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WO2014063929A1 - Composés pesticides de type pyrazole substitué - Google Patents

Composés pesticides de type pyrazole substitué Download PDF

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Publication number
WO2014063929A1
WO2014063929A1 PCT/EP2013/071230 EP2013071230W WO2014063929A1 WO 2014063929 A1 WO2014063929 A1 WO 2014063929A1 EP 2013071230 W EP2013071230 W EP 2013071230W WO 2014063929 A1 WO2014063929 A1 WO 2014063929A1
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formula
compound
compounds
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alkyl
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Inventor
Sebastian SÖRGEL
Daniel SÄLINGER
Birgit GOCKEL
Christian Defieber
Deborah L. Culbertson
Koshi Gunjima
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BASF SE
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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
    • C07D413/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms
    • C07D413/14—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and oxygen atoms as the only ring hetero atoms 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
  • D is a direct bond, d-Cs-alkylene, C2-Cs-alkenylene, or C2-Cs-alkynylene, which carbon chains can be partially or fully substituted by R a ;
  • R a is halogen, CN, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C4-alkoxy, Ci-C2-haloalkoxy, or S(0) n R b ;
  • n 0, 1 , or 2;
  • R b is H, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, or C 3 -C 6 -cycloalkyl,
  • R a can together form a 3- to 6-membered carbo- or heterocyclic ring, which heterocycle contains 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidised, which carbo- or heterocyclic ring is unsubstituted or partly or fully substituted by groups R c ;
  • R c is halogen, CN, N0 2 , Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, C 3 -C 6 -cycloalkyl, C1-C4- alkoxy, or Ci-C2-haloalkoxy
  • R A is H, Ci-Cs-alkyl, C2-Cs-alkenyl, C2-Cs-alkynyl, C3-C6-cycloalkyl, C3-C6-cycloalkenyl, 3- to 6-membered heterocycle, which may contain 1 or 2 heteroatoms selected from N-R d , O, and S, wherein S may be oxidised, which groups can be partially or fully substituted by R a ;
  • R d is H, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkylcarbonyl, or Ci-C2-alkoxycarbonyl;
  • R A and D together may form a 3- to 6-membered carbocyclic ring, or a 4- to 6-membered heterocyclic ring with a direct bond to the pyrazole moiety, which ring may contain 1 or 2 hetero- atom moieties selected from N-R d , O, and S, wherein S may be oxidised, and which ring can be partially or fully substituted by R a ;
  • T is O, S, NR T , NOR T , or NSR T ;
  • R T is a group mentioned for R A ;
  • R T and D together may form a 4- to 6-membered unsaturated non-aromatic N-containing heterocyclic ring, which ring may contain an additional heteroatom selected from O, and S, wherein S may be oxidised, and which ring can be partially or fully substituted by R a ; and the stereoisomers, salts, tautomers and N-oxides thereof.
  • 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 illustrated 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 2009/027393, WO 2010/034737, WO 2010/034738, and WO 2010/1 12177 describe derivatives of N-arylamides, 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 2009/027393 and WO 2010/034737 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, N-hydroxysuccinimides, hydroxybenzotriazol-1 -yl 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 T-A T-B, and T-C:
  • isomer T-A For reasons of clarity it is referred to isomer T-A only throughout the specification, but its description embraces disclosure of the other isomers as well.
  • 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,
  • heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members
  • heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members
  • ring members comprise pyrrolidin-2-onyl, pyrrolidin-2,5-dionyl, imidazolidin-2-onyl, oxazolidin-2-onyl, thiazolidin-2-onyl and the like.
  • particularly preferred embodiments of the intermediates correspond 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. In a further embodiment, 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.
  • T is O.
  • T is S. These compounds correspond to the formula 1.2. In another embodiment of formula I, T is NR T . These compounds correspond to the formula
  • T is NOR T . These compounds correspond to the formula another embodiment of formula I, T is NSR T . These compounds correspond to the formula
  • two groups R a together form a 3- to 6-membered carbo- or heterocyclic ring, which heterocycle may contain 1 or 2 heteroatoms selected from N, O, and S, wherein S may be oxidised, which ring is unsubstituted or partly or fully substituted by groups R c , wherein R c is halogen, CN, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, Cs-Ce-cycloalkyl, Ci- C 4 -alkoxy, or Ci-C2-haloalkoxy.
  • the ring is unsubstituted.
  • R c is present, it is preferably halogen, CN, NO2, Ci-C2-alkyl, halomethyl, Ci-C 4 -alkoxy, or Ci-C2-haloalkoxy.
  • two groups R a bonded to the same carbon atom together form a 3- to 6- membered carbo- or heterocyclic ring as defined above.
  • Preferably two groups R a represent (-CH2CH2-) and form with the carbon atom to which they are bound a cyclopropyl, or two groups R a represent (-CH2OCH2-) and form with the carbon atom to which they are bound an oxetanyl.
  • two groups R a bonded to adjacent carbon atoms together form a 3- to 6-membered carbo- or heterocyclic ring as defined above.
  • two groups R a represent (-CH2-) and form with the two adjacent carbon atoms to which they are bound a cyclopropyl, or two groups R a represent (-CH2CH2-) and form with the two adjacent carbon atoms to which they are bound a cyclobutyl.
  • R a is halogen, CN, NO2, Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, Ci-C 4 -alkoxy, Ci-C 2 -haloalkoxy, or S(0) n R b .
  • the formula I compounds comprise 0, 1 , or 2 groups R a .
  • D is a a-branched Ci-Cs-alkylene, C2-Cs-alkeny- lene or C2-C8-alkynylene, which carbon chains can be partially or fully substituted by R a , such compounds correspond to formula I.A: wherein
  • R 3 is Ci-C2-alkyl, Ci-C2-haloalkyl, C3-C6-cycloalkyl, or C3-C6-cycloalkyl-Ci-C2-alkyl, preferably
  • R 4 is H, or a group mentioned for R 3 , preferably H;
  • Da is a direct bond, Ci-C4-alkylene, C2-C4-alkenylene, or C2-C4-alkynylene, which carbon chains can be partially or fully substituted by R a ; preferably Da is a direct bond, or Ci-C 2 - alkylene.
  • R 3 and R a bound to the adjacent atom of Da, together represent -CH2-, or -CH2CH2-, and together form a cyclopropyl or a cyclobutyl ring.
  • D is a strait-chain Ci-Cs-alkylene, C2-C8-alkenylene or C2- Ce-alkynylene, which carbon chains can be partially or fully substituted R a .
  • Such compounds correspond to formula I.B:
  • R' is H, halogen, CN, NO2, or S(0) n R b ; preferably H, or halogen, particularly H;
  • R A is H, or Ci-C4-alkyl, preferably H, or CH3.
  • R T is H, or Ci-C4-alkyl, preferably CH3.
  • D is a direct bond.
  • Such compounds correspond to formula I.C:
  • DR is preferably a cyclobutyl (C-C4H5), or cyclohexyl ring (c-CeHg).
  • T stands preferably in para position of the carbocycle in formula I.D.
  • Such compounds correspond to formulae I.D1 and I.D2:
  • DR is a 4- to 6-membered, preferably a 5- or 6-membered heterocyclic ring with a direct bond to the pyrazole moiety, the ring contains preferably one heteroatom, such as an oxygen, or sulfur.
  • heteroatom such as an oxygen, or sulfur.
  • Such compounds correspond to formulae I.D3, I.D4, and I.D5, wherein A is N-R d , O or S, preferably oxygen, or sulphur.
  • heteroatom A is oxygen.
  • Preferred heterocycles are tetra- hydropyrane (THP), and tetrahydrofurane (THF), such as 4-THP, 3-THP, and 3-THF.
  • heteroatom A is sulfur.
  • Preferred heterocycles are tetrahydro- thiopyrane (THTP), and tetrahydrothiophene (THTF), such as 4-THTP, 3-THTP, and 3-THTF.
  • THTP tetrahydro- thiopyrane
  • THTF tetrahydrothiophene
  • the heterocyclic ring DR is optionally substituted by R a .
  • formula I.D3 T stands preferably in position 3.
  • formula I.D4 T stands preferably in position 2, 4, or 6.
  • formula I.D5 T stands in position 2, 4, or 5, preferably in position 4.
  • R T and D together form a 4-, 5- or 6-membered unsaturated non-aromatic N-containing heterocyclic ring DT, which is bound to the pyrazole moiety vi a spacer D'.
  • DT is a 5-membered ring.
  • DT is a 6-membered ring.
  • DT may be partly or fully substituted by R aa .
  • Such compounds correspond to formula I.E, wherein D' is Ci-C7-alkylene, C2-C7-alkenylene, or C2-C7-alkynylene, which can be partially or fully substituted by R a , and
  • R aa is H, or corresponds to one or more groups R a .
  • D' preferably is a branced Ci-C2-alkylene, particularly 1 ,1 -ethylene.
  • compounds DT is selected from dihydro-pyrrole, dihydro-isoxazole, tetrahydropyridine, and dihydro-oxazine.
  • DT preferably is optionally substi- tuted 3,4-dihydro-2H-pyrrol-4-yl, 4,5-dihydroisoxazol-4-yl, 2,3,4,5-tetrahydropyridin-5-yl, or 5,6- d i hyd ro-4 H-oxazi n-4-yl .
  • R T and D together form a 5- or 6-membered unsaturated non-aromatic N-containing heterocyclic ring DT, which is directly bound to the pyrazole moiety.
  • DT may be partly or fully substituted by R aa .
  • R aa denotes H, or corresponds to one or more groups R a .
  • 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 infestation 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 pesti- cidally 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 infesta- tion 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 ar- thropods 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, myriapedes and insects as well as nematodes, especially insects. They are especially suitable for efficiently combating or controlling the following pests:
  • Insects from the order of the lepidopterans for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autog- rapha gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheimatobia bru- mata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomo- nella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Earias insulana, Elasmo- palpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha
  • beetles Coldeoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Aphthona euphoridae, Athous haemorrhoidalis, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotoma trifurcata, Cetonia aurata, Ceuthorrhynchus assimilis, Ceuthor- rhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Ctenicera ssp., Diabrotica
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Dichromothrips ssp., Frankliniella fus- ca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci,
  • termites e.g. Calotermes flavicollis, Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Reticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria - Blattodea), e.g.
  • Blattella germanica Blattella asahinae, Periplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis;
  • ants e.g. Athalia rosae, Atta cephalotes, Atta capiguara, Atta cephalotes, Atta laevigata, Atta robusta, Atta sexdens, Atta texana,
  • Crematogaster spp. Hoplocampa minuta, Hoplocampa testudinea, Lasius niger, Mon- omorium pharaonis, Solenopsis geminata, Solenopsis invicta, Solenopsis richteri, Solenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole megacephala,
  • crickets grasshoppers, locusts (Orthoptera), e.g. Acheta domestica, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femurrubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Schistocerca americana, Schistocerca gregaria, Dociostaurus maroccanus, Tachycines asynamorus, Oedaleus senegalensis, Zonozerus variegatus, Hieroglyphus daganensis, Kraussaria angu- lifera, Calliptamus italicus, Chortoicetes terminifera, and Locustana pardalina;
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheo- pis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • silverfish, firebrat e.g. Lepisma saccharina and Thermobia domestica, centipedes (Chilopoda), e.g. Scutigera coleoptrata,
  • Earwigs e.g. forficula auricularia
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • insects e.g. Onychiurus ssp.
  • the compounds of the present invention 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 citri, Thrips oryzae, Thrips palmi and Thrips tabaci.
  • Diptera e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Ceratitis capitata, Chrysomya bezziana, Chrysomya hominivorax,
  • Hemiptera in particular aphids: Acyrthosiphon onobrychis, Adelges laricis, Aphidula na- sturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Brachycaudus cardui, Brachycaudus helichrysi, Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae,
  • the compounds of the present invention are particularly useful for controlling insects of the orders Hemiptera and Thysanop- tera.
  • 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 harmful fungi 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 pests 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 Grubemann, Formulation technology, Wiley VCH, Weinheim, 2001 ; or Knowles, New developments in crop protection product formulation, Agrow Reports DS243, T&F Informa, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, sur- factants, 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, tackifiers 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, tetrahydronaphtha- lene, alkylated naphthalenes; alcohols, e.g. ethanol, propanol, butanol, benzylalcohol, cyclo- hexanol; 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, tetrahydronaph
  • 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 vege- table 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
  • 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 colloid, 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 alco- hols, of ethoxylated alcohols, or of fatty acid esters.
  • Examples of phosphates are phosphate esters.
  • Examples of carboxylates are alkyl carboxylates, and carboxylated alcohol or al- kylphenol 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 ox- ide.
  • N-subsititued fatty acid amides are fatty acid glucamides or fatty acid alka- nolamides.
  • esters are fatty acid esters, glycerol esters or monoglycerides.
  • sugar-based surfactants are sorbitans, ethoxylated sorbitans, sucrose and glucose esters or alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, 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 polyethyleneamines.
  • Suitable adjuvants are compounds, which have a neglectable or even no pesticidal activi- ty 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 alkylisothia- zolinones 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
  • Suitable colorants are pigments of low water solubility and water-soluble dyes. Examples are inorganic colorants (e.g. iron oxide, titan oxide, iron hexacy- anoferrate) 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. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexanone). Dilution with water gives a dispersion.
  • dispersant e. g. polyvinylpyrrolidone
  • organic solvent e.g. cyclohexanone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • wa- ter-insoluble organic solvent e.g. aromatic hydrocarbon
  • Emulsions (EW, EO, ES)
  • 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 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 alcohol 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 alcohol 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. carboxymethylcellulose) 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. carboxymethylcellulose
  • 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 radical 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.
  • an isocyanate monomer e.g. di- phenylmethene-4,4'-diisocyanatae
  • a protective colloid e.g. polyvinyl alcohol
  • the addition of a polyamine results in the formation of a polyurea microcapsules.
  • 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
  • a compound I according to the invention are dissolved in up to 100 wt% organic solvent, e.g. aromatic hydrocarbon.
  • 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 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).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • At least one further compound B selected from the compounds of the following groups A.1 , A.2, A.3, A.4, A.5, A.6, A.7, A.8, A.9, A.10, A.1 1 , A.12, A.13, A.14, A.15, A.16, A.17, F.1 , F.2, F.3, F.4, F.5, F.6, F.7, F.8, F.9, F.10 and F.1 1 :
  • A.1 Carbamate compounds selected from the group consisting of methiocarb and thiodi- carb
  • A.2 Pyrethroid compounds selected from the group consisting of 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-cyper- methrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin,
  • Nicotinic receptor agonists/antagonists compounds selected from the group consisting of acetamiprid, bensultap, cartap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thiocyclam and thiosultap-sodium;
  • A.4 GABA gated chloride channel antagonist compounds selected from the group consist- ing of acetoprole, ethiprole and fipronil;
  • A.5 Chloride channel activators selected from the group consisting of abamectin,
  • A.8 Selective feeding blockers selected from the group consisting of pymetrozine and
  • A.9 Chitin synthesis inhibitors selected from the group consisting of teflubenzuron and novaluron;
  • A.10 Lipid biosynthesis inhibitors selected from the group consisting of spirodiclofen, spiro- mesifen and spirotetramat;
  • A.1 1 Diamide-type Ryanodine receptor modulators - Phthalamides selected from the group consisting of flubendiamide and (R)-, (S)-3-chloro-N1 - ⁇ 2-methyl-4-[1 ,2,2,2-tetrafluoro-1 - (trifluoromethyl)ethyl]phenyl ⁇ -N2-(1 -methyl-2-methylsulfonylethyl)phthalamide (A1 1.1 );
  • A.12 Isoxazoline compounds selected from the group consisting of 4-[5-(3,5-dichlorophe- nyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benz- amide (A12.1 ), 4-[5-(3,5-dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2- methyl-
  • A.14 Malononitrile compounds selected from the group consisting of 2-(2,2,3, 3,4,4, 5,5-octa- fluoropentyl)-2-(3,3,3-trifluoropropyl) malononitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2- CH2-CH2-CF3) (A14.1 ) and 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-penta- fluorobutyl)-malonodinitrile (CF 2 HCF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF2-CF3) (A14.2);
  • A.15 Microbial disruptors selected from the group consisting of Bacillus thuringiensis subsp.
  • A.16 Aminofuranone compounds selected from the group consisting of 4- ⁇ [(2-chloro-1 ,3-thi- azolo-5-yl)methyl](2-fluoroethyl)amino ⁇ furan-2(5H)-on (A16.1 ), 4- ⁇ [(6-chloropyrid-3- yl)methyl](2-fluoroethyl)amino ⁇ furan-2(5H)-on (A16.2), 4- ⁇ [(6-chloropyrid-3- yl)methyl](2,2-difluoroethyl)amino ⁇ furan-2(5H)-on (A16.3), 4- ⁇ [(6-chloro-5-fluoropyrid-3- yl)methyl](methyl)amino ⁇ furan-2(5H)-on (A16.4), 4- ⁇ [(6-chloro-5-fluoropyrid-3-yl)me- thyl](cyclopropyl)
  • A.17 Various compounds, selected from the group consisting of aluminium phosphide, ami- doflumet, benclothiaz, benzoximate, bifenazate, borax, bromopropylate, cryolite, cyanide, cyenopyrafen, cyflumetofen, chinomethionate, dicofol, fluensulfone, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartar emetic, sulfoxaflor, afidopyropen (cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R, 12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-deca- hydro
  • Respiration inhibitors selected from the following groups a), b), c) and d):
  • Inhibitors of complex III at Qo site e.g. strobilurins
  • strobilurins selected from the group consisting of azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fenaminstrobin, fenoxystrobin / flufenoxystrobin, fluoxastrobin, kresox- im-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrame- tostrobin, pyraoxystrobin, 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, p
  • inhibitors of complex II e. g. carboxamides
  • complex II e. g. carboxamides
  • carboxamides selected from the group consisting of benodanil, bixafen, boscalid, car
  • respiration inhibitors e.g. complex I, uncouplers
  • respiration inhibitors selected from the group consisting of diflumetorim; the nitrophenyl derivatives: binapacryl, dinobuton, di- nocap and fluazinam; ferimzone; fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide; ametoctradin; and silthiofam;
  • SBI fungicides selected from the following groups a), b) and c):
  • C14 demethylase inhibitors selected from the group consisting of the following triazoles: azaconazole, bitertanol, bromuconazole, cyprocona- zole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbucona- zole, fluquinconazole, flusilazole, flutriafol, hexaconazole, imibenconazole, ipco- representativesole, metconazole, myclobutanil, oxpoconazole, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, tri- adimefon, triadimenol, triticonazole and uniconazole; the following imidazoles: imazalil
  • Inhibitors of 3-keto reductase fenhexamid; F.3 Nucleic acid synthesis inhibitors selected from the following groups a) and b):
  • phenylamides or acyl amino acid fungicides selected from the group consisting of benalaxyl, benalaxyl-M, kiralaxyl, metalaxyl, metalaxyl-M (mefenoxam), ofu- race and oxadixyl;
  • nucleic acid synthesis inhibitors selected from the group consisting of hy- mexazole, octhilinone, oxolinic acid and bupirimate;
  • F.4 Inhibitors of cell division and cytoskeleton selected from the following groups a) and b): a) tubulin inhibitors, selected from the group consisting of benzimidazoles or thio- phanates such as benomyl, carbendazim, fuberidazole, thiabendazole or thio- phanate-methyl; and triazolopyrimidines such as 5-chloro-7-(4-methylpiperidin-1 - yl)-6-(2,4,6-trifluorophenyl)-[1 ,2,4]triazolo[1 ,5-a]pyrimidine;
  • cell division inhibitors selected from the group consisting of diethofencarb, ethaboxam, pencycuron, fluopicolide, zoxamide, metrafenone and pyriofenone;
  • F.5 Inhibitors of amino acid and protein synthesis selected from the following groups a) and b):
  • methionine synthesis inhibitors selected from the group consisting of cyprodinil, mepanipyrim and pyrimethanil;
  • protein synthesis inhibitors selected from the group consisting of blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomycin, streptomycin, oxytetracyclin, polyoxine and validamycin A;
  • F.6 Signal transduction inhibitors selected from the following groups a) and b):
  • MAP / histidine kinase inhibitors selected from the group consisting of fluoroimid, iprodione, procymidone, vinclozolin, fenpiclonil and fludioxonil;
  • Phospholipid biosynthesis inhibitors selected from the group consisting of edifen- phos, iprobenfos, pyrazophos and isoprothiolane;
  • b) compounds affecting lipid peroxidation selected from the group consisting of di- cloran, quintozene, tecnazene, tolclofos-methyl, biphenyl, chloroneb and etridi- azole;
  • F.8 Inhibitors with multi site action selected from the following groups a), b), c) and d): a) inorganic active substances selected from the group consisting of Bordeaux mix- ture, copper acetate, copper hydroxide, copper oxychloride, basic copper sulfate and sulfur; b) thio- and dithiocarbamates selected from the group consisting of ferbam, man- cozeb, maneb, metam, metiram, propineb, thiram, zineb and ziram; c) organochlorine compounds (e.g.
  • phthalimides, sulfamides, chloronitriles selected from the group consisting of anilazine, chlorothalonil, captafol, captan, folpet, dichlofluanid, dichlorophen, flusulfamide, hexachlorobenzene, pentachlorphenole and its salts, phthalide, tolylfluanid and N-(4-chloro-2-nitro-phenyl)-N-ethyl-4- methyl-benzenesulfonamide;
  • guanidines and others selected from the group consisting of guanidine, dodine, dodine free base, guazatine, guazatine-acetate, iminoctadine, iminoctadine-tri- acetate, iminoctadine-tris(albesilate) and dithianon;
  • inhibitors of glucan synthesis selected from the group consisting of validamycin and polyoxin B;
  • melanin synthesis inhibitors selected from the group consisting of pyroquilon, tri- cyclazole, carpropamid, dicyclometa and fenoxanil;
  • F.10 Plant defence inducers selected from the following groups a) and b):
  • phosphonates selected from the group consisting of fosetyl, fosetyl-aluminum, phosphorous acid and its salts;
  • F.1 1 Fungicides having an unknown mode of action selected from the group consisting of bronopol, chinomethionat, cyflufenamid, cymoxanil, dazomet, debacarb, diclomezine, difenzoquat, difenzoquat-methylsulfate, diphenylamin, fenpyrazamine, flumetover, flusulfamide, flutianil, methasulfocarb, nitrapyrin, nitrothal-isopropyl, oxin-copper, pro- quinazid, tebufloquin, tecloftalam, triazoxide, 2-butoxy-6-iodo-3-propylchromen-4-one,
  • 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 A.1 to A.17.
  • a preferred embodiment of the invention relates to pesticidal mixtures of a compound of formula I with one compound B from the groups A.1 to A.17.
  • 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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.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 A.16.
  • 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 A.17.
  • Binary mixtures of a compound of formula I and a compound B from the groups A.1 to A.17 are one preferred embodiment of the invention.
  • Ternary mixtures of a compound of formula I and two compounds B from the groups A.1 to A.17 are another preferred embodiment of the invention.
  • the compound B selected from group A.2 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 A.3 as defined above is preferably acetamiprid, clo- thianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram or thiacloprid.
  • the compound B selected from group A.4 as defined above is preferably ethiprole or fipronil, particularly fipronil.
  • the compound B selected from group A.5 as defined above is preferably abamectin, emamectin benzoate or lepimectin.
  • the compound B selected from group A.6 as defined above is preferably chlorfenapyr.
  • the compound B selected from group A.8 as defined above is preferably flonicamid or pymetrozine.
  • the compound B selected from group A.10 as defined above is preferably spiromesifen or spirotetramat
  • the compound B selected from group A.1 1 as defined above is preferably flubendiamide.
  • the compound B selected from group A.13 as defined above is preferably chloranthranili- prole (rynaxypyr) or cyantraniliprole.
  • the compound B selected from group A.16 as defined above is preferably4- ⁇ [(6-chloro- pyrid-3-yl)methyl](2,2-difluoroethyl)amino ⁇ furan-2(5H)-on (A16.3).
  • the compound B selected from group A.17 is preferably pyrifluquinazon, sulfoxaflor or afidopyropen (cyclopropaneacetic acid, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclo- propylacetyl)oxy]methyl]-1 ,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b- trimethyl-1 1 -oxo-9-(3-pyridinyl)-2H,1 1 H-naphtho[2,1 -b]pyrano[3,4-e]pyran-3,6-diyl] ester).
  • afidopyropen cyclopropaneacetic acid, [(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclo
  • 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- cypermethrin, thiamethoxam, abamectin, spirotetramat, imidacloprid, flonicamid, chloran- thraniliprole, pymetrozine, sulfoxaflor and afidopyropen.
  • active compound B selected from the group consisting of fipronil, alpha- cypermethrin, thiamethoxam, abamectin, spirotetramat, imidacloprid, flonicamid, chloran- thraniliprole, 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 afidopyren 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 the groups F.1 to F.1 1 .
  • Binary mixtures of a compound of formula I and a compound B from the groups 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 the 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 from each of the groups A.1 to A.17 and F.1 to F.1 1 are another preferred embodiment of the invention.
  • 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, pyra- clostrobin, 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, fluxapyroxad, 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 ametoctradin.
  • 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, epoxi- conazole, fluquinconazole, ipconazole, prothioconazole, tebuconazole, triticonazole, and prochloraz.
  • 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.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 thi- ophanate-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 pyrimethanil.
  • 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 active 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 active 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 man- cozeb.
  • 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 active 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, fluoxastrobin, picoxystrobin, pyraclostrobin, trifloxystrobin, fluxapyroxad, benthiavalicarb, iprovalicarb, fenhexamid, boscalid, mancozeb, ametoctradin, metalalxyl-m, pyrimethanil, cy- prodinil, carbendazim, iprodion, cyazofamid, prochloraz, chlorothalonil, penthiopyrad, difeno- conazole, epoxiconazole, ipconazole, prothioconazole and tebuconazole.
  • active compound B selected from the group consisting of azoxystrobin, fluoxastrobin, picoxystrobin, pyraclo
  • 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.
  • 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.
  • the component I is one compound of formula I specifically disclosed in the specification ("Compound XX").
  • table M-F represents preferred combinations of the active compounds I of formula I as defined in Tables 1 to 30, 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 phyto- pathogenic 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.
  • 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. feres on barley or D. tritici-repentis on wheat;
  • Gibberella species on cereals and rice for example Gibberella fujikuroi on rice ;
  • Michrodochium nivale on cereals Mycosphaerella species on cereals, bananas and peanuts, for
  • 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,
  • Ustilago species on cereals, corn and sugar cane for example, U. maydis on corn;
  • Venturia species scab
  • 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.
  • 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.
  • Ascomycetes such as Ophiostoma spp., Ceratocystis spp., Aureobasidium pullulans, Sclerophoma spp., Chaetomium spp., Humicola spp., Petriella spp., Trichurus spp.
  • Basidiomycetes such as Coniophora
  • Tyromyces spp. Deuteromycetes, such as Aspergillus spp., Cladosporium spp., Penicillium spp., Trichoderma spp., Alternaria 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
  • Method 1 RP-18 column (Chromolith® Speed ROD from Merck KgaA, Germany), 50 * 4.6 mm; mobile phase: acetonitrile + 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.
  • Method 2 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 electrospray ionization, 80 V (positive mode).
  • 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 concentrations 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.
  • 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 lighting 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% relative 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.
  • test unit For evaluating control of green peach aphid (Myzus persicae) through systemic means the test unit consisted of 96-well-microtiter plates containing liquid artificial diet under an artificial membrane.
  • the compounds were formulated in 25:75 (vohvol) DMSO:water. Different concentrations of formulated compounds were pipetted into the aphid diet, using a custom built pipetter, at two replications. After application, 5 to 8 adult aphids were placed on the artificial membrane inside the microtiter plate wells. The aphids were then allowed to suck on the treated aphid diet and incubated at about 23 + 1 °C and about 50 + 5 % relative humidity for 3 days. Aphid mortality and fecundity was then visually assessed.
  • the compounds were formulated in 3:1 (vohvol) water : DMSO.
  • 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. In this test, compounds I-4, 1-15, 1-16, and I-20 at 2500 ppm showed at least 75% mortality in comparison with untreated controls.

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Abstract

Cette invention concerne des pyrazoles substitués de formule (I) dont les variables ont la signification indiquée dans la description, des combinaisons de ces composés avec d'autres pesticides, des méthodes et l'utilisation de ces composés et combinaisons pour lutter contre les ravageurs invertébrés tels que les insectes, les arachnides ou les nématodes dans et sur les plantes, et pour empêcher ces plantes d'être infestées par des ravageurs, notamment pour protéger leur matériel de multiplication tel que leurs graines.
PCT/EP2013/071230 2012-10-23 2013-10-11 Composés pesticides de type pyrazole substitué Ceased WO2014063929A1 (fr)

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WO2015055497A1 (fr) * 2013-10-16 2015-04-23 Basf Se Composés pesticides de pyrazole substitué
JP2018515496A (ja) * 2015-05-11 2018-06-14 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ４−アミノ−ピリダジンを製造するための方法
KR20190117576A (ko) * 2017-02-14 2019-10-16 바스프 에스이 살충성 피리다진피라졸아미드의 안정한 제형

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WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés
WO2010112177A1 (fr) * 2009-04-03 2010-10-07 Bayer Cropscience Aktiengesellschaft Amines pyridines et –pyridazines acylées en tant qu'insecticides
WO2012084670A1 (fr) * 2010-12-20 2012-06-28 Basf Se Mélanges pesticides actifs contenant des composés pyrazole
WO2012143317A1 (fr) * 2011-04-21 2012-10-26 Basf Se Nouveaux composés pesticides à base de pyrazole

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Publication number Priority date Publication date Assignee Title
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés
WO2010112177A1 (fr) * 2009-04-03 2010-10-07 Bayer Cropscience Aktiengesellschaft Amines pyridines et –pyridazines acylées en tant qu'insecticides
WO2012084670A1 (fr) * 2010-12-20 2012-06-28 Basf Se Mélanges pesticides actifs contenant des composés pyrazole
WO2012143317A1 (fr) * 2011-04-21 2012-10-26 Basf Se Nouveaux composés pesticides à base de pyrazole

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015055497A1 (fr) * 2013-10-16 2015-04-23 Basf Se Composés pesticides de pyrazole substitué
JP2018515496A (ja) * 2015-05-11 2018-06-14 ビーエーエスエフ ソシエタス・ヨーロピアＢａｓｆ Ｓｅ ４−アミノ−ピリダジンを製造するための方法
US11046656B2 (en) 2015-05-11 2021-06-29 Basf Se Process for preparing 4-amino-pyridazines
US12162841B2 (en) 2015-05-11 2024-12-10 Basf Se Process for preparing 4-amino-pyridazines
KR20190117576A (ko) * 2017-02-14 2019-10-16 바스프 에스이 살충성 피리다진피라졸아미드의 안정한 제형
US11284619B2 (en) * 2017-02-14 2022-03-29 Basf Se Stable formulation of pesticidal pyridazinpyrazolamides
KR102550279B1 (ko) 2017-02-14 2023-07-03 바스프 에스이 살충성 피리다진피라졸아미드의 안정한 제형

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