers, e. g. M.9B pymetrozine, or M.9C flonicamid;
  • M.10 Mite growth inhibitors e. g. M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
  • M.1 1 Microbial disruptors of insect midgut membranes e. g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thu- ringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase e. g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on; M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e. g.
  • chlorfenapyr DNOC, or sulfluramid
  • Nicotinic acetylcholine receptor (nAChR) channel blockers e. g. nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
  • M.16 Inhibitors of the chitin biosynthesis type 1 e. g. buprofezin;
  • Ecdyson receptor agonists such as diacylhydrazines, e. g. methoxyfenozide, tebufeno- zide, halofenozide, fufenozide, or chromafenozide;
  • Octopamin receptor agonists e. g. amitraz
  • M.20 Mitochondrial complex III electron transport inhibitors e. g. M.20A hydramethylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
  • M.21 Mitochondrial complex I electron transport inhibitors e. g. M.21A METI acaricides, and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
  • M.22 Voltage-dependent sodium channel blockers e. g. M.22A indoxacarb, or M.22B meta- flumizone, or M.22C 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylide- ne]amino]-3-[4-(difluoromethoxy)phenyl]urea;
  • M.23 Inhibitors of the of acetyl CoA carboxylase such as Tetronic and Tetramic acid derivatives, e. g. spirodiclofen, spiromesifen, or spirotetramat;
  • M.24 Mitochondrial complex IV electron transport inhibitors e. g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
  • M.25 Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, e. g. cyenopyrafen, or cyflumetofen;
  • M.29 insecticidal active compounds of unknown or uncertain mode of action e. g. afidopyropen, azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, pyflubumide, or the compounds M.29.1 : 4-[5-(3,5- Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro- ethylcarbamoyl)-methyl]-benzamide, or M.29.2: 4-[5-[3-chloro-5-(tri
  • M.29.3 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9- azadispiro[4.2.4.2]-tetradec-1 1 -en-10-one
  • M.29.4 3-(4'-fluoro-2,4-dimethylbiphenyl-3- yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one
  • M.29.5 1 -[2-fluoro-4-methyl-5- [(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or M.29.6: a compound selected from M.29.6a) (E/Z)-N-[1
  • F.I Respiration Inhibitors: F.I-1 ) Inhibitors of complex III at Qo site: strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim- methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chlorodincarb, trifloxystrobin, 2-[2-(2,5- dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6- dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl- acetamide; oxazolidinediones and
  • carboxamides carboxanilides: benodanil, bixafen, boscalid, car- boxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, me- pronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5-carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3- difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2- yl)-3 difluoromethyl-1 -methyl-1 H pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- pheny
  • morpholines, piperidines morpho- lines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine; F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;
  • F.lll Nucleic acid synthesis inhibitors: F.III-1 ) RNA, DNA synthesis; phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl; isoxazoles and iosothiazolones: hymexazole, octhilinone; F.III-2) DNA topoisomerase inhibitors: oxolinic acid; F.III-3) Nucleotide metabolism (e.g. adenosin- deaminase), hydroxy (2-amino)-pyrimidines: bupirimate;
  • F.IV Inhibitors of cell division and or cytoskeleton: F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl; triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine; F.IV-2) Other cell division inhibitors: benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide; F.IV-3) Actin inhibitors: benzophenones: metrafenone;
  • F.V Inhibitors of amino acid and protein synthesis: F.V-1 ) Methionine synthesis inhibitors (ani- lino-pyrimidines): anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
  • F.V-2 Protein synthesis inhibitors (anilino-pyrimidines); antibiotics: blasticidin-S, kasug- amycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
  • F.VI Signal transduction inhibitors: F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino- pyrimidines); dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; phenyl- pyrroles: fenpiclonil, fludioxonil; F.VI-2) G protein inhibitors: quinolines: quinoxyfen;
  • F.VI I Lipid and membrane synthesis inhibitors: F.VI 1-1 ) Phospholipid biosynthesis inhibitors: organophosphorus compounds: edifenphos, iprobenfos, pyrazophos; dithiolanes: isopro- thiolane; F.VII-2) Lipid peroxidation: aromatic hydrocarbons: dicloran, quintozene, tec- clawene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; F.VII-3) Carboxyl acid amides
  • CAA fungicides cinnamic or mandelic acid amides: dimethomorph, flumorph, mandi- proamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester; F.VII-4) Compounds affecting cell membrane permeability and fatty acids: oxathiapiprolin, carbamates: propamocarb, propamocarb-hydrochlorid,
  • F.VIII Inhibitors with Multi Site Action: F.VIII-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VI 11- 2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, me- tiram, propineb, thiram, zineb, ziram; F.VIII-3) Organochlorine compounds (e.g.
  • F.IX Cell wall synthesis inhibitors: F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B; F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil;
  • F.X Plant defence inducers: F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl; F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl- aluminum, phosphorous acid and its salts;
  • N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide 5-chloro-1 (4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy- phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
  • F.XI Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassino- lide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, damino- zide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthi- acet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, tria- penthenol, tributyl phosphorot
  • Biological control agents antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest, Inc., USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. Sonata® and Ballad® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product Botry-Zen from Bacillus substilis strain with NRRL No. B-21661 (e.g. Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest, Inc., USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. Sonata® and Ballad® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product Botry-Zen
  • Chitosan e.g. Armour-Zen from BotriZen Ltd., New Zealand.
  • the quinoline derivative flometoquin is shown in WO 06/013896.
  • the aminofuranone compounds flupyradifurone is known from WO 07/1 15644.
  • the sulfoximine compound sulfoxaflor is known from WO 07/149134.
  • the pyrethroid momfluorothrin is known from US 6908945.
  • the pyrazole acaricide pyflubumide is known from WO 07/020986.
  • the isoxazoline compounds have been described likewise M.29.1 in WO 05/085216, M.29.2. in WO 09/002809 and in WO201 1/149749 and the isoxazoline M.29.9 in WO 13/050317.
  • the pyripyropene derivative afidopyropen has been described in WO 06/129714.
  • the spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO 06/089633 and the biphenyl-substituted spirocyclic ke- toenol derivative M.29.4 from WO 08/06791 1 .
  • triazoylphenylsulfide like M.29.5 have been described in WO 06/043635 and biological control agents on basis of bacillus firmus in WO 09/124707.
  • the neonicotionids 4A.1 is known from WO 120/069266 and WO 1 1/06946, the M.4.A.2 from WO 13/003977, the M4.A.3.from WO 10/069266.
  • the Metaflumizone analogue M.22C is described in CN 10171577.
  • the phthalamides M.28.1 and M.28.2 are both known from WO 07/101540.
  • the anthranilamide M.28.3 has been described in WO 05/077934.
  • the hydrazide compound M.28.4 has been described in WO
  • the anthranilamides M.28.5a) to M.28.5h) can be prepared as described in WO 07/006670, WO 13/024009 and WO 13/024010, the anthranilamide M.28.5i) is described in WO 1 1/085575, the M.28.5j) in WO 08/134969, the M.28.5k) in US 201 1/046186 and the M.28.5I) in WO 12/034403.
  • the diamide compounds M.28.6 and M.28.7 can be found in CN102613183.
  • M.29.6a to ⁇ .29.6 ⁇ listed in M.29.6 have been described in WO 12/029672.
  • the mesoionic antagonist compound M.29.7 was described in WO 12/0921 15, the nematicide M.29.8 in WO 13/055584 and the Pyridalyl-type analogue M.29.10 in WO 10/060379.
  • One embodiment of the invention relates to pesticidal mixtures of at least a compound of formula I with at least one compound B from the groups M.1 to M.29.
  • a preferred embodiment of the invention relates to pesticidal mixtures of a compound of formula I with one compound B from the groups M.1 to M.29.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.1.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.2.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.3.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.4.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.5.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.6.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.7.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.8.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.9.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.10.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.1 1.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.12.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.13.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.14.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.15.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.16.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.17.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.18.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.19.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.20.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.21 .
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.22.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.23.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.24.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.25.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.26.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.27.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.28.
  • a further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.29.
  • Binary mixtures of a compound of formula I and a compound B selected from a group M.1 to M.29 are one preferred embodiment of the invention.
  • Ternary mixtures of a compound of formula I and two compounds B from one or two groups M.1 to M.29 are another preferred embodiment of the invention.
  • the compound B selected from group M.2 as defined above is preferably ethiprole or fipronil, particularly fipronil.
  • the compound B selected from group M.3 as defined above is preferably acrinathrin, bifen- thrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta- cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, flucythrinate, tau- fluvalinate, silafluofen or tralomethrin.
  • the compound B selected from group M.4 as defined above is preferably acetamiprid, clothi- anidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram or thiacloprid.
  • the compound B selected from group M.6 as defined above is preferably abamectin, emamectin benzoate or lepimectin.
  • the compound B selected from group M.9 as defined above is preferably flonicamid or pymet- rozine.
  • the compound B selected from group M.13 as defined above is preferably chlorfenapyr.
  • the compound B selected from group M.23 as defined above is preferably spiromesifen, spirotetramat, or flubendiamide.
  • the compound B selected from group M.28 as defined above is preferably chloranthraniliprole (rynaxypyr) or cyantraniliprole.
  • the compound B selected from group M.29 as defined above is preferably flupyradifurone, pyrifluquinazon, sulfoxaflor or afidopyropen.
  • a particular group of embodiments of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group consisting of fipronil, alpha-cyper- methrin, thiamethoxam, abamectin, spirotetramat, imidacloprid, flonicamid, chloranthraniliprole, pymetrozine, sulfoxaflor and afidopyropen.
  • inventive mixtures wherein the compound B is fipronil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is alpha-cypermethrin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is thiamethoxam and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is abamectin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is spirotetramat and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is imidacloprid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is flonicamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is chloranthraniliprole (rynaxypyr) and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is pymetrozine and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is sulfoxaflor and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is afidopyropen and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • a further embodiment of the invention relates to mixtures of at least a compound of formula I with at least one compound B from one or more groups F.1 to F.1 1.
  • Binary mixtures of a compound of formula I and a compound B from a group F.1 to F.1 1 are one preferred embodiment of the invention.
  • Ternary mixtures of a compound of formula I and two compounds B from one or two groups F.1 to F.1 1 are another preferred embodiment of the invention.
  • Ternary mixtures of a compound of formula I and a compound B selected from each one group M.1 to M.29 and F.1 to F.1 1 are another preferred embodiment of the invention.
  • a further embodiment of the invention relates to an agricultural composition
  • an agricultural composition comprising a compound of formula I, particularly as defined in Tables 1 to 60 and Table I, and one compound B selected from the groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18, M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI.
  • a further embodiment of the invention relates to an agricultural composition
  • an agricultural composition comprising a compound of formula I, particularly as defined in Tables 1 to 60 and Table I, one compound B selected from the groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18, M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, and one compound selected from the groups F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI.
  • a further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 a), preferably from azoxystrobin, pyraclostrobin, fluoxastrobin, picoxystrobin, and trifloxystrobin.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group of the F.1 b), preferably cyazofamid.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 c), preferably from boscalid, fluopyram, fluxapy- roxad, penthiopyrad, and sedaxane.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 d), preferably selected from silthiofam and ametoc- tradin.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.2a), preferably from difenoconazole, epoxiconazole, fluquinconazole, ipconazole, prothioconazole, tebuconazole, triticonazole, and prochloraz.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.2b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.2c), preferably fenhexamid.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.3a), preferably from metalaxyl, and metalaxyl-M.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.3b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.4a), preferably from carbendazim, and thiophanate- methyl.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.4b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.5a), preferably selected from cyprodinil and pyrime- thanil.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.5b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.6a), preferably iprodione.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.6b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.7a).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.7b).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.7c), preferably selected from benthiavalicarb and iprovalicarb.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.7d).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8a).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8b), preferably selected from thiram and mancozeb.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8c), preferably chlorothalonil.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8d).
  • a further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.9.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.10.
  • a further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 1 of fungicides of unknown mode of action.
  • a particular group of embodiments of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group consisting of azoxystrobin, fluoxastro- bin, picoxystrobin, pyraclostrobin, trifloxystrobin, fluxapyroxad, benthiavalicarb, iprovalicarb, fenhexamid, boscalid, mancozeb, ametoctradin, metalalxyl-m, pyrimethanil, cyprodinil, car- bendazim, iprodion, cyazofamid, prochloraz, chlorothalonil, penthiopyrad, difenoconazole, epox- iconazole, ipconazole, prothioconazole, and tebuconazole.
  • active compound B selected from the group consisting of azoxystrobin, fluoxastro- bin, picoxystrobin,
  • inventive mixtures wherein the compound B is azoxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is fluoxastrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is picoxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is pyraclostrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is trifloxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is fluoxapyroxad and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is benthiavalicarb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is iprovalicarb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is fenhexamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is boscalid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is mancozeb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is ametoctradin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is metalalxyl-m and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is pyrimethanil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is cyprodinil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is carbendazim and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is iprodion and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is cyazofamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is prochloraz and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is chlorothalonil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is penthiopyrad and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is difenoconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is epoxiconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is ipconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is prothioconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • inventive mixtures wherein the compound B is tebuconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
  • Table M-l represents preferred combinations of the active compounds I of formula I as defined in Tables 1 to 60, and Table I, and the active compounds B in mixtures according to the invention.
  • the component I is one compound of for- mula I specifically disclosed in the specification ("Compound XX").
  • table M-F represents preferred combinations of the active compounds I of for- mula I as defined in Tables 1 to 60, and Table I, and the active compounds B of groups F.1 to F.1 1 in mixtures according to the invention:
  • the mixtures of the present invention have excellent activity against a broad spectrum of phytopathogenic fungi and animal pests.
  • inventive compounds and the mixtures of the present invention have excellent activity against a broad spectrum of animal pests.
  • invertebrate pests are in particular suitable for efficiently controlling invertebrate pests. Particularier, they are suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
  • the mixtures of at least a compound of formula I and a fungicidal compound have excellent activity against a broad spectrum of phytopathogenic fungi Ascomycetes, Basidiomycetes, Deu- teromycetes and Peronosporomycetes (syn. Oomycetes). Some of them are systemically effective and can be employed in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides. They can also be used for treating seed.
  • Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines;
  • Cochliobolus species on corn, cereals, rice for example Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice;
  • Drechslera species Pyrenophora species on corn, cereals, rice and lawns, for example, D. teres on barley or D. tritici-repentis on wheat;
  • Fusarium and Verticillium species on various plants for example, F. graminearum or F. culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes;
  • Gibberella species on cereals and rice for example Gibberella fujikuroi on rice ;
  • Peronospora species on cabbage and bulbous plants for example, P. brassicae on cabbage or P. destructor on onions;
  • Phytophthora species on various plants for example, P. capsici on bell pepper;
  • Pseudoperonospora on various plants for example, P. cubensis on cucumber or P. humili on hops;
  • Puccinia species on various plants for example, P. triticina, P. striformins,
  • Tilletia species on cereals Ustilago species on cereals, corn and sugar cane, for example, U. maydis on corn;
  • the mixtures according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products.
  • harmful fungi Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp.
  • Tyromyces spp. Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Altemaria spp., Paecilomy- ces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
  • inventive mixtures are especially useful for the control of Lepidoptera, Coleop- tera, Diptera, Thysanoptera and Hemiptera.
  • inventive mixtures are useful for the control of Thysanoptera and Hemiptera, especially Hemiptera.
  • the mixtures according to the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compounds according to the invention.
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compounds by weight, preferably 0.1 to 40% by weight.
  • HPLC-MS high performance liquid chromatography-coupled mass spectrometry
  • HPLC method 1 Phenomenex Kinetex 1 .7 ⁇ XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1 .Oml/min in 1.50 minutes at 60°C.
  • MS quadrupole elec- trospray ionization, 80 V (positive mode).
  • HPLC method 2 Merck Chromolith SpeedROD RP-18e, 50 x 4,6mm; mobile phase: acetoni- trile + 0.1 % trifluoroacetic acid (TFA)/water + 0.1 % TFA, using a gradient of 5:95 to 100:0 over 5 minutes at 40°C, flow rate 1.8 ml/min.
  • MS quadrupole electrospray ionization, 80 V (positive mode).
  • HPLC method 3 Phenomenex Kinetex 1 .7 ⁇ XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.25 minutes; 100% B 0.70 min; flow: 0.8-1.Oml/min in 1.50 minutes at 60°C.
  • MS quadrupole electrospray ionization, 80 V (positive mode).
  • test solutions were prepared as follows:
  • the active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : aceton.
  • the test solution was prepared at the day of use and in general at con- centrations of ppm (wt vol).
  • Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours.
  • the active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
  • Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent light- ing in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
  • the active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
  • Cotton plants at the cotyledon stage were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and 0.6 cm, nontoxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • Cups were covered with a reusable screened lid (150-micron mesh polyester screen Pe- Cap from Tetko, Inc.). Test plants were maintained in a growth room at 25°C and 20-40% rela- tive humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
  • a reusable screened lid 150-micron mesh polyester screen Pe- Cap from Tetko, Inc.
  • the active compounds were formulated in 3:1 (vohvol) water : DMSO with different concentrations of formulated compounds.
  • Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUSTM. The leaf disks were sprayed with 2.5 ⁇ of the test solution and 5 to 8 adult aphids were placed into the microtiter plates which were then closed and kept at 23 ⁇ 1 °C and 50 ⁇ 5% relative humidity under fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Aphid mortality and fecundity was then visually assessed.
  • the active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
  • Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24 hour photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
  • the compounds were formulated in 3:1 (vohvol) water : DMSO.
  • test unit For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well- microtiter plates containing an insect diet and 20-30 A. grandis eggs. Different concentrations of formulated compounds were sprayed onto the insect diet at 20 ⁇ , using a custom built micro atomizer, at two replications. After application, the microtiter plates were incubated at 23 ⁇ 1 °C and 50 ⁇ 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active compounds were formulated in 1 :1 (vohvol) water : aceton and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • the active compounds were formulated as a 1 :1 (vohvol) water : aceton solution.
  • Surfactant Alkamuls EL 620
  • Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • Rice seedlings were cleaned and washed 24 hours before spraying.
  • the active corn-pounds were formulated in 1 :1 (vohvol) water : aceton, and 0.1 % vol/vol surfactant (EL 620) was added.
  • Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inocu- lated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
  • the active compounds were formulated in 1 :1 (vohvol) water : aceton and 0.1 % (vol/vol) Al- kamuls EL 620 surfactant.
  • a 6 cm leaf disk of cabbage leaves was dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper. The leaf disk was inoculated with 10 third instar larvae and kept at 25-27°C and 50-60% humidity for 3 days. Mortality was assessed after 72 h of treatment.
  • the compounds I-37, I-38, I-80, 1-100, 1-101 , 1-125, and 1-126, respectively, at 500 ppm showed a mortality of at least 75% in comparison with untreated controls.
  • the tables show % mortality with the given concentration of active compounds in comparison to untreated controls.

Abstract

The present invention relates to substituted pyrazoles of formula (I) wherein the variables have the meaning as defined in the description, combinations of these compounds and other pesticides, methods and use of these compounds and combinations for combating invertebrate pests such as insects, arachnids or nematodes in and on plants, and for protecting such plants being infested with pests, especially also for protecting plant propagation material as like seeds.

Description

Substituted pesticidal pyrazole compounds
Description
The present invention relates to substituted pyrazoles of formula I
Figure imgf000002_0001
wherein
R1 is H, Ci-C2-alkyl, or Ci-C2-alkoxy-Ci-C2-alkyl;
R2 is CH3, or halomethyl;
R3 is H, F, CI, Br, CN, C C2-alkyl, or halomethyl;
D is a 3- to 6-membered non-aromatic carbo- or heterocycle, which heterocycle may contain
1 or 2 heteroatoms selected from O, and S, wherein S may be oxidised, which carbo- or heterocycle is partially or fully substituted by R4;
R4 is halogen, OH, CN, N02, Ci-Cio-alkyl, Ci-Ce-haloalkyl, Ci-C8-alkoxy, d-C8-halo- alkoxy, or S(0)nRa, C3-C6-cycloalkyl, or 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N-Rb, O, and S, wherein S may be oxidized,
which R4 groups are unsubstituted or partially or fully substituted by Rc; Ra is H, Ci-C4-alkyl, Ci-C2-haloalkyl, or C3-C6-cycloalkyl, which cycle may be par- tially or fully substituted by Rb, wherein Ra is not haloalkyl or unsubstituted cy- cloalkyl if D is a cycloalkyl or cycloalkenyl ring;
n is 0, 1 , or 2;
Rb is H, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkylcarbonyl, or Ci-C2-alkoxy- carbonyl;
Rc is halogen, OH, CN, N02, Ci-C4-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, Ci-C2- alkoxy, Ci-C2-haloalkoxy, or S(0)nRd;
Rd is H, Ci-C4-alkyl, Ci-C2-haloalkyl, or C3-C6-cycloalkyl, which cycle may be partially or fully substituted by Rb;
wherein two groups R4 connected to the same or adjacent ring atoms may together form a 3- to 6-membered carbo- or heterocycle which heterocycle may contain 1 or 2 heteroatoms selected from N-Rb, O, and S, wherein S may be oxidised, which cycles may be partially or fully substituted by R4 radicals;
and the stereoisomers, salts, tautomers and N-oxides thereof. Moreover, the invention relates to processes and intermediates for preparing the pyrazoles of formula I, and also to active compound combinations comprising them, to compositions comprising them and to their use for combating invertebrate pests. Furthermore, the invention relates to methods of applying such compounds.
Further embodiments of the present invention can be found in the claims, the description and the examples. It is to be understood that the features mentioned above and those still to be il- lustrated below of the subject matter of the invention can be applied not only in the respective given combination but also in other combinations without leaving the scope of the invention.
WO 2010/034737, WO 2010/1 12177, and WO 2012/143317 describe derivatives of pyrid- azineamides derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests.
Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, thereby causing large economic loss to the food supply and to property. There is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes. It is therefore an object of the present invention to provide compounds having a good pesticidal activity and showing a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control pests, such as insects.
It has been found that these objectives can be achieved by compounds of formula I, as defined in the outset, and by their stereoisomers, salts, tautomers and N-oxides, in particular their agriculturally acceptable salts.
The compounds according to the invention can be prepared analogously to the synthesis routes described in WO 2010/034737 and WO 2012/143317 according to standard processes of organic chemistry, for example according to the following synthesis route:
Compounds of formula I can be prepared e.g. by reacting activated pyrazole carboxylic acid derivative II with a 4-aminopyridazine of formula III (e.g. Houben-Weyl: "Methoden der organ. Chemie" [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp. 941 -1045).
Figure imgf000003_0001
Activated pyrazole carboxylic acid derivatives II are preferably halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluoro- phenyl esters, (2,5-dioxopyrrolidin-1 -yl) esters, benzotriazol-1 -yl esters, triazolo[4,5-b]pyridin-3- yl esters, or tripyrrolidin-1 -ylphosphaniumyl esters.
In formulae II and III, the radicals have the meanings mentioned above for formula I and in particular the meanings mentioned as being preferred, X is a suitable leaving group such as halogen, N3, p-nitrophenoxy or pentafluorophenoxy and the like.
Compounds of formula I wherein R1 is different from hydrogen can also be prepared by alkylating the amides I, in which R1 is hydrogen, using suitable alkylating agents in the presence of bases. The alkylation can be effected under standard conditions known from literature.
Figure imgf000004_0001
Formula I compounds may be present in three isomeric forms, hence formula I encompasses tautomers and isomers T-A, T-B, and T-C:
Figure imgf000004_0002
For reasons of clarity it is referred to isomer T-A only throughout the specification, but its de- scription embraces disclosure of the other isomers as well.
Isomer T-C can be obtained by alkylation of compounds I wherein R1 is hydrogen. The reaction can be performed by analogy to known N-alkylation of pyridazines. N-Alkylation of Pyri- dazines is known in literature and can be found in e.g.: J. Chem. Soc, Perkin Trans. Vol. 1 , p. 401 (1988), and J. Org. Chem. Vol. 46, p. 2467 (1981 ).
The compounds II and III are known in the art or are commercially available or can be prepared by methods known from the literature (cf. WO 05/040169; WO 08/074824; Journal of Fluorine chemistry 132(1 1 ), p.995 (201 1 )).
N-oxides of the compounds of formula I, can be prepared by oxidation of compounds I according to standard methods of preparing heteroaromatic N-oxides, e.g. by the method described in Journal of Organometallic Chemistry 1989, 370, 17-31 .
If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds I can advantageously be prepared from other compounds I by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or on silica gel. Some of the intermediates and end products may be obtained in the form of colorless or pale brown viscous oils which are freed or purified from volatile components under reduced pressure and at moderately elevated temperature. If the intermediates and end products are obtained as solids, they may be purified by recrystallization or trituration.
The term "compound(s) according to the invention", or "compounds of formula I" comprises the compound(s) as defined herein as well as a stereoisomer, salt, tautomer or N-oxide thereof. The term "compound(s) of the present invention" is to be understood as equivalent to the term "compound(s) according to the invention", therefore also comprising a stereoisomer, salt, tautomer or N-oxide thereof.
The radicals attached to the backbone of formula I may contain one or more centers of chirali- ty. In this case the formula I are present in the form of different enantiomers or diastereomers, depending on the substituents. The present invention relates to every possible stereoisomer of the formula I, i.e. to single enantiomers or diastereomers, as well as to mixtures thereof.
The compounds of formula I may be amorphous or may exist in one or more different crystalline states (polymorphs) which may have different macroscopic properties such as stability or show different biological properties such as activities. The present invention relates to amor- phous and crystalline compounds of formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally acceptable salts. They can be formed in a customary manner, e.g. by reacting the compound with an acid of the anion in question if the compound of formula I has a basic functionality.
Agriculturally useful salts of the compounds of formula I encompass especially the acid addition salts of those acids whose cations and anions, respectively, have no adverse effect on the pesticidal action of the compounds of formula I.
Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogensulfate, sulfate, dihydrogenphosphate, hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyrate. They can be formed by reacting compounds of formula I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
The term "N-oxide" includes any compound of formula I which has at least one tertiary nitro- gen atom that is oxidized to an N-oxide moiety.
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn- Cm indicates in each case the possible number of carbon atoms in the group.
The term "halogen" denotes in each case fluorine, bromine, chlorine or iodine, in particular flu- orine, chlorine or bromine.
The term "alkyl" as used herein and in the alkyl moieties of alkoxy, alkylcarbonyl, alkylthio, al- kylsulfinyl, alkylsulfonyl and alkoxyalkyi denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms and in particular from 1 to 3 carbon atoms. Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl, n- butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 -methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-di- methylpropyl, 1 -ethylpropyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2- methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethyl- butyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1 ,1 ,2- trimethylpropyl, 1 ,2,2-trimethylpropyl, 1 -ethyl-1 -methylpropyl, and 1 -ethyl-2-methylpropyl.
The term "haloalkyl" as used herein and in the haloalkyl moieties of haloalkoxy, haloalkylthio, haloalkylcarbonyl, haloalkylsulfonyl and haloalkylsulfinyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 6 carbon atoms, frequently from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms. Preferred haloalkyl moieties are selected from Ci-C2-haloalkyl, in particular from C1-C2- fluoroalkyl such as fluoromethyl, difluoromethyl, trifluoromethyl, 1 -fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2-trifluoroethyl, pentafluoroethyl, and the like.
The term "alkoxy" as used herein denotes in each case a straight-chain or branched alkyl group which is bound via an oxygen atom and has usually from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy, ethoxy, n-propoxy, iso-prop- oxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy, and the like.
The term "cycloalkyl" as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloal- kylmethyl denotes in each case a monocyclic cycloaliphatic radical having usually from 3 to 6 carbon atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
The term "alkenyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, e.g. vinyl, allyl (2-propen-1 -yl), 1 - propen-1 -yl, 2-propen-2-yl, methallyl (2-methylprop-2-en-1 -yl), 2-buten-1 -yl, 3-buten-1 -yl, 2- penten-1 -yl, 3-penten-1 -yl, 4-penten-1 -yl, 1 -methylbut-2-en-1 -yl, 2-ethylprop-2-en-1 -yl and the like.
The term "alkynyl" as used herein denotes in each case a singly unsaturated hydrocarbon radical having usually 2 to 6, preferably 2 to 4 carbon atoms, e.g. ethynyl, propargyl (2-propyn-1 - yl), 1 -propyn-1 -yl, 1 -methylprop-2-yn-1 -yl), 2-butyn-1 -yl, 3-butyn-1 -yl, 1 -pentyn-1 -yl, 3-pentyn-1 - yl, 4-pentyn-1 -yl, 1 -methylbut-2-yn-1 -yl, 1 -ethylprop-2-yn-1 -yl and the like.
The term "alkoxyalkyl" as used herein refers to alkyl usually comprising 1 to 2 carbon atoms, wherein 1 carbon atom carries an alkoxy radical usually comprising 1 or 2 carbon atoms as defined above. Examples are CH2OCH3, CH2-OC2H5, 2-(methoxy)ethyl, and 2-(ethoxy)ethyl.
The term "heterocyclyl" includes in general 5-, or 6-membered, in particular 6-membered monocyclic heterocyclic non-aromatic radicals. The heterocyclic non-aromatic radicals usually comprise 1 , 2, or 3 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
Examples of 5-, or 6-membered heterocyclic radicals comprise saturated or unsaturated, non- aromatic heterocyclic rings, such as oxiranyl, oxetanyl, thietanyl, thietanyl-S-oxid (S-oxothieta- nyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, pyrazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxo- dihydrothienyl, S-dioxodihydrothienyl, oxazolidinyl, oxazolinyl, thiazolinyl, oxathiolanyl, piperidi- nyl, piperazinyl, pyranyl, dihydropyranyl, tetrahydropyranyl, 1 ,3- and 1 ,4-dioxanyl, thiopyranyl, S.oxothiopyranyl, S-dioxothiopyranyl, dihydrothiopyranyl, S-oxodihydrothiopyranyl, S-dioxo- dihydrothiopyranyl, tetrahydrothiopyranyl, S-oxotetrahydrothiopyranyl, S-dioxotetrahydrothio- pyranyl, morpholinyl, thiomorpholinyl, S-oxothiomorpholinyl, S-dioxothiomorpholinyl, thiazinyl and the like. Examples for heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.
With respect to the variables, the particularly preferred embodiments of the intermediates cor- respond to those of the groups of the formula I.
In a particular embodiment, the variables of the compounds of the formula I have the following meanings, these meanings, both on their own and in combination with one another, being particular embodiments of the compounds of the formula I: In a first embodiment, R1 is H.
In a further embodiment, R1 is Ci-C2-alkyl, preferably CH3.
In a further embodiment, R1 is CH2CH3.
In a further embodiment, R1 is Ci-C2-alkoxy-Ci-C2-alkyl, preferably Ci-C2-alkoxy-methyl, particularly CH2OCH3. In a first embodiment, R2 is CH3.
In a further embodiment, R2 is halomethyl, preferably fluoromethyl, particularly CHF2, or CF3.
In one embodiment of formula I R3 is H.
In another embodiment R3 is selected from F, CN, CH3, C2H5, CH2F, CHF2, and CF3.
In a first preferred embodiment of formula I, D is substituted by one or two, particularly two groups R4.
In a preferred embodiment of formula I, D is a saturated ring.
In another embodiment of formula I, D is a carbocycle.
In a first preferred embodiment of formula I, D is a cycloalkyl ring (formula I.A), preferably a cyclohexyl ring. Such compounds correspond to formula I.A1 :
Figure imgf000007_0001
wherein
R3 is H, halogen, CN, Ci-C2-alkyl, halomethyl, preferably H, CN, CH3, CH2F, CHF2, or CF3. R4 is as defined in the outset, preferably halogen, OH, CN, Ci-C4-alkyl, Ci-C2-haloalkyl, Ci-
C2-alkoxy, Ci-C2-haloalkoxy, C3-C6-cycloalkyl, or S(0)nRb;
z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
Another embodiment of formula I.A are compounds wherein D is a cyclopentyl ring; such compounds correspond to formula I.A2, wherein the variables have the meanings given above.
Figure imgf000007_0002
Another embodiment of formula I.A are compounds wherein D is a cyclobutyl ring; such com pounds correspond to formula I.A3, wherein the variables have the meanings given above.
Figure imgf000007_0003
In formula I.A compounds R4 preferably is in ortho or para position to the connection to the py- razole, particularly in para position. In another embodiment R4 stands preferably in ortho posi- tion.
If z is an integer greater than 1 , then two groups R4 are preferably positioned at the same carbon atom. In another preferred embodiment of formula I, D is a saturated heterocyclic ring, preferably a six-membered ring (formula I.B), such as a tetrahydropyrane, particularly a 4-tetrahydropyrane. Such compounds correspond to formula I.B1 :
Figure imgf000008_0001
wherein R3, R4 are each as defined and preferred above;
z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
Another embodiment of formula I.B are compounds wherein D is a 3-tetrahydropyrane; such compounds correspond to formula I.B2, wherein the variables have the meanings given above.
Figure imgf000008_0002
Another embodiment of formula I.B are compounds wherein D is a 2-tetrahydropyrane; such compounds correspond to formula I.B3, wherein the variables have the meanings given above.
Figure imgf000008_0003
In formula I.B R4 preferably is in ortho position to the connection to the pyrazole. If z is an inte- ger greater than 1 , then two groups R4 are preferably positioned at the same carbon atom.
In another preferred embodiment of formula I, D is a saturated five-membered heterocyclic ring, such as a tetrahydrofurane (formula I.C), particularly a 2-tetrahydrofurane. Such compounds correspond to formula I.C1 :
Figure imgf000008_0004
wherein
R3, R4 are each as defined and preferred above;
z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
In formula I.C1 R4 preferably is in 3- or in 5-position. If z is an integer greater than 1 , then two groups R4 are preferably positioned at the same carbon atom.
Another embodiment of formula I.C are compounds wherein D is a 3-tetrahydrofurane; such compounds correspond to formula I.C2, wherein the variables have the meanings given above.
Figure imgf000009_0001
In formula I.C2 R4 preferably is in 4-position. If z is an integer greater than 1 , then two groups R4 are preferably positioned at the same carbon atom.
In another preferred embodiment of formula I, D is a saturated four-membered heterocyclic ring, such as an oxetane, particularly a 3-oxetane. Such compounds correspond to formula I.D1 :
Figure imgf000009_0002
wherein
R3, R4 are each as defined and preferred above;
z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2.
In another preferred embodiment of formula I, D is a saturated four-membered heterocyclic ring, such as a thietane, thietane-1 -oxide, and thietane-1 ,1 -dioxide, particularly a 3-thietane. Such compounds correspond to formula I.D2:
Figure imgf000009_0003
wherein
R3, R4 are each as defined and preferred above;
z is 1 , 2, 3, or 4; preferably 1 or 2, particularly 2 and
n is 0, 1 , or 2.
In formula I.D R4 preferably is in 2-position. If z is an integer greater than 1 , then two groups R4 are preferably positioned at the same carbon atom.
In a further embodiment R4 is halogen, preferably F.
In a further embodiment R4 is CN.
In a further embodiment R4 is alkyl, preferably CH3, C2H5, CH(CH3)2 or C(CH3)3, particularly CH3.
In a further embodiment R4 is haloalkylalkyl, preferably CHF3, CH2F, or CF3.
In a further embodiment R4 is alkoxy, preferably OCH3.
In a further embodiment R4 is haloalkylalkoxy, preferably OCHF3, OCH2F, or OCF3. In a further embodiment R4 is cycloalkyi or cycloalkylalkyl, preferably C-C3H5 or CH2-C-C3H5. The cycloalkyi moiety is unsubstituted or substituted by one or two groups Rc, which are preferably selected from halogen, such as fluoro, alkyl, such as CH3, and CN.
In a further embodiment R4 is S(0)nRa, with n being 0, 1 , and 2, and Ra being preferably CH3.
In particular with a view to their use, preference is given to the compounds of the formula I compiled in the tables below. Each of the groups mentioned for a substituent in the tables is furthermore per se, independently of the combination in which it is mentioned, a particularly preferred aspect of the substituent in question.
Table 1
Compounds of the formula I in which R1 is H, R2 is CH3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 2
Compounds of the formula I in which R1 is H, R2 is CHF2, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 3
Compounds of the formula I in which R1 is H, R2 is CF3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 4
Compounds of the formula I in which R1 and R2 are CH3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 5
Compounds of the formula I in which R1 is CH3, R2 is CHF2, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 6
Compounds of the formula I in which R1 is CH3, R2 is CF3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 7
Compounds of the formula I in which R1 is CH2CH3, R2 is CH3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 8
Compounds of the formula I in which R1 is CH2CH3, R2 is CHF2, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 9
Compounds of the formula I in which R1 is CH2CH3, R2 is CF3, R3 is H, and the combination of D and R4z for a compound corresponds in each case to one row of Table A
Table 10
Compounds of the formula I in which R1 is CH2OCH3, R2 is CH3, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 1 1
Compounds of the formula I in which R1 is CH2OCH3, R2 is CHF2, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A Table 12
Compounds of the formula I in which R1 is CH2OCH3, R2 is CF3, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 13
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CH3, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 14
Compounds of the formula I .A in which R1 is CH2OCH2CH3, R2 is CHF2, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 15
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CF3, R3 is H, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 16
Compounds of the formula I in which R1 is H, R2 is CH3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 17
Compounds of the formula I in which R1 is H, R2 is CHF2, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 18
Compounds of the formula I in which R1 is H, R2 is CF3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 19
Compounds of the formula I in which R1 and R2 are CH3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 20
Compounds of the formula I in which R1 is CH3, R2 is CHF2, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 21
Compounds of the formula I in which R1 is CH3, R2 is CF3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 22
Compounds of the formula I in which R1 is CH2CH3, R2 is CH3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 23
Compounds of the formula I in which R1 is CH2CH3, R2 is CHF2, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 24
Compounds of the formula I in which R1 is CH2CH3, R2 is CF3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 25
Compounds of the formula I in which R1 is CH2OCH3, R2 is CH3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A Table 26
Compounds of the formula I in which R1 is CH2OCH3, R2 is CHF2, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 27
Compounds of the formula I in which R1 is CH2OCH3, R2 is CF3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 28
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CH3, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 29
Compounds of the formula I .A in which R1 is CH2OCH2CH3, R2 is CHF2, R3 is CN, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 30
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CF3, R3 is CN, and the combina- tion of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 31
Compounds of the formula I in which R1 is H, R2 is CH3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 32
Compounds of the formula I in which R1 is H, R2 is CHF2, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 33
Compounds of the formula I in which R1 is H, R2 is CF3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 34
Compounds of the formula I in which R1 and R2 are CH3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 35
Compounds of the formula I in which R1 is CH3, R2 is CHF2, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 36
Compounds of the formula I in which R1 is CH3, R2 is CF3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 37
Compounds of the formula I in which R1 is CH2CH3, R2 is CH3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 38
Compounds of the formula I in which R1 is CH2CH3, R2 is CHF2, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 39
Compounds of the formula I in which R1 is CH2CH3, R2 is CF3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A Table 40
Compounds of the formula I in which R1 is CH2OCH3, R2 is CH3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 41
Compounds of the formula I in which R1 is CH2OCH3, R2 is CHF2, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 42
Compounds of the formula I in which R1 is CH2OCH3, R2 is CF3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 43
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CH3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 44
Compounds of the formula I .A in which R1 is CH2OCH2CH3, R2 is CHF2, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 45
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CF3, R3 is CH3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 46
Compounds of the formula I in which R1 is H, R2 is CH3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 47
Compounds of the formula I in which R1 is H, R2 is CHF2, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 48
Compounds of the formula I in which R1 is H, R2 is CF3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 49
Compounds of the formula I in which R1 and R2 are CH3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 50
Compounds of the formula I in which R1 is CH3, R2 is CHF2, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 51
Compounds of the formula I in which R1 is CH3, R2 is CF3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 52
Compounds of the formula I in which R1 is CH2CH3, R2 is CH3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 53
Compounds of the formula I in which R1 is CH2CH3, R2 is CHF2, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A Table 54
Compounds of the formula I in which R1 is CH2CH3, R2 is CF3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 55
Compounds of the formula I in which R1 is CH2OCH3, R2 is CH3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 56
Compounds of the formula I in which R1 is CH2OCH3, R2 is CHF2, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 57
Compounds of the formula I in which R1 is CH2OCH3, R2 is CF3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 58
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CH3, R3 is CF3, and the combi- nation of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 59
Compounds of the formula I .A in which R1 is CH2OCH2CH3, R2 is CHF2, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table 60
Compounds of the formula I in which R1 is CH2OCH2CH3, R2 is CF3, R3 is CF3, and the combination of D and R4 Z for a compound corresponds in each case to one row of Table A
Table A
No. D R4 Z No. D R4 Z
A-1 c-CeHg 2-F A-21 c-CeHg 4-OCF3
A-2 c-CeHg 3-F A-22 C-CeHg 2-OCHF2
A-3 c-C6H9 4-F A-23 C-CeHg 3-OCHF2
A-4 C-CeHg 2-CN A-24 C-CeHg 4-OCHF2
A-5 C-CeHg 3-CN A-25 C-CeHg 2-SCH3
A-6 C-CeHg 4-CN A-26 C-CeHg 3-SCH3
A-7 C-CeHg 2-OH A-27 C-CeHg 4-SCH3
A-8 C-CeHg 3-OH A-28 C-CeHg 2-S(0)CH3
A-9 C-CeHg 4-OH A-29 C-CeHg 3-S(0)CH3
A-10 C-CeHg 2-CH3 A-30 C-CeHg 4-S(0)CH3
A-1 1 C-CeHg 3-CH3 A-31 C-CeHg 2-S(0)2CH3
A-12 C-CeHg 4-CH3 A-32 C-CeHg 3-S(0)2CH3
A-13 C-CeHg 2-CF3 A-33 C-CeHg 4-S(0)2CH3
A-14 C-CeHg 3-CF3 A-34 c-CeH8 2,2-F2
A-15 C-CeHg 4-CF3 A-35 c-CeH8 3,3-F2
A-16 C-CeHg 2-OCH3 A-36 c-CeH8 4,4-F2
A-17 C-CeHg 3-OCH3 A-37 c-C6H7 2,4,4-F3
A-18 C-CeHg 4-OCH3 A-38 c-CeH8 2,2-(CN)2
A-19 C-CeHg 2-OCF3 A-39 c-CeH8 3,3-(CN)2
A-20 C-CeHg 3-OCF3 A-40 c-CeH8 4,4-(CN)2
Figure imgf000015_0001
Figure imgf000016_0001
Figure imgf000017_0001
Due to their excellent activity, the compounds of the present invention may be used for controlling invertebrate pests.
Accordingly, the present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of the present invention or a composition as defined above.
The present invention also relates to a method for protecting growing plants from attack or in- festation by invertebrate pests, preferably of the group of insects, which method comprises contacting a plant, or soil or water in which the plant is growing or may grow, with a pesticidally effective amount of at least one compound according to the invention including a stereoisomer, salt, tautomer or N-oxide thereof or a composition according to the invention. Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from invertebrate pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesticidally effective amount of a compound of the present invention as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated. In the sense of the present invention, "invertebrate pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes. In the sense of the present invention, "invertebrate pests" are most preferably insects.
The compounds of the present invention, including their salts, stereoisomers and tautomers, are in particular suitable for efficiently controlling arthropodal pests such as arachnids, myriape- des and insects as well as nematodes, especially insects.
The compounds of the formula I are especially suitable for efficiently combating the following pests:
insects from the order of the lepidopterans (Lepidoptera), for example Acronicta major, Adox- ophyes orana, Aedia leucomelas, Agrotis spp. such as Agrotis fucosa, Agrotis segetum, Agrotis ypsilon; Alabama argillacea, Anticarsia gemmatalis, Anticarsia spp., Argyresthia conjugella, Au- tographa gamma, Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia murinana, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp. such as Chilo suppressalis; Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Clysia ambiguella, Cnaphalocerus spp., Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmopalpus lignosellus, Ephestia cautella, Ephestia kuehniella, Eupoecilia ambiguella, Euproctis chrysorrhoea, Euxoa spp., Evetria bouliana, Feltia spp. such as Feltia subterranean; Galleria mellonella, Grapholitha fune- brana, Grapholitha molesta, Helicoverpa spp. such as Helicoverpa armigera, Helicoverpa zea; Heliothis spp. such as Heliothis armigera, Heliothis virescens, Heliothis zea; Hellula undalis, Hibernia defoliaria, Hofmannophila pseudospretella, Homona magnanima, Hyphantria cunea, Hyponomeuta padella, Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria, Laphygma spp. such as Laphygma exigua; Leucoptera coffeella, Leucoptera scitella, Lithocolletis blancardella, Lithophane antennata, Lobesia botrana, Loxagrotis albicosta, Loxo- sfege sticticalis, Lymantria spp. such as Lymantria dispar, Lymantria monacha; Lyonetia clerkel- la, Malacosoma neustria, Mamestra spp. such as Mamestra brassicae; Mods repanda, Mythim- na separata, Orgyia pseudotsugata, Oria spp., Ostrinia spp. such as Ostrinia nubilalis; Oulema oryzae, Panolis flammea, Pectinophora spp. such as Pectinophora gossypiella; Peridroma sau- cia, Phalera bucephala, Phthorimaea spp. such as Phthorimaea operculella; Phyllocnistis citrel- la, Pieris spp. such as Pieris brassicae, Pieris rapae; Plathypena scabra, Plutella maculipennis, Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera spp. such as Spodoptera frugiperda, Spodoptera littoralis, Spodoptera litura; Thaumatopoea pityocampa, Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp. such as Trichoplusia ni; Tuta absoluta, and Zeiraphera canadensis,
beetles (Coleoptera), for example Acanthoscehdes obtectus, Adoretus spp., Agelastica alni, Agrilus sinuatus, Agriotes spp. such as Agriotes fuscicollis, Agriotes lineatus, Agriotes obscurus; Amphimallus solstitialis, Anisandrus dispar, Anobium punctatum, Anomala rufocuprea, Ano- plophora spp. such as Anoplophora glabripennis; Anthonomus spp. such as Anthonomus gran- dis, Anthonomus pomorum; Anthrenus spp., Aphthona euphoridae, Apogonia spp., Athous haemorrhoidalis, Atomaria spp. such as Atomaria linearis; Attagenus spp., Aulacophora femoralis, Blastophagus piniperda, Blitophaga undata, Bruchidius obtectus, Bruchus spp. such as Bruchus lentis, Bruchus pisorum, Bruchus rufimanus; Byctiscus betulae, Callosobruchus chinensis, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorhynchus spp. such as Ceuthorrhynchus assimilis, Ceuthorrhynchus napi; Chaetocnema tibialis, Cleonus mendicus, Conoderus spp. such as Conoderus vespertinus; Cosmopolites spp., Costelytra zealandica, Crioceris asparagi, Cryptorhynchus lapathi, Ctenicera ssp. such as Ctenicera destructor; Cur- culio spp., Dectes texanus, Dermestes spp., Diabrotica spp. such as Diabrotica 12-punctata Diabrotica speciosa, Diabrotica longicornis, Diabrotica semipunctata, Diabrotica virgifera; Epi- lachna spp. such as Epilachna varivestis, Epilachna vigintioctomaculata; Epitrix spp. such as Epitrix hirtipennis; Eutinobothrus brasiliensis, Faustinus cubae, Gibbium psylloides, Heter- onychus arator, Hylamorpha elegans, Hylobius abietis, Hylotrupes bajulus, Hypera brunneipen- nis, Hypera postica, Hypothenemus spp., Ips typographus, Lachnosterna consanguinea, Lema bilineata, Lema melanopus, Leptinotarsa spp. such as Leptinotarsa decemlineata; Limonius californicus, Lissorhoptrus oryzophilus, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp. such as Lyctus bruneus; Melanotus communis, Meligethes spp. such as Meligethes aeneus; Melolon- tha hippocastani, Melolontha melolontha, Migdolus spp., Monochamus spp. such as Monocha- mus alternatus; Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzae- philus surinamensis, Otiorrhynchus sulcatus, Otiorrhynchus ovatus, Otiorrhynchus sulcatus, Oulema oryzae, Oxycetonia jucunda, Phaedon cochleariae, Phyllobius pyri, Phyllopertha horti- cola, Phyllophaga spp., Phyllotreta spp. such as Phyllotreta chrysocephala, Phyllotreta nemorum, Phyllotreta striolata; Phyllophaga spp., Phyllopertha horticola, Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis , Rhizopertha dominica, Sitona lineatus, Sitophilus spp. such as Sitophilus granaria, Sitophilus zeamais; Sphenophorus spp. such as Sphenophorus levis; Sternechus spp. such as Sternechus sub- signatus; Symphyletes spp., Tenebrio molitor, Tribolium spp. such as Tribolium castaneum; Trogoderma spp., Tychius spp., Xylotrechus spp., and Zabrus spp. such as Zabrus tenebri- oides,
flies, mosquitoes (Diptera), e.g. Aedes spp. such as Aedes aegypti, Aedes albopictus, Aedes vexans; Anastrepha ludens, Anopheles spp. such as Anopheles albimanus, Anopheles crucians, Anopheles freeborni, Anopheles gambiae, Anopheles leucosphyrus, Anopheles maculi- pennis, Anopheles minimus, Anopheles quadrimaculatus, Anopheles sinensis; Bibio hortulanus, Calliphora erythrocephala, Calliphora vicina, Cerafitis capitata, Ceratitis capitata, Chrysomyia spp. such as Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria; Chrysops atlanticus, Chrysops discalis, Chrysops silacea, Cochliomyia spp. such as Cochliomyia hominivorax; Contarinia spp. such as Contarinia sorghicola; Cordylobia anthropophaga, Culex spp. such as Culex nigripalpus, Culex pipiens, Culex quinquefasciatus, Culex tarsalis, Culex tri- taeniorhynchus; Culicoides furens, Culiseta inomata, Culiseta melanura, Cuterebra spp., Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Delia spp. such as Delia antique, Delia coarc- tata, Delia platura, Delia radicum; Dermatobia hominis, Drosophila spp., Fannia spp. such as Fannia canicularis; Gastraphilus spp. such as Gasterophilus intestinalis; Geomyza Tripunctata, Glossina fuscipes, Glossina morsitans, Glossina palpalis, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia spp. such as Hylemyia platura; Hy- poderma spp. such as Hypoderma lineata; Hyppobosca spp., Leptoconops torrens, Liriomyza spp. such as Liriomyza sativae, Liriomyza trifolii; Lucilia spp. such as Lucilia caprina, Lucilia cuprina, Lucilia sericata; Lycoria pectoralis, Mansonia titillanus, Mayetiola spp. such as Mayetio- la destructor; Musca spp. such as Musca autumnalis, Musca domestica; Muscina stabulans, Oestrus spp. such as Oestrus ovis; Opomyza florum, Oscinella spp. such as Oscinella frit; Pe- gomya hysocyami, Phlebotomus argentipes, Phorbia spp. such as Phorbia antiqua, Phorbia brassicae, Phorbia coarctata; Prosimulium mixtum, Psila rosae, Psorophora columbiae, Psoro- phora discolor, Rhagoletis cerasi, Rhagoletis pomonella, Sarcophaga spp. such as Sarcophaga haemorrhoidalis; Simulium vittatum, Stomoxys spp. such as Stomoxys calcitrans; Tabanus spp. such as Tabanus atratus, Tabanus bovinus, Tabanus lineola, Tabanus similis; Tannia spp., Tip- ula oleracea, Tipula paludosa, and Wohlfahrtia spp.,
thrips (Thysanoptera), e.g. Baliothrips biformis, Dichromothrips corbetti, Dichromothrips ssp., Enneothrips flavens, Frankliniella spp. such as Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici; Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp. such as Scirtothrips citri; Taeniothrips cardamoni, Thrips spp. such as Thrips oryzae, Thrips palmi, Thrips tabaci;
termites (Isoptera), e.g. Calotermes flavicollis, Coptotermes formosanus, Heterotermes aureus, Heterotermes longiceps, Heterotermes tenuis, Leucotermes flavipes, Odontotermes spp., Reticulitermes spp. such as Reticulitermes speratus, Reticulitermes flavipes, Reticulitermes grassei, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes virginicus; Termes natalensis,
cockroaches (Blattaria - Blattodea), e.g. Acheta domesticus, Blatta orientalis, Blattella asa- hinae, Blattella germanica, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Periplaneta australasiae, Periplaneta brunnea, Periplaneta fulig- ginosa, Periplaneta japonica,
bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g. Acrosternum spp. such as Acrosternum hilare; Acyrthosipon spp. such as Acyrthosiphon onobrychis, Acyrthosiphon pisum; Adelges laricis, Aeneolamia spp., Agonoscena spp., Aleurodes spp., Al- eurolobus barodensis, Aleurothrixus spp., Amrasca spp., Anasa tristis, Antestiopsis spp., Anu- raphis cardui, Aonidiella spp., Aphanostigma piri, Aphidula nasturtii, Aphis spp. such as Aphis fabae, Aphis forbesi, Aphis gossypii, Aphis grossulariae, Aphis pomi, Aphis sambuci, Aphis schneideri, Aphis spiraecola; Arboridia apicalis, Arilus critatus, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp. such as Bemisia argentifolii, Bemisia tabaci; Blissus spp. such as Blissus leucopterus; Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Calocoris spp., Campylomma livida, Capitophorus horni, Carneocephala fulgida, Cavelerius spp., Ceraplastes spp., Ceratovacuna lanigera, Cercopidae, Cerosipha gossypii, Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis ju- glandicola, Chrysomphalus ficus, Cicadulina mbila, Cimex spp. such as Cimex hemipterus, Ci- mex lectularius; Coccomytilus halli, Coccus spp., Creontiades dilutus, Cryptomyzus ribis, Cryp- tomyzus ribis, Cyrtopeltis notatus, Dalbulus spp., Dasynus pi peris, Dialeurades spp., Diaphorina spp., Diaspis spp., Dichelops eatus, Diconocoris hewetti, Doralis spp., Dreyfusia nordmanni- anae, Dreyfusia piceae, Drosicha spp., Dysaphis spp. such as Dysaphis plantaginea, Dysaphis pyri, Dysaphis radicola; Dysaulacorthum pseudosolani, Dysdercus spp. such as Dysdercus cin- gulatus, Dysdercus intermedius; Dysmicoccus spp., Empoasca spp. such as Empoasca fabae, Empoasca solana; Eriosoma spp., Erythroneura spp., Eurygaster spp. such as Eurygaster in- tegriceps; Euscelis bilobatus, Euschistus spp. such as Euschistuos heros, Euschistus impic- tiventris, Euschistus servus; Geococcus coffeae, Halyomorpha spp. such as Halyomorpha halys; Heliopeltis spp., Homalodisca coagulata, Horcias nobilellus, Hyalopterus pruni, Hy- peromyzus lactucae, lcerya spp., Idiocerus spp., Idioscopus spp., Laodelphax striatellus, Leca- nium spp., Lepidosaphes spp., Leptocorisa spp., Leptoglossus phyllopus, Lipaphis erysimi, Lygus spp. such as Lygus hesperus, Lygus lineolaris, Lygus pratensis; Macropes excavatus, Macrosiphum spp. such as Macrosiphum rosae, Macrosiphum avenae, Macrosiphum euphorbi- ae; Mahanarva fimbriolata, Megacopta cribraria, Megoura viciae, Melanaphis pyrarius, Melanaphis sacchari, Metcafiella spp., Metopolophium dirhodum, Miridae spp., Monellia cos- talis, Monelliopsis pecanis, Myzus spp. such as Myzus ascalonicus, Myzus cerasi, Myzus persi- cae, Myzus varians; Nasonovia ribis-nigri, Nephotettix spp. such as Nephotettix malayanus, Nephotettix nigropictus, Nephotettix parvus, Nephotettix virescens; Nezara spp. such as Nezara viridula; Nilaparvata lugens, Oebalus spp., Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp. such as Pemphigus bursarius; Pen- torn idae, Peregrin us maidis, Perkinsiella saccharicida, Phenacoccus spp., Phloeomyzus pas- serinii, Phorodon humuli, Phylloxera spp., Piesma quadrata, Piezodorus spp. such as Piezodo- rus guildinii, Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Psallus seria- tus, Pseudacysta persea, Pseudaulacaspis pentagona, Pseudococcus spp. such as Pseudo- coccus comstocki; Psylla spp. such as Psylla mail, Psylla piri; Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Reduvius senilis, Rhodnius spp., Rhopalomyzus ascalonicus, Rhopalosiphum spp. such as Rhopalosiphum pseudobrassicas, Rhopalosiphum insertum, Rhopalosiphum maidis, Rhopalosiphum padi; Sagatodes spp., Sahl- bergella singularis, Saissetia spp., Sappaphis mala, Sappaphis mail, Scaphoides titan us, Schi- zaphis graminum, Schizoneura lanuginosa, Scotinophora spp., Selenaspidus articulatus, Sitobi- on avenae, Sogata spp., Sogatella furcifera, Solubea insularis , Stephanitis nashi, Stictocephala festina, Tenalaphara malayensis, Thyanta spp. such as Thyanta perditor; Tibraca spp., Tinocal- lis caryaefoliae, Tomaspis spp., Toxoptera spp. such as Toxoptera aurantii; Trialeurodes spp. such as Trialeurodes vaporariorum; Triatoma spp., Trioza spp., Typhlocyba spp., Unaspis spp. such as Unaspis yanonensis; and Viteus vitifolii,
ants, bees, wasps, sawflies (Hymenoptera), e.g. Athalia rosae, Atta capiguara, Atta cephalo- tes, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana, Bombus spp., Camponotus floridanus, Crematogaster spp., Dasymutilla occidentalis, Diprion spp., Doli- chovespula maculata, Hoplocampa spp. such as Hoplocampa minuta, Hoplocampa testudinea; Lasius spp. such as Lasius niger, Linepithema humile, Monomorium pharaonis, Paravespula germanica, Paravespula pennsylvanica, Paravespula vulgaris, Pheidole megacephala, Pogo- nomyrmex barbatus, Pogonomyrmex californicus, Polistes rubiginosa, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Vespa spp. such as Vespa crabro, and Vespula squamosa,
crickets, grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Calliptamus italicus, Chortoicetes terminifera, Dociostaurus maroccanus, Gryllotalpa africana, Gryllotalpa gryllotalpa, Hieroglyphus daganensis, Kraussaria angulifera, Locusta migratoria, Locustana pardalina, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Oedaleus senegalensis, Schistocerca ameri- cana, Schistocerca gregaria, Tachycines asynamorus, and Zonozerus variegatus,
arachnids (Arachnida), such as acari,e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma spp. (e.g. Amblyomma americanum, Amblyomma variegatum, Amblyom- ma maculatum), Argas spp. (e.g. Argas persicus), Boophilus spp. (e.g. Boophilus annulatus, Boophilus decoloratus, Boophilus microplus), Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hyalomma spp. (e.g. Hyalomma truncatum), Ixodes spp. (e.g. Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus), Ornithodo- rus spp. (e.g. Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata), Ornithonys- sus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes spp. (e.g. Psoroptes ovis), Rhipicephalus spp. (e.g. Rhipicephalus sanguineus, Rhipicephalus appendiculatus, Rhipicephalus evertsi), Rhizoglyphus spp., Sarcoptes spp. (e.g. Sarcoptes scabies), and Eriophyidae spp. such as Acaria sheldoni, Aculops spp. (e.g. Aculops pelekassi) Aculus spp. (e.g. Aculus schlechten- dali), Epitrimerus pyri, Phyllocoptruta oleivora and Eriophyes spp. (e.g. Eriophyes sheldoni); Tarsonemidae spp. such as Hemitarsonemus spp., Phytonemus pallidus and Polyphagotar- sonemus latus, Stenotarsonemus spp.; Tenuipalpidae spp. such as Brevipalpus spp. (e.g. Brevipalpus phoenicis); Tetranychidae spp. such as Eotetranychus spp., Eutetranychus spp., Oligonychus spp., Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae; Bryobia praetiosa, Panonychus spp. (e.g. Panonychus ulmi, Panonychus citri), Metatetranychus spp. and Oligonychus spp. (e.g. Oligonychus pratensis), Vasates lycopersici; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa. And Acarus siro, Chorioptes spp., Scorpio maurus
fleas (Siphonaptera), e.g. Ceratophyllus spp., Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
silverfish, firebrat (Thysanura), e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Geophilus spp., Scutigera spp. such as Scutigera coleoptrata; millipedes (Diplopoda), e.g. Blaniulus guttulatus, Narceus spp.,
Earwigs (Dermaptera), e.g. forficula auricularia,
lice (Phthiraptera), e.g. Damalinia spp., Pediculus spp. such as Pediculus humanus capitis, Pediculus humanus corporis; Pthirus pubis, Haematopinus spp. such as Haematopinus eu- rysternus, Haematopinus suis; Linognathus spp. such as Linognathus vituli; Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus, Trichodectes spp., springtails (Collembola ), e.g. Onychiurus ssp. such as Onychiurus armatus,
They are also suitable for controlling nematodes: plant parasitic nematodes such as root knot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogyne javanica, and other Meloidogyne species; cyst-forming nematodes, Globodera rostochiensis and other Globodera species; Heterodera avenae, Heterodera glycines, Heterodera schachtii, Heterodera trifolii, and other Heterodera species; Seed gall nematodes, Anguina species; Stem and foliar nematodes, Aphelenchoides species such as Aphelenchoides besseyi ; Sting nematodes, Belonolaimus longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus lignicolus Mamiya et Kiyohara, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocricone- ma species; Stem and bulb nematodes, Ditylenchus destructor, Ditylenchus dipsaci and other Ditylenchus species; Awl nematodes, Dolichodorus species; Spiral nematodes, Heliocotylen- chus multicinctus and other Helicotylenchus species; Sheath and sheathoid nematodes, Hemi- cycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Lesion nematodes, Pratylenchus brachy- urus, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus, Rotylenchus reniformis and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primi- f/vus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhyn- chus claytoni, Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrus nematodes, Tylenchulus species such as Tylenchulus semipenetrans; Dagger nematodes,
Xiphinema species; and other plant parasitic nematode species.
Examples of further pest species which may be controlled by compounds of fomula (I) include: from the class of the Bivalva, for example, Dreissena spp.; from the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.; from the class of the helminths, for example, Ancy- lostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., As- caris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp., Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp. such as Haemonchus contortus; Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercora lis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti; from the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber; from the order of the Symphyla, for example, Scutigerella immaculata.
Further examples of pest species which may be controlled by compounds of formula (I) include: Anisoplia austriaca, Apamea spp., Austroasca viridigrisea, Baliothrips biformis, Caeno- rhabditis elegans, Cephus spp., Ceutorhynchus napi, Chaetocnema aridula, Chilo auricilius, Chilo indicus , Chilo polychrysus, Chortiocetes terminifera, Cnaphalocroci medinalis, Cnaphalo- crosis spp., Colias eurytheme, Collops spp., Cornitermes cumulans, Creontiades spp., Cy- clocephala spp., Dalbulus maidis, Deraceras reticulatum , Diatrea saccharalis, Dichelops furca- tus, Dicladispa armigera , Diloboderus spp. such as Diloboderus abderus; Edessa spp., Epino- tia spp., Formicidae, Geocoris spp., Globitermes sulfureus, Gryllotalpidae, Halotydeus destructor, Hipnodes bicolor, Hydrellia philippina, Julus spp., Laodelphax spp., Leptocorsia acuta , Leptocorsia oratorius , Liogenys fuscus, Lucillia spp., Lyogenys fuscus, Mahanarva spp., Ma lad era matrida, Marasmia spp., Mastotermes spp., Mealybugs, Megascelis ssp, Metamasius hemipter- us, Microtheca spp., Mods latipes, Murgantia spp., Mythemina separata , Neocapritermes opa- cus, Neocapritermes parvus, Neomegalotomus spp., Neotermes spp., Nymph ula depunctalis, Oebalus pugnax, Orseolia spp. such as Orseolia oryzae; Oxycaraenus hyalinipennis, Plusia spp., Pomacea canaliculata, Procornitermes ssp, Procornitermes triacifer , Psylloides spp., Ra- chiplusia spp., Rhodopholus spp., Scaptocoris castanea, Scaptocoris spp., Scirpophaga spp. such as Scirpophaga incertulas , Scirpophaga innotata; Scotinophara spp. such as Scotinopha- ra coarctata; Sesamia spp. such as Sesamia inferens, Sogaella frucifera, Solenapsis geminata, Spissistilus spp., Stalk borer, Stenchaetothrips biformis, Steneotarsonemus spinki, Sylepta derogata, Telehin licus, Trichostrongylus spp..
The compounds of the present invention, including their salts, stereoisomers and tautomers, are particularly useful for controlling insects, preferably sucking or piercing insects such as insects from the genera Thysanoptera, Diptera and Hemiptera, in particular the following species: Thysanoptera: Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips cit- ri, Thrips oryzae, Thrips palmi and Thrips tabaci.
The compounds of the present invention, including their salts, stereoisomers and tautomers, are particularly useful for controlling insects of the orders Hemiptera and Thysanoptera as outlined above.
The invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I according to the invention.
An agrochemical composition comprises a pesticidally effective amount of a compound I. The term "effective amount" denotes an amount of the composition or of the compounds I, which is sufficient for controlling invertebrate pests on cultivated plants or in the protection of materials and which does not result in a substantial damage to the treated plants. Such an amount can vary in a broad range and is dependent on various factors, such as the species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I used.
The compounds I, their N-oxides and salts can be converted into customary types of agrochemical compositions, e. g. solutions, emulsions, suspensions, dusts, powders, pastes, granules, pressings, capsules, and mixtures thereof. Examples for composition types are suspensions (e.g. SC, OD, FS), emulsifiable concentrates (e.g. EC), emulsions (e.g. EW, EO, ES, ME), capsules (e.g. CS, ZC), pastes, pastilles, wettable powders or dusts (e.g. WP, SP, WS, DP, DS), pressings (e.g. BR, TB, DT), granules (e.g. WG, SG, GR, FG, GG, MG), insecticidal articles (e.g. LN), as well as gel formulations for the treatment of plant propagation materials such as seeds (e.g. GF). These and further compositions types are defined in the "Catalogue of pesticide formulation types and international coding system", Technical Monograph No. 2, 6th Ed. May 2008, CropLife International.
The compositions are prepared in a known manner, such as described by Mollet and
Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
Examples for suitable auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfac- tants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, attractants, feeding stimulants, compatibilizers, bactericides, anti-freezing agents, anti-foaming agents, colorants, tackifi- ers and binders.
Suitable solvents and liquid carriers are water and organic solvents, such as mineral oil fractions of medium to high boiling point, e.g. kerosene, diesel oil; oils of vegetable or animal origin; aliphatic, cyclic and aromatic hydrocarbons, e. g. toluene, paraffin, tetrahydronaphthalene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclohexanol; glycols; DMSO; ketones, e.g. cyclohexanone; esters, e.g. lactates, carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phosphonates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mixtures thereof.
Suitable solid carriers or fillers are mineral earths, e.g. silicates, silica gels, talc, kaolins, limestone, lime, chalk, clays, dolomite, diatomaceous earth, bentonite, calcium sulfate, magnesium sulfate, magnesium oxide; polysaccharide powders, e.g. cellulose, starch; fertilizers, e.g. ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas; products of vegetable origin, e.g. cereal meal, tree bark meal, wood meal, nutshell meal, and mixtures thereof.
Suitable surfactants are surface-active compounds, such as anionic, cationic, nonionic and amphoteric surfactants, block polymers, polyelectrolytes, and mixtures thereof. Such surfactants can be used as emusifier, dispersant, solubilizer, wetter, penetration enhancer, protective col- loid, or adjuvant. Examples of surfactants are listed in McCutcheon's, Vol.1 : Emulsifiers & Detergents, McCutcheon's Directories, Glen Rock, USA, 2008 (International Ed. or North American Ed.).
Suitable anionic surfactants are alkali, alkaline earth or ammonium salts of sulfonates, sulfates, phosphates, carboxylates, and mixtures thereof. Examples of sulfonates are alkylaryl- sulfonates, diphenylsulfonates, alpha-olefin sulfonates, lignine sulfonates, sulfonates of fatty acids and oils, sulfonates of ethoxylated alkylphenols, sulfonates of alkoxylated arylphenols, sulfonates of condensed naphthalenes, sulfonates of dodecyl- and tridecylbenzenes, sulfonates of naphthalenes and alkylnaphthalenes, sulfosuccinates or sulfosuccinamates. Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethox- ylated alcohols, or of fatty acid esters. Examples of phosphates are phosphate esters. Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or alkylphenol ethoxylates.
Suitable nonionic surfactants are alkoxylates, N-subsituted fatty acid amides, amine oxides, esters, sugar-based surfactants, polymeric surfactants, and mixtures thereof. Examples of alkoxylates are compounds such as alcohols, alkylphenols, amines, amides, arylphenols, fatty acids or fatty acid esters which have been alkoxylated with 1 to 50 equivalents. Ethylene oxide and/or propylene oxide may be employed for the alkoxylation, preferably ethylene oxide. Examples of N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alkanolamides. Examples of esters are fatty acid esters, glycerol esters or monoglycerides. Examples of sugar- based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or al- kylpolyglucosides. Examples of polymeric surfactants are home- or copolymers of vinylpyrroli- done, vinylalcohols, or vinylacetate.
Suitable cationic surfactants are quaternary surfactants, for example quaternary ammonium compounds with one or two hydrophobic groups, or salts of long-chain primary amines. Suitable amphoteric surfactants are alkylbetains and imidazolines. Suitable block polymers are block polymers of the A-B or A-B-A type comprising blocks of polyethylene oxide and polypropylene oxide, or of the A-B-C type comprising alkanol, polyethylene oxide and polypropylene oxide. Suitable polyelectrolytes are polyacids or polybases. Examples of polyacids are alkali salts of polyacrylic acid or polyacid comb polymers. Examples of polybases are polyvinylamines or pol- yethyleneamines.
Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activity themselves, and which improve the biological performance of the compound I on the target. Examples are surfactants, mineral or vegetable oils, and other auxilaries. Further examples are listed by Knowles, Adjuvants and additives, Agrow Reports DS256, T&F Informa UK, 2006, chapter 5.
Suitable thickeners are polysaccharides (e.g. xanthan gum, carboxymethylcellulose), anorganic clays (organically modified or unmodified), polycarboxylates, and silicates.
Suitable bactericides are bronopol and isothiazolinone derivatives such as alkylisothiazoli- nones and benzisothiazolinones.
Suitable anti-freezing agents are ethylene glycol, propylene glycol, urea and glycerin.
Suitable anti-foaming agents are silicones, long chain alcohols, and salts of fatty acids.
Suitable colorants (e.g. in red, blue, or green) are pigments of low water solubility and water- soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacyanofer- rate) and organic colorants (e.g. alizarin-, azo- and phthalocyanine colorants).
Suitable tackifiers or binders are polyvinylpyrrolidone, polyvinylacetates, polyvinyl alcohols, polyacrylates, biological or synthetic waxes, and cellulose ethers.
Examples for composition types and their preparation are:
i) Water-soluble concentrates (SL, LS)
10-60 wt% of a compound I according to the invention and 5-15 wt% wetting agent (e.g. alcohol alkoxylates) are dissolved in water and/or in a water-soluble solvent (e.g. alcohols) up to 100 wt%. The active substance dissolves upon dilution with water.
ii) Dispersible concentrates (DC)
5-25 wt% of a compound I according to the invention and 1 -10 wt% dispersant (e. g. polyvi- nylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
iii) Emulsifiable concentrates (EC)
15-70 wt% of a compound I according to the invention and 5-10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in up to 100 wt% water- insoluble organic solvent (e.g. aromatic hydrocarbon). Dilution with water gives an emulsion. iv) Emulsions (EW, EO, ES)
5-40 wt% of a compound I according to the invention and 1 -10 wt% emulsifiers (e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate) are dissolved in 20-40 wt% water-insoluble organic solvent (e.g. aromatic hydrocarbon). This mixture is introduced into up to 100 wt% water by means of an emulsifying machine and made into a homogeneous emulsion. Dilution with water gives an emulsion.
v) Suspensions (SC, OD, FS)
In an agitated ball mill, 20-60 wt% of a compound I according to the invention are comminuted with addition of 2-10 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alco- hol ethoxylate), 0,1 -2 wt% thickener (e.g. xanthan gum) and up to 100 wt% water to give a fine active substance suspension. Dilution with water gives a stable suspension of the active substance. For FS type composition up to 40 wt% binder (e.g. polyvinylalcohol) is added,
vi) Water-dispersible granules and water-soluble granules (WG, SG)
50-80 wt% of a compound I according to the invention are ground finely with addition of up to 100 wt% dispersants and wetting agents (e.g. sodium lignosulfonate and alcohol ethoxylate) and prepared as water-dispersible or water-soluble granules by means of technical appliances (e. g. extrusion, spray tower, fluidized bed). Dilution with water gives a stable dispersion or solution of the active substance.
vii) Water-dispersible powders and water-soluble powders (WP, SP, WS)
50-80 wt% of a compound I according to the invention are ground in a rotor-stator mill with addition of 1 -5 wt% dispersants (e.g. sodium lignosulfonate), 1 -3 wt% wetting agents (e.g. alcohol ethoxylate) and up to 100 wt% solid carrier, e.g. silica gel. Dilution with water gives a stable dispersion or solution of the active substance.
viii) Gel (GW, GF)
In an agitated ball mill, 5-25 wt% of a compound I according to the invention are comminuted with addition of 3-10 wt% dispersants (e.g. sodium lignosulfonate), 1 -5 wt% thickener (e.g. car- boxymethylcellulose) and up to 100 wt% water to give a fine suspension of the active substance. Dilution with water gives a stable suspension of the active substance.
ix) Microemulsion (ME)
5-20 wt% of a compound I according to the invention are added to 5-30 wt% organic solvent blend (e.g. fatty acid dimethylamide and cyclohexanone), 10-25 wt% surfactant blend (e.g. alkohol ethoxylate and arylphenol ethoxylate), and water up to 100 %. This mixture is stirred for 1 h to produce spontaneously a thermodynamically stable microemulsion.
x) Microcapsules (CS)
An oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), 2-15 wt% acrylic monomers (e.g.
methylmethacrylate, methacrylic acid and a di- or triacrylate) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). Radical polymerization initiated by a radi- cal initiator results in the formation of poly(meth)acrylate microcapsules. Alternatively, an oil phase comprising 5-50 wt% of a compound I according to the invention, 0-40 wt% water insoluble organic solvent (e.g. aromatic hydrocarbon), and an isocyanate monomer (e.g. diphenylme- thene-4,4'-diisocyanatae) are dispersed into an aqueous solution of a protective colloid (e.g. polyvinyl alcohol). The addition of a polyamine (e.g. hexamethylenediamine) results in the for- mation of a polyurea microcapsules. The monomers amount to 1 -10 wt%. The wt% relate to the total CS composition.
xi) Dustable powders (DP, DS)
1 -10 wt% of a compound I according to the invention are ground finely and mixed intimately with up to 100 wt% solid carrier, e.g. finely divided kaolin.
xii) Granules (GR, FG)
0.5-30 wt% of a compound I according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate). Granulation is achieved by extrusion, spray-drying or the fluidized bed.
xiii) Ultra-low volume liquids (UL) 1 -50 wt% of a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
The compositions types i) to xi) may optionally comprise further auxiliaries, such as 0,1 -1 wt% bactericides, 5-15 wt% anti-freezing agents, 0,1 -1 wt% anti-foaming agents, and 0,1 -1 wt% colorants.
The agrochemical compositions generally comprise between 0.01 and 95%, preferably between 0.1 and 90%, and most preferably between 0.5 and 75%, by weight of active substance. The active substances are employed in a purity of from 90% to 100%, preferably from 95% to 100% (according to NMR spectrum).
Water-soluble concentrates (LS), Suspoemulsions (SE), flowable concentrates (FS), powders for dry treatment (DS), water-dispersible powders for slurry treatment (WS), water-soluble powders (SS), emulsions (ES), emulsifiable concentrates (EC) and gels (GF) are usually employed for the purposes of treatment of plant propagation materials, particularly seeds. The compositions in question give, after two-to-tenfold dilution, active substance concentrations of from 0.01 to 60% by weight, preferably from 0.1 to 40% by weight, in the ready-to-use preparations. Application can be carried out before or during sowing. Methods for applying or treating compound I and compositions thereof, respectively, on to plant propagation material, especially seeds include dressing, coating, pelleting, dusting, soaking and in-furrow application methods of the propagation material. Preferably, compound I or the compositions thereof, respectively, are applied on to the plant propagation material by a method such that germination is not induced, e. g. by seed dressing, pelleting, coating and dusting.
When employed in plant protection, the amounts of active substances applied are, depending on the kind of effect desired, from 0.001 to 2 kg per ha, preferably from 0.005 to 2 kg per ha, more preferably from 0.05 to 0.9 kg per ha, in particular from 0.1 to 0.75 kg per ha.
In treatment of plant propagation materials such as seeds, e. g. by dusting, coating or drenching seed, amounts of active substance of from 0.1 to 1000 g, preferably from 1 to 1000 g, more preferably from 1 to 100 g and most preferably from 5 to 100 g, per 100 kilogram of plant propagation material (preferably seed) are generally required.
When used in the protection of materials or stored products, the amount of active substance applied depends on the kind of application area and on the desired effect. Amounts customarily applied in the protection of materials are 0.001 g to 2 kg, preferably 0.005 g to 1 kg, of active substance per cubic meter of treated material.
Various types of oils, wetters, adjuvants, fertilizer, or micronutrients, and other pesticides (e.g. herbicides, insecticides, fungicides, growth regulators, safeners) may be added to the active substances or the compositions comprising them as premix or, if appropriate not until immediately prior to use (tank mix). These agents can be admixed with the compositions according to the invention in a weight ratio of 1 :100 to 100:1 , preferably 1 :10 to 10:1.
The user applies the composition according to the invention usually from a predosage de- vice, a knapsack sprayer, a spray tank, a spray plane, or an irrigation system. Usually, the agrochemical composition is made up with water, buffer, and/or further auxiliaries to the desired application concentration and the ready-to-use spray liquor or the agrochemical composition according to the invention is thus obtained. Usually, 20 to 2000 liters, preferably 50 to 400 liters, of the ready-to-use spray liquor are applied per hectare of agricultural useful area. According to one embodiment, individual components of the composition according to the invention such as parts of a kit or parts of a binary or ternary mixture may be mixed by the user himself in a spray tank and further auxiliaries may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances from the groups A) to O), may be mixed by the user in a spray tank and further auxiliaries and additives may be added, if appropriate.
In a further embodiment, either individual components of the composition according to the invention or partially premixed components, e. g. components comprising compounds I and/or active substances from the groups A) to O), can be applied jointly (e.g. after tank mix) or consecutively.
In the methods and uses of this invention, the compounds according to the invention may be applied with other active ingredients, for example with other pesticides, insecticides, herbicides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the above-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
Moreover, it has also been found that simultaneous, that is joint or separate, application of one or more active compounds A of formula I and one or more active compounds B or successive application of one or more active compounds A and one or more active compounds B allows enhanced control of pests compared to the control rates that are possible with the individ- ual compounds.
1 ) at least one pyrazole compound A selected from the compounds of formula I as defined and preferred in the outset
and
2) at least one further compound B selected from the compounds of the following groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18,
M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI:
M.1 Acetylcholine esterase (AChE) inhibitors from the class of M.1A carbamates, e. g. aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, e. g.
acephate, azamethiphos, azinphos-ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethyl- vinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthi- on, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl 0-(methoxyaminothio- phosphoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion- methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, tri- chlorfon, and vamidothion;
M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organochlorine compounds, e. g. endosulfan, or chlordane; or M.2B fiproles (phenylpyrazoles), e. g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
M.3 Sodium channel modulators from the class of M.3A pyrethroids, e. g. acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta- cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tet- ramethrin, tralomethrin and transfluthrin; or M.3B sodium channel modulators, such as DDT, or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neonicotinoids, e. g. acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thia- methoxam; or the compounds M.4A.1 : 1 -[(6-chloro-3-pyridinyl)methyl]-2,3,5,6,7,8- hexahydro-9-nitro-(5S,8R)-5,8-Epoxy-1 H-imidazo[1 ,2-a]azepine; or M.4A.2: 1 -[(6-chloro- 3-pyridyl)methyl]-2-nitro-1 -[(E)-pentylideneamino]guanidine; or M4.A.3: 1 -[(6-chloro-3- pyridyl)methyl]-7-methyl-8-nitro-5-propoxy-3,5,6,7-tetrahydro-2H-imidazo[1 ,2-a]pyridine; or M.4B nicotine;
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns,
e. g. spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, e. g.
abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;
M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydroprene, ki- noprene and methoprene; or others, as M.7B fenoxycarb, or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, e. g. M.8A alkyl halides as methyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, e. g. M.9B pymetrozine, or M.9C flonicamid;
M.10 Mite growth inhibitors, e. g. M.10A clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
M.1 1 Microbial disruptors of insect midgut membranes, e. g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thu- ringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: CrylAb, CrylAc, Cry1 Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
M.12 Inhibitors of mitochondrial ATP synthase, e. g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, or M.12C propargite, or M.12D tetrad if on; M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e. g.
chlorfenapyr, DNOC, or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, e. g. nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium;
M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas, e.g. bistrifluron,
chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, no- valuron, noviflumuron, teflubenzuron, or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , e. g. buprofezin;
M.17 Moulting disruptors, Dipteran, e. g. cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, e. g. methoxyfenozide, tebufeno- zide, halofenozide, fufenozide, or chromafenozide;
M.19 Octopamin receptor agonists, e. g. amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, e. g. M.20A hydramethylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, e. g. M.21A METI acaricides, and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers, e. g. M.22A indoxacarb, or M.22B meta- flumizone, or M.22C 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-(trifluoromethyl)phenyl]ethylide- ne]amino]-3-[4-(difluoromethoxy)phenyl]urea;
M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, e. g. spirodiclofen, spiromesifen, or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, e. g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide; M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, e. g. cyenopyrafen, or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, e. g. flubendiamide,
chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), or the phthalamide compounds M.28.1 : (R)-3-Chlor-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluoro-1 -(trifluorome- thyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, and M.28.2: (S)-3-
Chloro-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluoro-1 -(trifluoromethyl)ethyl]phenyl}-N2-(1 -methyl- 2-methylsulfonylethyl)phthalamid, or M.28.3: 3-bromo-N-{2-bromo-4-chloro-6-[(1 - cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chlorpyridin-2-yl)-1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or M.28.4: methyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3- chlorpyridin-2-yl)-1 H-pyrazol-5-yl]carbonyl}amino)benzoyl]-1 ,2-dimethylhydrazine- carboxylate; or a compound selected from M.28.5a) to M.28.5I): M.28.5a) N-[4,6-dichloro- 2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide; M.28.5b) N-[4-chloro-2-[(diethyl-lambda-4-sulfanyl- idene)carbamoyl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6- methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2- pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5e) N-[4,6-dichloro-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(diflu- oromethyl)pyrazole-3-carboxamide; M.28.5f) N-[4,6-dibromo-2-[(di-2-propyl-lambda-4- sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyndyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5g) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-6- cyano-phenyl]-2-(3-chloro-2-pyndyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2- pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5i) N-[2-(5-amino-1 ,3,4- thiadiazol-2-yl)-4-chloro-6-methyl-phenyl]-5-bromo-2-(3-chloro-2-pyridyl)pyrazole-3- carboxamide; M.28.5j) 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(1 -cyano-1 - methyl-ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide; M.28.5k) 5-bromo-N-[2,4-di- chloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2-pyridyl)pyrazole-3-carboxamide; M.28.5I) N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5- (fluoromethoxy)pyrazole-3-carboxamide; or a compound selected from M.28.6 N2-(1 - cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthalamide; or M.28.7 3-chloro- N2-(1 -cyano-1 -methyl-ethyl)-N 1 -(2,4-dimethylphenyl)phthalamide;
M.29 insecticidal active compounds of unknown or uncertain mode of action, e. g. afidopyropen, azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, pyflubumide, or the compounds M.29.1 : 4-[5-(3,5- Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro- ethylcarbamoyl)-methyl]-benzamide, or M.29.2: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5- (trifluoromethyl)-4H-isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-
1 - carboxamide, or M.29.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9- azadispiro[4.2.4.2]-tetradec-1 1 -en-10-one, or M.29.4: 3-(4'-fluoro-2,4-dimethylbiphenyl-3- yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, or M.29.5: 1 -[2-fluoro-4-methyl-5- [(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4-triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or M.29.6: a compound selected from M.29.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide; M.29.6c) (E/Z)-2,2,2-trifluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylide- ne]acetamide; M.29.6d) (E/Z)-N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2- trifluoro-acetamide; M.29.6f) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2- difluoro-acetamide; M.29.6g) (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2- pyridylidene]-2,2-difluoro-acetamide; M.29.6h) (E/Z)-N-[1 -[(2-chloropyrimidin-5-yl)methyl]-
2- pyridylidene]-2,2,2-trifluoro-acetamide and M.29.6i) (E/Z)-N-[1 -[(6-chloro-3- pyridyl)methyl]-2-pyridylidene]-2,2,3,3,3-pentafluoro-propanamide.); or of M.29.7: 3-[3- chloro-5-(trifluoromethyl)phenyl]-4-oxo-1 -(pyrimidin-5-ylmethyl)pyrido[1 ,2-a]pyrimidin-1 - ium-2-olate; or M.29.8: 8-chloro-N-[2-chloro-5-methoxyphenyl)sulfonyl]-6-trifluoromethyl)- imidazo[1 ,2-a]pyridine-2-carboxamide; or M.29.9: 4-[5-(3,5-dichlorophenyl)-5- (trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 -oxothietan-3-yl)benzamide; or M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyloxy)phenoxy]propoxy]-1 H-pyrazole.
F.I) Respiration Inhibitors: F.I-1 ) Inhibitors of complex III at Qo site: strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim- methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chlorodincarb, trifloxystrobin, 2-[2-(2,5- dimethyl-phenoxymethyl)-phenyl]-3-methoxy-acrylic acid methyl ester and 2 (2-(3-(2,6- dichlorophenyl)-1 -methyl-allylideneaminooxymethyl)-phenyl)-2-methoxyimino-N methyl- acetamide; oxazolidinediones and imidazolinones: famoxadone, fenamidone; F.I-2) Inhibi- tors of complex II (e.g. carboxamides): carboxanilides: benodanil, bixafen, boscalid, car- boxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, me- pronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluzamide, tiadinil, 2-amino-4 methyl-thiazole-5-carboxanilide, N-(3',4',5' trifluorobiphenyl-2 yl)-3- difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-trifluoromethylthiobiphenyl-2- yl)-3 difluoromethyl-1 -methyl-1 H pyrazole-4-carboxamide, N-(2-(1 ,3,3-trimethyl-butyl)- phenyl)-1 ,3-dimethyl-5 fluoro-1 H-pyrazole-4 carboxamide, 3-(difluoromethyl)-1 -methyl-N- (1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 ,1 ,3- trimethylindan-4-yl)pyrazole-4-carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4- yl)pyrazole-4-carboxamide and 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide; F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom,
3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl-4,9-dioxo-8- (phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate; F.I-4) Other respiration inhibitors (complex I, uncouplers) diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam; nitro- phenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organo- metal compounds: fentin salts, such as fentin-acetate, fentin chloride, or fentin hydroxide; F.ll) Sterol biosynthesis inhibitors (SBI fungicides): F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles): triazoles: azaconazole, bitertanol, bromuconazole, cy- proconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbucona- zole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uni- conazole; imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole; pyrim- idines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, 1 -[rel-(2S;3R)-3-
(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H-[1 ,2,4]triazole, 2- [rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-2H-[1 ,2,4]triazole-3- thiol; F.II-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines): morpho- lines: aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketalamines: spiroxamine; F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides: fenhexamid;
F.lll) Nucleic acid synthesis inhibitors: F.III-1 ) RNA, DNA synthesis; phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl; isoxazoles and iosothiazolones: hymexazole, octhilinone; F.III-2) DNA topoisomerase inhibitors: oxolinic acid; F.III-3) Nucleotide metabolism (e.g. adenosin- deaminase), hydroxy (2-amino)-pyrimidines: bupirimate;
F.IV) Inhibitors of cell division and or cytoskeleton: F.IV-1 ) Tubulin inhibitors: benzimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate- methyl; triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 -yl)-6-(2,4,6-trifluorophenyl)- [1 ,2,4]triazolo[1 ,5 a]pyrimidine; F.IV-2) Other cell division inhibitors: benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide; F.IV-3) Actin inhibitors: benzophenones: metrafenone;
F.V) Inhibitors of amino acid and protein synthesis: F.V-1 ) Methionine synthesis inhibitors (ani- lino-pyrimidines): anilino-pyrimidines: cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
F.V-2) Protein synthesis inhibitors (anilino-pyrimidines); antibiotics: blasticidin-S, kasug- amycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors: F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino- pyrimidines); dicarboximides: fluoroimid, iprodione, procymidone, vinclozolin; phenyl- pyrroles: fenpiclonil, fludioxonil; F.VI-2) G protein inhibitors: quinolines: quinoxyfen;
F.VI I) Lipid and membrane synthesis inhibitors: F.VI 1-1 ) Phospholipid biosynthesis inhibitors: organophosphorus compounds: edifenphos, iprobenfos, pyrazophos; dithiolanes: isopro- thiolane; F.VII-2) Lipid peroxidation: aromatic hydrocarbons: dicloran, quintozene, tec- nazene, tolclofos-methyl, biphenyl, chloroneb, etridiazole; F.VII-3) Carboxyl acid amides
(CAA fungicides); cinnamic or mandelic acid amides: dimethomorph, flumorph, mandi- proamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4-cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4- fluorophenyl) ester; F.VII-4) Compounds affecting cell membrane permeability and fatty acids: oxathiapiprolin, carbamates: propamocarb, propamocarb-hydrochlorid,
F.VIII) Inhibitors with Multi Site Action: F.VIII-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VI 11- 2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, me- tiram, propineb, thiram, zineb, ziram; F.VIII-3) Organochlorine compounds (e.g.
phthalimides, sulfamides, chloronitriles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorophenole and its salts, phthalide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl- benzenesulfonamide; F.VIII-4) Guanidines and other: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminoctadine- tris(albesilate), 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole-1 ,3,5,7(2H,6H)- tetraone; F.VIII-5) Ahtraquinones: dithianon;
F.IX) Cell wall synthesis inhibitors: F.IX-1 ) Inhibitors of glucan synthesis: validamycin, polyoxin B; F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, carpropamide, dicyclomet, fenoxanil;
F.X) Plant defence inducers: F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl; F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium; phosphonates: fosetyl, fosetyl- aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, flumetover, flusulfamide, flutianil, methasulfocarb, oxin-copper, proquinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one, N-(cyclopropylmethoxyimino-(6- difluoro-methoxy-2,3-difluoro-phenyl)-methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3- trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4- fluoro-3-trifluoromethyl-phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'- (2-methyl-5-trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-met formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl- N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-dimethyl-quinolin-4-yl ester, and 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine, pyrisoxazole, 5- amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro-pyrazole-1 carbothioic acid S-allyl ester,
N-(6-methoxy-pyridin-3-yl) cyclopropanecarboxylic acid amide, 5-chloro-1 (4,6-dimethoxy- pyrimidin-2-yl)-2-methyl-1 H-benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy- phenyl)-isoxazol-5-yl]-2-prop-2-ynyloxy-acetamide;
F.XI) Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassino- lide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, damino- zide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthi- acet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, tria- penthenol, tributyl phosphorotrithioate, 2,3,5 tri iodobenzoic acid, trinexapac-ethyl and uniconazole;
F.XI I) Biological control agents: antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 (e.g. Rhapsody®, Serenade® MAX and Serenade® ASO from AgraQuest, Inc., USA.), Bacillus pumilus strain with NRRL No. B-30087 (e.g. Sonata® and Ballad® Plus from AgraQuest, Inc., USA), Ulocladium oudemansii (e.g. the product Botry-Zen from
BotriZen Ltd., New Zealand), Chitosan (e.g. Armour-Zen from BotriZen Ltd., New Zealand).
The commercially available compounds of the group M listed above may be found in The Pes- ticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.
The quinoline derivative flometoquin is shown in WO 06/013896. The aminofuranone compounds flupyradifurone is known from WO 07/1 15644. The sulfoximine compound sulfoxaflor is known from WO 07/149134. The pyrethroid momfluorothrin is known from US 6908945. The pyrazole acaricide pyflubumide is known from WO 07/020986. The isoxazoline compounds have been described likewise M.29.1 in WO 05/085216, M.29.2. in WO 09/002809 and in WO201 1/149749 and the isoxazoline M.29.9 in WO 13/050317. The pyripyropene derivative afidopyropen has been described in WO 06/129714. The spiroketal-substituted cyclic ketoenol derivative M.29.3 is known from WO 06/089633 and the biphenyl-substituted spirocyclic ke- toenol derivative M.29.4 from WO 08/06791 1 . Finally triazoylphenylsulfide like M.29.5 have been described in WO 06/043635 and biological control agents on basis of bacillus firmus in WO 09/124707. The neonicotionids 4A.1 is known from WO 120/069266 and WO 1 1/06946, the M.4.A.2 from WO 13/003977, the M4.A.3.from WO 10/069266.
The Metaflumizone analogue M.22C is described in CN 10171577. The phthalamides M.28.1 and M.28.2 are both known from WO 07/101540. The anthranilamide M.28.3 has been described in WO 05/077934. The hydrazide compound M.28.4 has been described in WO
07/043677. The anthranilamides M.28.5a) to M.28.5h) can be prepared as described in WO 07/006670, WO 13/024009 and WO 13/024010, the anthranilamide M.28.5i) is described in WO 1 1/085575, the M.28.5j) in WO 08/134969, the M.28.5k) in US 201 1/046186 and the M.28.5I) in WO 12/034403. The diamide compounds M.28.6 and M.28.7 can be found in CN102613183.
The compounds M.29.6a) to Μ.29.6Ϊ) listed in M.29.6 have been described in WO 12/029672. The mesoionic antagonist compound M.29.7 was described in WO 12/0921 15, the nematicide M.29.8 in WO 13/055584 and the Pyridalyl-type analogue M.29.10 in WO 10/060379.
Further especially preferred embodiments of the invention are pesticidal combinations wherein in each case the pyrazole compound A selected from compounds of formula I as defined in the outset, and especially those compounds preferred.
One embodiment of the invention relates to pesticidal mixtures of at least a compound of formula I with at least one compound B from the groups M.1 to M.29.
A preferred embodiment of the invention relates to pesticidal mixtures of a compound of formula I with one compound B from the groups M.1 to M.29.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.1.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.2.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.3.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.4.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.5.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.6.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.7.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.8.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.9.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.10.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.1 1.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.12.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.13.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.14.
A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.15. A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group M.16.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.17.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.18.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.19.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.20.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.21 .
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.22.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.23.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.24.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.25.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.26.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.27.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.28.
A further embodiment of relates to mixtures of a compound of the formula with at least one active compound B selected from the group M.29. Binary mixtures of a compound of formula I and a compound B selected from a group M.1 to M.29 are one preferred embodiment of the invention.
Ternary mixtures of a compound of formula I and two compounds B from one or two groups M.1 to M.29 are another preferred embodiment of the invention.
With respect to their use in the pesticidal mixtures of the present invention, particular prefer- ence is given to the compounds B from the groups M.1 to M.29 as listed in the paragraphs below:
The compound B selected from group M.2 as defined above is preferably ethiprole or fipronil, particularly fipronil.
The compound B selected from group M.3 as defined above is preferably acrinathrin, bifen- thrin, cyfluthrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin, beta-cypermethrin, zeta- cypermethrin, deltamethrin, esfenvalerate, etofenprox, fenpropathrin, flucythrinate, tau- fluvalinate, silafluofen or tralomethrin.
The compound B selected from group M.4 as defined above is preferably acetamiprid, clothi- anidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram or thiacloprid. The compound B selected from group M.6 as defined above is preferably abamectin, emamectin benzoate or lepimectin.
The compound B selected from group M.9 as defined above is preferably flonicamid or pymet- rozine.
The compound B selected from group M.13 as defined above is preferably chlorfenapyr.
The compound B selected from group M.23 as defined above is preferably spiromesifen, spirotetramat, or flubendiamide.
The compound B selected from group M.28 as defined above is preferably chloranthraniliprole (rynaxypyr) or cyantraniliprole.
The compound B selected from group M.29 as defined above is preferably flupyradifurone, pyrifluquinazon, sulfoxaflor or afidopyropen.
A particular group of embodiments of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group consisting of fipronil, alpha-cyper- methrin, thiamethoxam, abamectin, spirotetramat, imidacloprid, flonicamid, chloranthraniliprole, pymetrozine, sulfoxaflor and afidopyropen.
Especially preferred are inventive mixtures wherein the compound B is fipronil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is alpha-cypermethrin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is thiamethoxam and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is abamectin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is spirotetramat and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is imidacloprid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is flonicamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is chloranthraniliprole (rynaxypyr) and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is pymetrozine and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is sulfoxaflor and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is afidopyropen and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
A further embodiment of the invention relates to mixtures of at least a compound of formula I with at least one compound B from one or more groups F.1 to F.1 1.
Binary mixtures of a compound of formula I and a compound B from a group F.1 to F.1 1 are one preferred embodiment of the invention.
Ternary mixtures of a compound of formula I and two compounds B from one or two groups F.1 to F.1 1 are another preferred embodiment of the invention. Ternary mixtures of a compound of formula I and a compound B selected from each one group M.1 to M.29 and F.1 to F.1 1 are another preferred embodiment of the invention.
A further embodiment of the invention relates to an agricultural composition comprising a compound of formula I, particularly as defined in Tables 1 to 60 and Table I, and one compound B selected from the groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18, M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI.
A further embodiment of the invention relates to an agricultural composition comprising a compound of formula I, particularly as defined in Tables 1 to 60 and Table I, one compound B selected from the groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18, M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, and one compound selected from the groups F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI. A further embodiment of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 a), preferably from azoxystrobin, pyraclostrobin, fluoxastrobin, picoxystrobin, and trifloxystrobin.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group of the F.1 b), preferably cyazofamid.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 c), preferably from boscalid, fluopyram, fluxapy- roxad, penthiopyrad, and sedaxane.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 d), preferably selected from silthiofam and ametoc- tradin.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.2a), preferably from difenoconazole, epoxiconazole, fluquinconazole, ipconazole, prothioconazole, tebuconazole, triticonazole, and prochloraz.
A further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.2b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.2c), preferably fenhexamid.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.3a), preferably from metalaxyl, and metalaxyl-M. A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.3b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.4a), preferably from carbendazim, and thiophanate- methyl.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.4b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.5a), preferably selected from cyprodinil and pyrime- thanil. A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.5b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.6a), preferably iprodione.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.6b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.7a).
A further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.7b).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.7c), preferably selected from benthiavalicarb and iprovalicarb.
A further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.7d).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8a).
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8b), preferably selected from thiram and mancozeb. A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8c), preferably chlorothalonil.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.8d).
A further embodiment relates to mixtures of a compound of the formula I with at least one ac- tive compound B selected from the group F.9.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.10.
A further embodiment relates to mixtures of a compound of the formula I with at least one active compound B selected from the group F.1 1 of fungicides of unknown mode of action.
A particular group of embodiments of relates to mixtures of a compound of the formula I with at least one active compound B selected from the group consisting of azoxystrobin, fluoxastro- bin, picoxystrobin, pyraclostrobin, trifloxystrobin, fluxapyroxad, benthiavalicarb, iprovalicarb, fenhexamid, boscalid, mancozeb, ametoctradin, metalalxyl-m, pyrimethanil, cyprodinil, car- bendazim, iprodion, cyazofamid, prochloraz, chlorothalonil, penthiopyrad, difenoconazole, epox- iconazole, ipconazole, prothioconazole, and tebuconazole.
Especially preferred are inventive mixtures wherein the compound B is azoxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is fluoxastrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is picoxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is pyraclostrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I. Especially preferred are inventive mixtures wherein the compound B is trifloxystrobin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is fluoxapyroxad and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is benthiavalicarb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is iprovalicarb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is fenhexamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is boscalid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is mancozeb and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is ametoctradin and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is metalalxyl-m and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is pyrimethanil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is cyprodinil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is carbendazim and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is iprodion and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is cyazofamid and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is prochloraz and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is chlorothalonil and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is penthiopyrad and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is difenoconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is epoxiconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is ipconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is prothioconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I.
Especially preferred are inventive mixtures wherein the compound B is tebuconazole and the compound I of formula I is a compound of Tables 1 to 60, and Table I. The following table M-l represents preferred combinations of the active compounds I of formula I as defined in Tables 1 to 60, and Table I, and the active compounds B in mixtures according to the invention. In each of the mixtures M.1 to M.74 the component I is one compound of for- mula I specifically disclosed in the specification ("Compound XX").
Table M-l:
No. Comp. I Comp. B
M.1 XX acrinathrin
M.2 XX bifenthrin
M.3 XX cyfluthrin
M.4 XX lambda-cyhalothrin
M.5 XX cypermethrin
M.6 XX alpha-cypermethrin
M.7 XX beta-cypermethrin
M.8 XX zeta-cypermethrin
M.9 XX deltamethrin
M.10 XX esfenvalerate
M.1 1 XX etofenprox
M.12 XX fenpropathrin
M.13 XX flucythrinate
M.14 XX tau-fluvalinate
M.15 XX silafluofen
M.16 XX tralomethrin
M.17 XX acetamiprid
M.18 XX clothianidin
M.19 XX dinotefuran
Figure imgf000043_0001
M.20 XX imidacloprid
M.21 XX thiamethoxam
The following table M-F represents preferred combinations of the active compounds I of for- mula I as defined in Tables 1 to 60, and Table I, and the active compounds B of groups F.1 to F.1 1 in mixtures according to the invention:
Table M-F:
No. Comp. I Comp. B No. Comp. I Comp. B
M.41 XX pyraclostrobin M.54 XX epoxiconazol
M.42 XX trifloxystrobin M.55 XX difenoconazol
M.43 XX fluoxastrobin M.56 XX ipconazole
M.44 XX picoxystrobin M.57 XX prothioconazole
M.45 XX azoxystrobin M.58 XX tebuconazole
M.46 XX cyazofamid M.59 XX fluquinconazole
M.47 XX boscalid M.60 XX triticonazole
M.48 XX fluopyram M.61 XX prochloraz
M.49 XX fluxapyroxad M.62 XX fenhexamid
M.50 XX penthiopyrad M.63 XX metalaxyl
M.51 XX sedaxane M.64 XX metalaxyl-M
M.52 XX silthiofam M.65 XX carbendazim
M.53 XX ametoctradin M.66 XX thiophanate-methyl No. Comp. I Comp. B No. Comp. I Comp. B
M.67 XX cyprodinil M.72 XX thiram
M.68 XX pyrimethanil M.73 XX mancozeb
M.69 XX iprodione M.74 XX chlorothalonil
M.70 XX benthiavalicarb
M.71 XX iprovalicarb
The mixtures of the present invention have excellent activity against a broad spectrum of phytopathogenic fungi and animal pests.
The inventive compounds and the mixtures of the present invention have excellent activity against a broad spectrum of animal pests.
They are in particular suitable for efficiently controlling invertebrate pests. Particularier, they are suitable for efficiently controlling arthropodal pests such as arachnids, myriapedes and insects as well as nematodes.
The mixtures of at least a compound of formula I and a fungicidal compound have excellent activity against a broad spectrum of phytopathogenic fungi Ascomycetes, Basidiomycetes, Deu- teromycetes and Peronosporomycetes (syn. Oomycetes). Some of them are systemically effective and can be employed in crop protection as foliar fungicides, as fungicides for seed dressing and as soil fungicides. They can also be used for treating seed.
They are particularly important in the control of a multitude of fungi on various cultivated plants, such as wheat, rye, barley, oats, rice, corn, lawns, bananas, cotton, soybean, coffee, sugar cane, grapevines, fruits and ornamental plants, and vegetables such as cucumbers, beans, tomatoes, potatoes and cucurbits, and on the seeds of these plants.
They are especially suitable for controlling the following plant diseases:
Alternaria species on vegetables, oilseed rape, sugar beet and fruit and rice, for example, A. solani or A. alternata on potatoes and tomatoes;
Aphanomyces species on sugar beet and vegetables;
- Ascochyta species on cereals and vegetables;
Bipolaris and Drechslera species on corn, cereals, rice and lawns, for example, D. maydis on corn;
Blumeria graminis (powdery mildew) on cereals;
Botrytis cinerea (gray mold) on strawberries, vegetables, flowers and grapevines;
- Bremia lactucae on lettuce;
Cercospora species on corn, soybeans, rice and sugar beet;
Cochliobolus species on corn, cereals, rice, for example Cochliobolus sativus on cereals, Cochliobolus miyabeanus on rice;
Colletotricum species on soybeans and cotton;
- Drechslera species, Pyrenophora species on corn, cereals, rice and lawns, for example, D. teres on barley or D. tritici-repentis on wheat;
Esca on grapevines, caused by Phaeoacremonium chlamydosporium, Ph. Aleophilum and Formitipora punctata (syn. Phellinus punctatus);
Exserohilum species on corn;
Erysiphe cichoracearum and Sphaerotheca fuliginea on cucumbers;
Fusarium and Verticillium species on various plants, for example, F. graminearum or F. culmorum on cereals or F. oxysporum on a multitude of plants, such as, for example, tomatoes;
Gaeumanomyces graminis on cereals;
Gibberella species on cereals and rice (for example Gibberella fujikuroi on rice ;
Grainstaining complex on rice;
Helminthosporium species on corn and rice;
Michrodochium nivale on cereals;
Mycosphaerella species on cereals, bananas and peanuts, for
example, M. graminicola on wheat or M.fijiensis on bananas;
Peronospora species on cabbage and bulbous plants, for example, P. brassicae on cabbage or P. destructor on onions;
Phakopsara pachyrhizi and Phakopsara meibomiae on soybeans;
Phomopsis species on soybeans and sunflowers;
Phytophthora infestans on potatoes and tomatoes;
Phytophthora species on various plants, for example, P. capsici on bell pepper;
Plasmopara viticola on grapevines;
Podosphaera leucotricha on apples;
Pseudocercosporella herpotrichoides on cereals;
Pseudoperonospora on various plants, for example, P. cubensis on cucumber or P. humili on hops;
Puccinia species on various plants, for example, P. triticina, P. striformins,
P. hordei or P.graminis on cereals or P. asparagi on asparagus;
Pyricularia oryzae, Corticium sasakii, Sarocladium oryzae, S.attenuatum,
Entyloma oryzae on rice;
Pyricularia grisea on lawns and cereals;
Pythium spp. on lawns, rice, corn, cotton, oilseed rape, sunflowers, sugar beet, vegetables and other plants, for example, P. ultiumum on various plants,
P. aphanidermatum on lawns;
Rhizoctonia species on cotton, rice, potatoes, lawns, corn, oilseed rape, sugar beet, vegetables and on various plants, for example, R. solani on beet and various plants;
Rhynchosporium secalis on barley, rye and triticale;
Sclerotinia species on oilseed rape and sunflowers;
Septoria tritici and Stagonospora nodorum on wheat;
Erysiphe (syn. Uncinula) necator on grapevines;
Setospaeria species on corn and lawns;
Sphacelotheca reilinia on corn;
Thievaliopsis species on soybeans and cotton;
Tilletia species on cereals; Ustilago species on cereals, corn and sugar cane, for example, U. maydis on corn;
Venturia species (scab) on apples and pears, for example, V. inaequalis on apples.
The mixtures according to the invention are also suitable for controlling harmful fungi in the protection of materials (for example wood, paper, paint dispersions, fibers or fabrics) and in the protection of stored products. In the protection of wood, particular attention is paid to the following harmful fungi: Ascomycetes, such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.; Basidiomycetes, such as Coniophora spp., Coriolus spp., Gloeophyllum spp., Lentinus spp., Pleurotus spp., Poria spp., Serpula spp. and Tyromyces spp., Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Altemaria spp., Paecilomy- ces spp. and Zygomycetes, such as Mucor spp., additionally in the protection of materials the following yeasts: Candida spp. and Saccharomyces cerevisae.
Moreover, the inventive mixtures are especially useful for the control of Lepidoptera, Coleop- tera, Diptera, Thysanoptera and Hemiptera.
In particular the inventive mixtures are useful for the control of Thysanoptera and Hemiptera, especially Hemiptera.
The mixtures according to the present invention can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compounds according to the invention.
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compounds by weight, preferably 0.1 to 40% by weight.
Examples
A. Preparation examples With appropriate modification of the starting materials, the procedures given in the synthesis description were used to obtain further compounds II. The compounds obtained in this manner are listed in the table that follows, together with physical data.
The products shown below were characterized by melting point determination, by NMR spectroscopy or by the masses ([m/z]) or retention time (RT; [min.]) determined by HPLC-MS or HPLC spectrometry.
HPLC-MS = high performance liquid chromatography-coupled mass spectrometry;
HPLC method 1 : Phenomenex Kinetex 1 .7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.50 minutes; 100% B 0.20 min; flow: 0.8-1 .Oml/min in 1.50 minutes at 60°C. MS: quadrupole elec- trospray ionization, 80 V (positive mode). HPLC method 2: Merck Chromolith SpeedROD RP-18e, 50 x 4,6mm; mobile phase: acetoni- trile + 0.1 % trifluoroacetic acid (TFA)/water + 0.1 % TFA, using a gradient of 5:95 to 100:0 over 5 minutes at 40°C, flow rate 1.8 ml/min. MS: quadrupole electrospray ionization, 80 V (positive mode). HPLC method 3: Phenomenex Kinetex 1 .7 μηι XB-C18 100A; 50 x 2.1 mm; mobile phase: A: water + 0.1 % trifluoroacetic acid (TFA); B: acetonitrile + 0.1 % TFA; gradient: 5-100% B in 1.25 minutes; 100% B 0.70 min; flow: 0.8-1.Oml/min in 1.50 minutes at 60°C. MS: quadrupole electrospray ionization, 80 V (positive mode). Example 1 : Preparation of 1 -(4-cyano-4-ethyl-cyclohexyl)-N-ethyl-5-methyl-N-pyridazin-4-yl- pyrazole-4-carboxamide (I-94):
A solution of 771 mg 1 -(4-cyano-4-ethyl-cyclohexyl)-5-methyl-pyrazole-4-carbonyl chloride in 5 ml THF was added dropwise to a solution of 339 mg N-ethylpyridazin-4-amine and 348 mg tri- ethylamine in 30 ml THF at 0°C. The mixture was stirred at room temperature for about 20 h, the solvent was evaporated and the residue was diluted with 70 ml. dichloromethane, washed twice with 0.1 N hydrochloric acid and once with water, dried over MgSC and evaporated. Purification by flash chromatography (CH2CI2/CH3OH 9:1 ) gave 685 mg of the title compound as a mixture of isomers. HPLC-MS: RT 0.856 min and 0.975, m/z [MH]+ 367.7
Example 2 - Preparation of N-ethyl-1 -[4-hydroxy-4-(trifluoromethyl)cyclohexyl]-5-methyl-N- pyridazin-4-yl-pyrazole-4-carboxamide (1-105):
A solution of 1 g of 1 -[4-hydroxy-4-(trifluoromethyl)cyclohexyl]-5-methyl-pyrazole-4-carboxylic acid in 30 ml dichloromethane was added to 527 mg N-ethylpyridazin-4-amine and 2 g PyBrop [Bromotripyrrolidinophosphonium hexafluorophosphate]. The mixture was cooled to 0°C and 1 .8 g N-ethyl-N-isopropyl-propan-2-amine were added dropwise. The resulting mixture was stirred at room temperature (20-25°C) overnight, diluted with dichloromethane, washed with 0.1 N hydrochloric acid, dried over MgSC and evaporated. Purification by flash chromatography (EtOAc/acetone, 100:0 -> 9:1 ) gave 406 mg of the title compound as a mixture of isomers. HPLC-MS: RT 0.783 min and 0.81 1 min, m/z [MH]+ 397.8
Figure imgf000047_0001
If not indicated otherwise the compounds were obtained as a mixture of isomers, HPLC-MS data are given for the major isomer.
Figure imgf000047_0002
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Figure imgf000052_0001
-Isomer 5 THF2 = tetrahydrofuran-2-yl DOA5 = 1 ,3-dioxan-5-yl
<B> cis: trans 80:20 THF3 = tetrahydrofuran-3-yD
<c) cis:trans 95:5 THP2 = tetrahydropyran-2-yl
<°) trans-lsomer THP4 = tetrahydropyran-4-yl
Biological exam
The activity of the compounds of formula I of the present invention could be demonstrated and evaluated in biological tests described in the following.
If not otherwise specified the test solutions were prepared as follows:
The active compound was dissolved at the desired concentration in a mixture of 1 :1 (vohvol) distilled water : aceton. The test solution was prepared at the day of use and in general at con- centrations of ppm (wt vol).
B.1 Cowpea aphid (Aphis craccivora)
Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population had been recorded. Population reduction was assessed after 24, 72, and 120 hours.
In this test, the compounds 1-1 , I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, 1-10, 1-1 1 , 1-12, 1-13, 1-14, 1-15, 1-16, 1-18, 1-19, I-20, 1-21 , I-24, I-25, I-26, I-28, I-30, 1-31 , I-32, I-33, I-34, I-35, I-36, I-37, I-38, I- 39, I-40, 1-41 , I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, 1-51 , I-52, I-53, I-54, I-55, I-56, I-57, I-58, I-60, 1-61 , I-66, I-68, I-70, 1-71 , I-72, I-73, I-74, I-75, I-76, I-77, I-79, I-80, 1-81 , I-82, I-83, I- 84, I-85, I-86, I-87, I-88, I-89, I-90, 1-91 , I-92, I-93, I-94, I-95, I-96, I-97, I-98, I-99, 1-100, 1-101 , I- 102, 1-103, 1-104, 1-105, 1-106, 1-107, 1-108, 1-109, 1-1 10, 1-1 1 1 , 1-1 12, 1-1 13, 1-1 14, 1-1 15, 1-1 16, 1-1 17, 1-1 18, 1-1 19, 1-120, 1-121 , 1-122, 1-123, 1-124, 1-125, 1-126, 1-127, 1-128, 1-129, 1-130, 1-131 , 1-132, 1-135, 1-136, 1-137, 1-138, 1-139, 1-140, 1-141 , 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151 , 1-152, 1-153, 1-154, 1-155, 1-156, 1-157, 1-158, 1-159, 1-160, 1-161 , and 1-162, respectively, at 300 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.2 Cotton aphid (Aphis gossypii, mixed life stages)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Cotton plants at the cotyledon stage were infested with aphids prior to treatment by placing a heavily infested leaf from the main aphid colony on top of each cotyledon. Aphids were allowed to transfer overnight to accomplish an infestation of 80-100 aphids per plant and the host leaf was removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed from the sprayer, and then maintained in a growth room under fluorescent light- ing in a 24-hr photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, the compounds 1-1 , I-5, I-6, I-8, I-9, 1-10, 1-1 1 , 1-13, 1-16, 1-18, 1-19, I-20, 1-21 , I-24, I-26, I-34, I-35, I-36, I-38, I-43, I-46, I-47, I-48, I-49, I-50, I-54, I-55, I-58, I-60, 1-61 , I-62, I-63, I- 64, I-65, I-66, I-67, I-68, I-69, I-76, I-77, 1-81 , I-82, I-84, I-85, I-94, I-97, I-98, I-99, 1-100, 1-101 , I- 102, 1-103, 1-104, 1-105, 1-106, 1-1 1 1 , 1-1 12, 1-1 14, 1-1 15, 1-129, 1-130, 1-131 , 1-135, 1-137, 1-140, 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151 , 1-152, 1-153, 1-154, 1-155, 1-156, 1-158, 1-159, 1-160, 1-161 , 1-162, 1-163, 1-164, 1-165, and 1-166, respectively, at 300 ppm showed a mortality of at least 75% in comparison with untreated controls. B.3 Silverleaf whitefly (Bemisia argentifolii, adult)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Cotton plants at the cotyledon stage (one plant per pot) were sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood and then removed from the sprayer. Each pot was placed into a plastic cup and 10 to 12 whitefly adults (approximately 3-5 days old) were introduced. The insects were collected using an aspirator and 0.6 cm, nontoxic Tygon® tubing (R-3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. Cups were covered with a reusable screened lid (150-micron mesh polyester screen Pe- Cap from Tetko, Inc.). Test plants were maintained in a growth room at 25°C and 20-40% rela- tive humidity for 3 days, avoiding direct exposure to fluorescent light (24 hour photoperiod) to prevent trapping of heat inside the cup. Mortality was assessed 3 days after treatment, compared to untreated control plants.
In this test, the compounds 1-1 , I-5, I-6, I-8, I-9, 1-10, 1-1 1 , 1-13, 1-16, 1-18, 1-19, I-20, 1-21 , I-24, I-26, I-34, I-35, I-36, I-37, I-38, I-39, I-42, I-43, I-46, I-47, I-48, I-49, I-50, I-54, I-55, I-58, I-60, I- 61 , I-62, I-63, I-64, I-65, I-66, I-67, I-68, I-69, I-76, I-77, I-78, I-79, 1-81 , I-82, I-84, I-85, I-87, I-94, I-97, I-98, I-99, 1-100, 1-101 , 1-102, 1-103, 1-104, 1-105, 1-106, 1-1 1 1 , 1-1 12, 1-1 14, 1-1 15, 1-129, I- 130, 1-132, 1-133, 1-134, 1-135, 1-136, 1-137, 1-138, 1-140, 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151 , 1-152, 1-153, 1-154, 1-155, 1-156, 1-157, 1-158, 1-159, 1-160, 1-161 , 1-162, 1-163, 1-164, 1-165, and 1-166, respectively, at 300 ppm showed a mortality of at least 75% in comparison with untreated controls. B.4 Vetch aphid (Megoura viciae)
The active compounds were formulated in 3:1 (vohvol) water : DMSO with different concentrations of formulated compounds.
Bean leaf disks were placed into microtiterplates filled with 0.8% agar-agar and 2.5 ppm OPUS™. The leaf disks were sprayed with 2.5 μΙ of the test solution and 5 to 8 adult aphids were placed into the microtiter plates which were then closed and kept at 23 ± 1 °C and 50 ± 5% relative humidity under fluorescent light for 6 days. Mortality was assessed on the basis of vital, reproduced aphids. Aphid mortality and fecundity was then visually assessed.
In this test, the compounds 1-1 , I-2, I-3, I-4, I-5, I-6, I-7, I-8, I-9, 1-10, 1-1 1 , 1-12, 1-13, 1-14, 1-15, 1-16, 1-17, 1-18, 1-19, I-20, I-23, I-24, I-25, I-26, I-27, I-28, I-29, I-30, 1-31 , I-32, I-33, I-34, I-35, I- 36, I-37, I-38, I-39, I-40, 1-41 , I-42, I-43, I-44, I-45, I-46, I-47, I-48, I-49, I-50, I-53, I-54, I-55, I-56, I-57, I-58, I-60, 1-61 , I-66, I-68, I-70, 1-71 , I-72, I-73, I-74, I-75, I-76, I-77, I-80, 1-81 , I-82, I-83, I- 83, I-85, I-86, I-87, I-88, I-89, I-90, 1-91 , I-92, I-93, I-94, I-95, I-97, I-98, I-99, 1-100, 1-101 , 1-102, 1-103, 1-104, 1-105, 1-106, 1-107, 1-108, 1-109, 1-1 10, 1-1 1 1 , 1-1 12, 1-1 13, 1-1 14, 1-1 15, 1-1 16, 1-1 17, 1-1 18, 1-1 19, 1-120, 1-121 , 1-122, 1-123, 1-124, 1-125, 1-126, 1-127, 1-128, 1-129, 1-130, 1-131 , 1-132, 1-135, 1-138, 1-139, 1-140, 1-141 , 1-142, 1-143, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151 , 1-152, 1-153, 1-154, 1-155, 1-156, 1-157, 1-158, 1-159, 1-160, 1-161 , 1-162, 1-163, 1-164, 1-165, 1-166, and I- 167, respectively, at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls. B.5 Green peach aphid (Myzus persicae)
The active compounds were formulated in cyclohexanone as a 10,000 ppm solution supplied in 1 .3 ml ABgene® tubes. These tubes were inserted into an automated electrostatic sprayer equipped with an atomizing nozzle and they served as stock solutions for which lower dilutions were made in 1 :1 (vohvol) water : aceton. A nonionic surfactant (Kinetic®) was included in the solution at a volume of 0.01 % (v/v).
Bell pepper plants at the first true-leaf stage were infested prior to treatment by placing heavily infested leaves from the main colony on top of the treatment plants. Aphids were allowed to transfer overnight to accomplish an infestation of 30-50 aphids per plant and the host leaves were removed. The infested plants were then sprayed by an automated electrostatic plant sprayer equipped with an atomizing spray nozzle. The plants were dried in the sprayer fume hood, removed, and then maintained in a growth room under fluorescent lighting in a 24 hour photoperiod at 25°C and 20-40% relative humidity. Aphid mortality on the treated plants, relative to mortality on untreated control plants, was determined after 5 days.
In this test, the compounds 1-1 , I-2, I-4, I-5, I-6, I-7, I-8, I-9, 1-10, 1-1 1 , 1-12, 1-13, 1-14, 1-15, 1-16, 1-18, 1-19, I-20, 1-21 , I-28, I-30, 1-31 , I-32, I-33, I-35, I-36, I-37, I-38, I-39, I-42, I-46, I-47, I-48, I- 49, I-50, I-52, I-54, I-55, I-58, I-60, 1-61 , I-62, I-63, I-64, I-65, I-66, I-67, I-68, I-69, I-76, I-77, 1-81 , I-82, I-84, I-85, I-97, I-98, I-99, 1-100, 1-101 , 1-102, 1-103, 1-104, 1-105, 1-106, 1-107, 1-108, 1-109, 1-1 10, 1-1 1 1 , 1-1 12, 1-1 14, 1-1 15, 1-1 17, 1-1 18, 1-1 19, 1-122, 1-123, 1-124, 1-125, 1-126, 1-127, 1-128, 1-129, 1-130, 1-133, 1-137, 1-140, 1-142, 1-143, 1-144, 1-145, 1-146, 1-147, 1-148, 1-149, 1-150, 1-151 , 1-152, 1-153, 1-154, 1-155, 1-156, 1-157, 1-158, 1-159, 1-160, 1-161 , 1-162, 1-163, 1-164, 1-165, and I- 166, respectively, at 10 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.6 Boll weevil (Anthonomus grandis)
The compounds were formulated in 3:1 (vohvol) water : DMSO.
For evaluating control of boll weevil (Anthonomus grandis) the test unit consisted of 24-well- microtiter plates containing an insect diet and 20-30 A. grandis eggs. Different concentrations of formulated compounds were sprayed onto the insect diet at 20 μΙ, using a custom built micro atomizer, at two replications. After application, the microtiter plates were incubated at 23 ± 1 °C and 50 ± 5 % relative humidity for 5 days. Egg and larval mortality was then visually assessed.
In this test, the compounds 1-14, I-49, I-57, I-58, I-68, I-87, I-88, I-97, I-98, I-99, 1-1 10, 1-1 1 1 , I- 121 , and 1-143, respectively, at 2500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.7 Rice plant hopper (Nilaparvata lugens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active compounds were formulated in 1 :1 (vohvol) water : aceton and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inoculated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compounds 1-14, I-30, I-70, I-73, I-90, I-92, 1-1 1 1 , 1-132, 1-140, 1-141 , 1-142, I- 143, 1-144, 1-145, 1-146, 1-147, 1-149, and 1-150, respectively, at 500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.8 Orchid thrips (Dichromothrips corbetti)
The active compounds were formulated as a 1 :1 (vohvol) water : aceton solution. Surfactant (Alkamuls EL 620) was added at the rate of 0.1 % (vol/vol). Vanda orchids petals were cleaned, washed and air dried prior to spraying. Petals were dipped into the test solution for 3 seconds, air dried, placed inside a resealable plastic and inoculated with 20 adults. The treated petals were kept inside the holding room at 28-29 °C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compounds I-8, I-9, 1-10, I-37, I-76, I-77, I-84, I-85, I-94, 1-100, 1-101 , 1-108, I- 1 12, 1-1 18, 1-129, 1-130, 1-135, 1-136, 1-140, 1-149, and 1-150, respectively, at 500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.9 Rice green leafhopper (Nephotettix virescens)
Rice seedlings were cleaned and washed 24 hours before spraying. The active corn-pounds were formulated in 1 :1 (vohvol) water : aceton, and 0.1 % vol/vol surfactant (EL 620) was added. Potted rice seedlings were sprayed with 5 ml test solution, air dried, placed in cages and inocu- lated with 10 adults. Treated rice plants were kept at 28-29°C and relative humidity of 50-60%. Percent mortality was recorded after 72 hours.
In this test, the compounds 1-10, I-46, I-49, I-70, I-72, I-73, I-74, I-90, I-92, I-97, 1-100, 1-1 1 1 , I- 139, 1-140, 1-141 , 1-142, 1-143, 1-145, 1-146, 1-148, 1-149, and 1-150, respectively, at 500 ppm showed a mortality of at least 75% in comparison with untreated controls.
B.10 Diamondback moth (Plutella xylostella)
The active compounds were formulated in 1 :1 (vohvol) water : aceton and 0.1 % (vol/vol) Al- kamuls EL 620 surfactant. A 6 cm leaf disk of cabbage leaves was dipped in the test solution for 3 seconds and allowed to air dry in a Petri plate lined with moist filter paper. The leaf disk was inoculated with 10 third instar larvae and kept at 25-27°C and 50-60% humidity for 3 days. Mortality was assessed after 72 h of treatment.
In this test, the compounds I-37, I-38, I-80, 1-100, 1-101 , 1-125, and 1-126, respectively, at 500 ppm showed a mortality of at least 75% in comparison with untreated controls.
The beneficial activity of the compounds according to the invention over structurally close compounds known from prior art was demonstrated by the following comparative experiments:
The tables show % mortality with the given concentration of active compounds in comparison to untreated controls.
Tests B.1 (Cowpea aphid)
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000057_0003
10
Figure imgf000057_0004
Figure imgf000057_0002
Tests B.3 (Silverleaf Whitefly)
Figure imgf000058_0003
Figure imgf000058_0001
Tests B.5 (Greenpeach Aphid)
Figure imgf000058_0004
Figure imgf000058_0002

Claims

Claims
Substituted pyrazole compounds of formula I
Figure imgf000059_0001
wherein
R1 is H, Ci-C2-alkyl, or Ci-C2-alkoxy-Ci-C2-alkyl;
R2 is CH3, or halomethyl;
R3 is H, F, CI, Br, CN, Ci-C2-alkyl, or halomethyl;
D is a 4- to 6-membered non-aromatic carbo- or heterocycle, which heterocycle may contain 1 or 2 heteroatoms selected from O, and S, wherein S may be oxidised, which carbo- or heterocycle is partially or fully substituted by R4;
R4 is halogen, OH, CN, N02, Ci-Cio-alkyl, Ci-C8-haloalkyl, Ci-C8-alkoxy, Ci-C8- haloalkoxy, or S(0)nRa, C3-C6-cycloalkyl, or 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N-Rb, O, and S, wherein S may be oxidized,
which R4 groups are unsubstituted or partially or fully substituted by Rc;
Ra is H, Ci-C4-alkyl, Ci-C2-haloalkyl, or C3-C6-cycloalkyl, which cycle may be partially or fully substituted by Rb, wherein Ra is not haloalkyl or unsubstituted cycloalkyl if D is a cycloalkyl or cycloalkenyl ring;
n is 0, 1 , or 2;
Rb is H, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkylcarbonyl, or Ci-C2-alkoxy- carbonyl;
Rc is halogen, OH, CN, N02, Ci-C4-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, Ci-C2-alkoxy, Ci-C2-haloalkoxy, or S(0)nRd;
Rd is H, Ci-C4-alkyl, Ci-C2-haloalkyl, or C3-C6-cycloalkyl, which cycle may be partially or fully substituted by Rb;
wherein two groups R4 connected to adjacent ring atoms may together form a 3- to 6- membered carbo- or heterocycle which heterocycle may contain 1 or 2 heteroatoms selected from N-Rb, O, and S, wherein S may be oxidised, which cycles may be partially or fully substituted by R4 radicals;
and the stereoisomers, salts, tautomers and N-oxides thereof.
The compounds of formula I according to claim 1 , wherein R1 is H, Ci-C2-alkyl, or Ci-C2- alkoxymethyl.
3. The compounds of formula I according to claim 1 or 2, wherein R1 is H, CH3, or C2H5.
4. The compounds of formula I as claimed in any of the preceding claims, wherein R2 is CH3, CHF2, or CF3.
5. The compounds of formula I as claimed in any of the preceding claims, wherein R3 is H. The compounds of formula I as claimed in any of the preceding claims, wherein D is a car- bocycle.
The compounds of formula I as claimed in any of the preceding claims, wherein D is a cy- cloalkyl ring.
The compounds of formula I as claimed in any of claims 1 to 4, wherein D is a saturated heterocyclic ring with one oxygen atom.
A composition comprising at least one compound according to any one of claims 1 to 8 and at least one inert liquid and/or solid carrier.
0. An agricultural composition for combating animal pests comprising at least one compound as defined in any of claims 1 to 8 and at least one inert liquid and/or solid acceptable carrier and, if desired, at least one surfactant.
1 . A composition according to claims 9 or 10, comprising at least one inert liquid and/or solid carrier, and
A) at least one compound of formula I according to any one of claims 1 to 8 and
B) at least one further compound B selected from the compounds of the following
groups M.1 , M.2, M.3, M.4, M.5, M.6, M.7, M.8, M.9, M.10, M.1 1 , M.12, M.13, M.14, M.15, M.16, M.17, M.18, M.19, M.20, M.21 , M.22, M.23, M.24, M.25, M.26, M.27, M.28, M.29, F.I, F.ll, F.lll, F.IV, F.V, F.VI, F.VII, F.VIII, F.IX, F.X and F.XI:
M.1 Acetylcholine esterase (AChE) inhibitors from the class of M.1A carbamates, e. g. aldicarb, alanycarb, bendiocarb, benfuracarb, butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathi- ocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, prop- oxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of M.1 B organophosphates, e. g. acephate, azamethiphos, azinphos- ethyl, azinphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, di- azinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur, fenamiphos, fenitrothion, fenthion, fosthiaza- te, heptenophos, imicyafos, isofenphos, isopropyl 0-(methoxyaminothio-phos- phoryl) salicylate, isoxathion, malathion, mecarbam, methamidophos, methida- thion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, para- thion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphami- don, phoxim, pirimiphos- methyl, profenofos, propetamphos, prothiofos, pyraclo- fos, pyridaphenthion, quinalphos, sulfotep, tebupirimfos, temephos, terbufos, tet- rachlorvinphos, thiometon, triazophos, trichlorfon, and vamidothion; M.2. GABA-gated chloride channel antagonists such as: M.2A cyclodiene organo- chlorine compounds, e. g. endosulfan, or chlordane; or M.2B fiproles (phenylpy- razoles), e. g. ethiprole, fipronil, flufiprole, pyrafluprole, and pyriprole;
M.3 Sodium channel modulators from the class of M.3A pyrethroids, e. g. acrina- thrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioal- lethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cypermethrin, alpha-cyper- methrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, meperfluthrin, metofluthrin, momfluorothrin, permethrin, phenothrin, prallethrin, profluthrin, pyre- thrin (pyrethrum), resmethrin, silafluofen, tefluthrin, tetramethylfluthrin, tetrame- thrin, tralomethrin and transfluthrin; or M.3B sodium channel modulators, such as DDT, or methoxychlor;
M.4 Nicotinic acetylcholine receptor agonists (nAChR) from the class of M.4A neon- icotinoids, e. g. acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid, and thiamethoxam; or the compounds M.4A.1 : 1 -[(6-chloro-3-pyridi- nyl)methyl]-2,3,5,6,7,8-hexahydro-9-nitro-(5S,8R)-5,8-Epoxy-1 H-imidazo[1 ,2- a]azepine; or M.4A.2: 1 -[(6-chloro-3-pyridyl)methyl]-2-nitro-1 -[(E)-pentylidene- amino]guanidine; or M4.A.3: 1 -[(6-chloro-3-pyridyl)methyl]-7-methyl-8-nitro-5- propoxy-3,5,6,7-tetrahydro-2H-imidazo[1 ,2-a]pyridine; or M.4B nicotine;
M.5 Nicotinic acetylcholine receptor allosteric activators from the class of spinosyns, e. g. spinosad or spinetoram;
M.6 Chloride channel activators from the class of avermectins and milbemycins, e. g. abamectin, emamectin benzoate, ivermectin, lepimectin, or milbemectin;
M.7 Juvenile hormone mimics, such as M.7A juvenile hormone analogues as hydro- prene, kinoprene and methoprene; or others, as M.7B fenoxycarb, or M.7C pyriproxyfen;
M.8 miscellaneous non-specific (multi-site) inhibitors, e. g. M.8A alkyl halides as me- thyl bromide and other alkyl halides, or M.8B chloropicrin, or M.8C sulfuryl fluoride, or M.8D borax, or M.8E tartar emetic;
M.9 Selective homopteran feeding blockers, e. g. M.9B pymetrozine, or M.9C floni- camid;
M.10 Mite growth inhibitors, e. g. M.1 OA clofentezine, hexythiazox and diflovidazin, or M.10B etoxazole;
M.1 1 Microbial disruptors of insect midgut membranes, e. g. bacillus thuringiensis or bacillus sphaericus and the insecticdal proteins they produce such as bacillus thuringiensis subsp. israelensis, bacillus sphaericus, bacillus thuringiensis subsp. aizawai, bacillus thuringiensis subsp. kurstaki and bacillus thuringiensis subsp. tenebrionis, or the Bt crop proteins: Cry1 Ab, Cry1 Ac, Cry1 Fa, Cry2Ab, mCry3A,
Cry3Ab, Cry3Bb and Cry34/35Ab1 ; M.12 Inhibitors of mitochondrial ATP synthase, e. g. M.12A diafenthiuron, or M.12B organotin miticides such as azocyclotin, cyhexatin, or fenbutatin oxide, or M.12C propargite, or M.12D tetradifon;
M.13 Uncouplers of oxidative phosphorylation via disruption of the proton gradient, e. g. chlorfenapyr, DNOC, or sulfluramid;
M.14 Nicotinic acetylcholine receptor (nAChR) channel blockers, e. g. nereistoxin analogues as bensultap, cartap hydrochloride, thiocyclam, or thiosultap sodium; M.15 Inhibitors of the chitin biosynthesis type 0, such as benzoylureas, e.g. bistriflu- ron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron, or triflumuron;
M.16 Inhibitors of the chitin biosynthesis type 1 , e. g. buprofezin;
M.17 Moulting disruptors, Dipteran, e. g. cyromazine;
M.18 Ecdyson receptor agonists such as diacylhydrazines, e. g. methoxyfenozide, tebufenozide, halofenozide, fufenozide, or chromafenozide;
M.19 Octopamin receptor agonists, e. g. amitraz;
M.20 Mitochondrial complex III electron transport inhibitors, e. g. M.20A hydrame- thylnon, or M.20B acequinocyl, or M.20C fluacrypyrim;
M.21 Mitochondrial complex I electron transport inhibitors, e. g. M.21A METI acari- cides, and insecticides such as fenazaquin, fenpyroximate, pyrimidifen, pyrida- ben, tebufenpyrad or tolfenpyrad, or M.21 B rotenone;
M.22 Voltage-dependent sodium channel blockers, e. g. M.22A indoxacarb, or
M.22B metaflumizone, or M.22C 1 -[(E)-[2-(4-cyanophenyl)-1 -[3-
(trifluoromethyl)phenyl]ethylidene]amino]-3-[4-(difluoromethoxy)phenyl]urea; M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, e. g. spirodiclofen, spiromesifen, or spirotetramat;
M.24 Mitochondrial complex IV electron transport inhibitors, e. g. M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or M.24B cyanide;
M.25 Mitochondrial complex II electron transport inhibitors, such as beta-ketonitrile derivatives, e. g. cyenopyrafen, or cyflumetofen;
M.28 Ryanodine receptor-modulators from the class of diamides, e. g. flubendiami- de, chlorantraniliprole (rynaxypyr®), cyantraniliprole (cyazypyr®), or the phthal- amide compounds M.28.1 : (R)-3-Chlor-N 1 -{2-methyl-4-[1 ,2,2,2 -tetrafluoro-1 -(tri- fluoromethyl)ethyl]phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, and M.28.2: (S)-3-Chloro-N1 -{2-methyl-4-[1 ,2,2,2 -tetrafluoro-1 -(trifluoromethyl)ethyl] phenyl}-N2-(1 -methyl-2-methylsulfonylethyl)phthalamid, or M.28.3: 3-bromo-N-{2- bromo-4-chloro-6-[(1 -cyclopropylethyl)carbamoyl]phenyl}-1 -(3-chlorpyridin-2-yl)- 1 H-pyrazole-5-carboxamide (proposed ISO name: cyclaniliprole), or M.28.4: me- thyl-2-[3,5-dibromo-2-({[3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5-yl]carbo- nyl}amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate; or a compound selected from M.28.5a) to M.28.5I): M.28.5a) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfa- nylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3- carboxamide; M.28.5b) N-[4-chloro-2-[(diethyl-lambda-4-sulfanylidene)carbamo- yl]-6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbox- amide; M.28.5c) N-[4-chloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]- 6-methyl-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carbox- amide; M.28.5d) N-[4,6-dichloro-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamo- yl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5e) N-[4,6-dichloro-2-[(diethyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]- 2-(3-chloro-2-pyridyl)-5-(difluoromethyl)pyrazole-3-carboxamide; M.28.5f) N-[4,6- dibromo-2-[(di-2-propyl-lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2- pyridyl)-5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5g) N-[4-chloro-2-[(di-2- propyl-lambda-4-sulfanylidene)carbamoyl]-6-cyano-phenyl]-2-(3-chloro-2-pyridyl)- 5-(trifluoromethyl)pyrazole-3-carboxamide; M.28.5h) N-[4,6-dibromo-2-[(diethyl- lambda-4-sulfanylidene)carbamoyl]-phenyl]-2-(3-chloro-2-pyridyl)-5-(trifluoro- methyl)pyrazole-3-carboxamide; M.28.5i) N-[2-(5-amino-1 ,3,4-thiadiazol-2-yl)-4- chloro-6-methyl-phenyl]-5-bromo-2-(3-chloro-2-pyridyl)pyrazole-3-carboxarriide; M.28.5j) 5-chloro-2-(3-chloro-2-pyridyl)-N-[2,4-dichloro-6-[(1 -cyano-1 -methyl- ethyl)carbamoyl]phenyl]pyrazole-3-carboxamide; M.28.5k) 5-bromo-N-[2,4-di- chloro-6-(methylcarbamoyl)phenyl]-2-(3,5-dichloro-2-pyridyl)pyrazole-3-carbox- amide; M.28.5I) N-[2-(tert-butylcarbamoyl)-4-chloro-6-methyl-phenyl]-2-(3-chloro- 2-pyridyl)-5-(fluoromethoxy)pyrazole-3-carboxamide; or a compound selected from M.28.6 N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphenyl)-3-iodo-phthal- amide; or M.28.7 3-chloro-N2-(1 -cyano-1 -methyl-ethyl)-N1 -(2,4-dimethylphe- nyl)phthalamide;
9 insecticidal active compounds of unknown or uncertain mode of action, e. g. afidopyropen, azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropy- late, chinomethionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flu- pyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, pyflubu- mide, or the compounds M.29.1 : 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5- dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-benz- amide, or M.29.2: 4-[5-[3-chloro-5-(trifluoromethyl)phenyl]-5-(trifluoromethyl)-4H- isoxazol-3-yl]-N-[2-oxo-2-(2,2,2-trifluoroethylamino)ethyl]naphthalene-1 -carbox- amide, or M.29.3: 1 1 -(4-chloro-2,6-dimethylphenyl)-12-hydroxy-1 ,4-dioxa-9-aza- dispiro[4.2.4.2]-tetradec-1 1 -en-10-one, or M.29.4: 3-(4'-fluoro-2,4-dimethylbi- phenyl-3-yl)-4-hydroxy-8-oxa-1 -azaspiro[4.5]dec-3-en-2-one, or M.29.5: 1 -[2- fluoro-4-methyl-5-[(2,2,2-trifluoroethyl)sulfinyl]phenyl]-3-(trifluoromethyl)-1 H-1 ,2,4- triazole-5-amine, or actives on basis of bacillus firmus (Votivo, 1-1582); or M.29.6: a compound selected from M.29.6a) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-py- ridylidene]-2,2,2-trifluoro-acetamide; M.29.6b) (E/Z)-N-[1 -[(6-chloro-5-fluoro-3-py- ridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide; M.29.6c) (E/Z)-2,2,2-tri- fluoro-N-[1 -[(6-fluoro-3-pyridyl)methyl]-2-pyridylidene]acetamide; M.29.6d) (E/Z)- N-[1 -[(6-bromo-3-pyridyl)methyl]-2-pyridylidene]-2,2,2-trifluoro-acetamide;
M.29.6e) (E/Z)-N-[1 -[1 -(6-chloro-3-pyridyl)ethyl]-2-pyridylidene]-2,2,2-trifluoro- acetamide; M.29.6f) (E/Z)-N-[1 -[(6-chloro-3-pyridyl)methyl]-2-pyridylidene]-2,2- difluoro-acetamide; M.29.6g) (E/Z)-2-chloro-N-[1 -[(6-chloro-3-pyridyl)methyl]-2- pyridylidene]-2,2-difluoro-acetamide; M.29.6h) (E/Z)-N-[1 -[(2-chloropyrimidin-5- yl)methyl]-2-pyndylidene]-2,2,2-trifluoro-acetamide and Μ.29.6Ϊ) (E/Z)-N-[1 -[(6- chloro-3-pyndyl)methyl]-2-pyndylidene]-2,2,3,3,3-pentafluoro-propanamide.); or of M.29.7: 3-[3-chloro-5-(trifluoromethyl)phenyl]-4-oxo-1 -(pyrimidin-5-ylmethyl)py- rido[1 ,2-a]pyrimidin-1 -ium-2-olate; or M.29.8: 8-chloro-N-[2-chloro-5-methoxyphe- nyl)sulfonyl]-6-trifluoromethyl)-imidazo[1 ,2-a]pyridine-2-carboxamide; or M.29.9: 4-[5-(3,5-dichlorophenyl)-5-(trifluoromethyl)-4H-isoxazol-3-yl]-2-methyl-N-(1 -oxo- thietan-3-yl)benzamide; or M.29.10: 5-[3-[2,6-dichloro-4-(3,3-dichloroallyl- oxy)phenoxy]propoxy]-1 H-pyrazole.
F.I) Respiration Inhibitors: F.I-1 ) Inhibitors of complex III at Qo site: strobilurins: azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, enestroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, py- raclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chloro- dincarb, trifloxystrobin, 2-[2-(2,5-dimethyl-phenoxymethyl)-phenyl]-3-methoxy- acrylic acid methyl ester and 2 (2-(3-(2,6-dichlorophenyl)-1 -methyl-allylidene- aminooxymethyl)-phenyl)-2-methoxyimino-N methyl-acetamide; oxazolidinedi- ones and imidazolinones: famoxadone, fenamidone; F.I-2) Inhibitors of complex II (e.g. carboxamides): carboxanilides: benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopyram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, oxycarboxin, penflufen, penthiopyrad, sedaxane, tecloftalam, thifluza- mide, tiadinil, 2-amino-4 methyl-thiazole-5-carboxanilide, N-(3',4',5' trifluorobi- phenyl-2 yl)-3-difluoromethyl-1 -methyl-1 H-pyrazole-4 carboxamide, N-(4'-triflu- oromethylthiobiphenyl-2-yl)-3 difluoromethyl-1 -methyl-1 H pyrazole-4-carboxami- de, N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1 ,3-dimethyl-5 fluoro-1 H-pyrazole-4 carboxamide, 3-(difluoromethyl)-1 -methyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide, 3-(trifluoromethyl)-1 -methyl-N-(1 , 1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide, 1 ,3-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carboxamide, 3-(trifluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carbox- amide, 3-(difluoromethyl)-1 ,5-dimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4- carboxamide and 1 ,3,5-trimethyl-N-(1 ,1 ,3-trimethylindan-4-yl)pyrazole-4-carbox- amide; F.I-3) Inhibitors of complex III at Qi site: cyazofamid, amisulbrom, 3S,6S,7R,8R)-3-[[(3-hydroxy-4-methoxy-2-pyridinyl)carbonyl]amino]-6-methyl- 4,9-dioxo-8-(phenylmethyl)-1 ,5-dioxonan-7-yl 2-methylpropanoate; F.I-4) Other respiration inhibitors (complex I, uncouplers) diflumetorim; tecnazen; ferimzone; ametoctradin; silthiofam; nitrophenyl derivates: binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fen- tin-acetate, fentin chloride, or fentin hydroxide;
F.ll) Sterol biosynthesis inhibitors (SBI fungicides): F.II-1 ) C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles): triazoles: azaconazole, biterta- nol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole- M, epoxiconazole, fenbuconazole, fluquinconazole, flusilazole, flutriafol, hexa- conazole, imibenconazole, ipconazole, metconazole, myclobutanil, paclobutra- zole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; imidazoles: imazalil, pefurazoate, oxpoconazole, prochloraz, triflumizole; pyrimidines, pyridines and piperazines: fenarimol, nuarimol, pyrifenox, triforine, 1 -[rel-(2S;3R)-3- (2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranylmethyl]-5-thiocyanato-1 H- [1 ,2,4]triazole, 2-[rel-(2S;3R)-3-(2-chlorophenyl)-2-(2,4-difluorophenyl)-oxiranyl- methyl]-2H-[1 ,2,4]triazole-3-thiol; F.II-2) Delta14-reductase inhitors (Amines, e.g. morpholines, piperidines): morpholines: aldimorph, dodemorph, dodemorph-ace- tate, fenpropimorph, tridemorph; piperidines: fenpropidin, piperalin; spiroketal- amines: spiroxamine; F.II-3) Inhibitors of 3-keto reductase: hydroxyanilides:
fenhexamid;
F.lll) Nucleic acid synthesis inhibitors: F.III-1 ) RNA, DNA synthesis; phenylamides or acyl amino acid fungicides: benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalax- yl-M (mefenoxam), ofurace, oxadixyl; isoxazoles and iosothiazolones: hymex- azole, octhilinone; F.III-2) DNA topisomerase inhibitors: oxolinic acid; F.III-3) Nu- cleotide metabolism (e.g. adenosin-deaminase), hydroxy (2-amino)-pyrimidines: bupirimate;
F.IV) Inhibitors of cell division and or cytoskeleton: F.IV-1 ) Tubulin inhibitors: ben- zimidazoles and thiophanates: benomyl, carbendazim, fuberidazole, thiabendazole, thiophanate-methyl; triazolopyrimidines: 5-chloro-7 (4-methylpiperidin-1 - yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5 a]pyrimidine; F.IV-2) Other cell division inhibitors: benzamides and phenyl acetamides: diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide; F.IV-3) Actin inhibitors: benzophenones: metrafenone;
F.V) Inhibitors of amino acid and protein synthesis: F.V-1 ) Methionine synthesis in- hibitors (anilino-pyrimidines): anilino-pyrimidines: cyprodinil, mepanipyrim, nitra- pyrin, pyrimethanil; F.V-2) Protein synthesis inhibitors (anilino-pyrimidines); antibiotics: blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildio- mycin, streptomycin, oxytetracyclin, polyoxine, validamycin A;
F.VI) Signal transduction inhibitors: F.VI-1 ) MAP / Histidine kinase inhibitors (e.g. anilino-pyrimidines); dicarboximides: fluoroimid, iprodione, procymidone, vinclo- zolin; phenylpyrroles: fenpiclonil, fludioxonil; F.VI-2) G protein inhibitors: quino- lines: quinoxyfen;
F.VII) Lipid and membrane synthesis inhibitors: F.VII-1 ) Phospholipid biosynthesis inhibitors: organophosphorus compounds: edifenphos, iprobenfos, pyrazophos; dithiolanes: isoprothiolane; F.VII-2) Lipid peroxidation: aromatic hydrocarbons: dicloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb, etridiazo- le; F.VII-3) Carboxyl acid amides (CAA fungicides); cinnamic or mandelic acid amides: dimethomorph, flumorph, mandiproamid, pyrimorph; valinamide carbamates: benthiavalicarb, iprovalicarb, pyribencarb, valifenalate and N-(1 -(1 -(4- cyano-phenyl)ethanesulfonyl)-but-2-yl) carbamic acid-(4-fluorophenyl) ester;
F.VII-4) Compounds affecting cell membrane permeability and fatty acids: oxa- thiapiprolin, carbamates: propamocarb, propamocarb-hydrochlorid, F.VIII) Inhibitors with Multi Site Action: F.VIII-1 ) Inorganic active substances: Bordeaux mixture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate, sulfur; F.VIII-2) Thio- and dithiocarbamates: ferbam, mancozeb, maneb, metam, methasulphocarb, metiram, propineb, thiram, zineb, ziram;
F.VIII-3) Organochlorine compounds (e.g. phthalimides, sulfamides, chloroni- triles): anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichloro- phen, flusulfamide, hexachlorobenzene, pentachlorophenole and its salts, phthal- ide, tolylfluanid, N-(4-chloro-2-nitro-phenyl)-N-ethyl-4-methyl-benzenesulfon- amide; F.VIII-4) Guanidines and other: guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-triacetate, iminocta- dine-tris(albesilate), 2,6-dimethyl-1 H,5H-[1 ,4]dithiino[2,3-c:5,6-c']dipyrrole- 1 ,3,5,7(2H,6H)-tetraone; F.VIII-5) Ahtraquinones: dithianon;
F.IX) Cell wall synthesis inhibitors: F.IX-1 ) Inhibitors of glucan synthesis: validamy- cin, polyoxin B; F.IX-2) Melanin synthesis inhibitors: pyroquilon, tricyclazole, car- propamide, dicyclomet, fenoxanil;
F.X) Plant defence inducers: F.X-1 ) Salicylic acid pathway: acibenzolar-S-methyl; F.X-2) Others: probenazole, isotianil, tiadinil, prohexadione-calcium; phospho- nates: fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
F.XI) Unknown mode of action:bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphe- nylamin, flumetover, flusulfamide, flutianil, methasulfocarb, oxin-copper, pro- quinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4- one, N-(cyclopropylmethoxyimino-(6-difluoro-methoxy-2,3-difluoro-phenyl)- methyl)-2-phenyl acetamide, N'-(4-(4-chloro-3-trifluoromethyl-phenoxy)-2,5-di- methyl-phenyl)-N-ethyl-N methyl formamidine, N' (4-(4-fluoro-3-trifluoromethyl- phenoxy)-2,5-dimethyl-phenyl)-N-ethyl-N-methyl formamidine, N'-(2-methyl-5- trifluoromethyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N-ethyl-N-methyl formamidine, N'-(5-difluoromethyl-2 methyl-4-(3-trimethylsilanyl-propoxy)-phenyl)-N- ethyl-N-methyl formamidine, methoxy-acetic acid 6-tert-butyl-8-fluoro-2,3-di- methyl-quinolin-4-yl ester, and 3-[5-(4-chloro-phenyl)-2,3-dimethyl-isoxazolidin-3 yl]-pyridine, pyrisoxazole, 5-amino-2-isopropyl-3-oxo-4-ortho-tolyl-2,3-dihydro- pyrazole-1 carbothioic acid S-allyl ester, N-(6-methoxy-pyridin-3-yl) cyclopro- panecarboxylic acid amide, 5-chloro-1 (4,6-dimethoxy-pyrimidin-2-yl)-2-methyl- 1 H-benzoimidazole, 2-(4-chloro-phenyl)-N-[4-(3,4-dimethoxy-phenyl)-isoxazol-5- yl]-2-prop-2-ynyloxy-acetamide;
F.XI) Growth regulators: abscisic acid, amidochlor, ancymidol, 6-benzylaminopurine, brassinolide, butralin, chlormequat (chlormequat chloride), choline chloride, cyclanilide, daminozide, dikegulac, dimethipin, 2,6-dimethylpuridine, ethephon, flumetralin, flurprimidol, fluthiacet, forchlorfenuron, gibberellic acid, inabenfide, indole-3-acetic acid, maleic hydrazide, mefluidide, mepiquat (mepiquat chloride), naphthaleneacetic acid, N 6-benzyladenine, paclobutrazol, prohexadione (prohexadione-calcium), prohydrojasmon, thidiazuron, triapenthenol, tributyl phos- phorotrithioate, 2,3,5 tri iodobenzoic acid, trinexapac-ethyl and uniconazole; F.XII) Biological control agents: antifungal biocontrol agents: Bacillus substilis strain with NRRL No. B-21661 , Bacillus pumilus strain with NRRL No. B-30087, Ulo- cladium oudemansii, Chitosan.
2. A method for combating or controlling invertebrate pests, which method comprises contacting said pest or its food supply, habitat or breeding grounds with a pesticidally effective amount of at least one compound as defined in any one of claims 1 to 8, or a composition as defined in any of claims 9 to 1 1 .
3. A method for protecting growing plants from attack or infestation by invertebrate pests, which method comprises contacting a plant, or soil or water in which the plant is growing, with a pesticidally effective amount of at least one compound as defined in any of claims 1 to 8, or a composition as defined in any of claims 9 to 1 1 .
4. Seed comprising a compound as defined in any of claims 1 to 8, or the enantiomers, dia- stereomers or salts thereof, in an amount of from 0.1 g to 10 kg per 100 kg of seed.
15. The use of the compounds as defined in any of claims 1 to 8, or a composition as defined in any of claims 9 to 1 1 , for protecting growing plants from attack or infestation by invertebrate pests.
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