WO2014064129A1 - Composés de pyrazole pour lutter contre les ravageurs invertébrés - Google Patents

Composés de pyrazole pour lutter contre les ravageurs invertébrés Download PDF

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WO2014064129A1
WO2014064129A1 PCT/EP2013/072113 EP2013072113W WO2014064129A1 WO 2014064129 A1 WO2014064129 A1 WO 2014064129A1 EP 2013072113 W EP2013072113 W EP 2013072113W WO 2014064129 A1 WO2014064129 A1 WO 2014064129A1
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alkyl
radicals
compounds
alkoxy
formula
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PCT/EP2013/072113
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English (en)
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Sebastian SÖRGEL
Daniel SÄLINGER
Birgit GOCKEL
Christian Defieber
Karsten KÖRBER
Ronan Le Vezouet
Steffen Gross
Deborah L. Culbertson
Koshi Gunjima
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Basf Se
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Publication of WO2014064129A1 publication Critical patent/WO2014064129A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings 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
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • 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
    • 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

Definitions

  • the present invention relates to a novel pyrazole compounds which can be used for combating or controlling invertebrate pests, in particular arthropod pests.
  • the present invention further relates to a method for controlling invertebrate pests, a method for protecting plant propagation material and/or the plants growing therefrom and a method for treating or protecting an animal from infestation or infection by parasites by using these compounds.
  • the present invention further relates to plant propagation material and to an agricultural or veterinary composition comprising said compounds.
  • 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. While a large number of pesticidal agents are known, due to the ability of target pests to develop resistance to said agents, there is an ongoing need for new agents for combating invertebrate pests such as insects, arachnids and nematodes.
  • WO 2004/106324, WO 2004/035545 and WO 2005/040152 describe N-aryl and N-hetarylamides and the corresponding thioamides derived from carboxylic acids com- prising a 5-membered heterocycle. These compounds are mentioned to be useful as herbicides.
  • WO 2009/027393, WO 2010/034737, WO 2010/034738, and WO 2010/1 12177 describe derivatives of N-(het)arylamides, derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests.
  • PCT/EP2012/056875 describes N-pyridazinyl carboxamide compounds derived from pyrazole carboxylic acids. These compounds are mentioned to be useful for combating invertebrate pests. However, this document does not describe compounds having the characteristic substituents as claimed in the present invention.
  • the invention relates to acrylamide compounds of formula I
  • R 1 is selected from hydrogen, CN, NO2, Ci-Cio-alkyl, C2-Cio-alkenyl and C2-C10- alkynyl, wherein the three last mentioned radicals may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2 or 3 identical or different radicals R x ,
  • R is further selected from OR a , SR a , C(Y)R b , C(Y)OR c , S(0)R d , S(0) 2 R d , NR e R f , C(Y)NR9R h , S(0) m NR e R f , C(Y)NR'NR e R f , Ci-C 5 -alkylene-OR a , Ci-C 5 - alkylene-CN, Ci-C 5 -alkylene-C(Y)R b , Ci-C 5 -alkylene-C(Y)OR c , Ci-C 5 -alkylene- NR e R f , Ci-C 5 -alkylene-C(Y)NR 9 R h , Ci-C 5 -alkylene-S(0) m R a , Ci-C 5 -alkylene- S(0)mNR e R f , d-Cs-alkylene-NR i
  • R 1 is further selected from R 1a and d-Cs-alkylene-R 13 , wherein R 1a is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from N-Ri, O, and S(0) m as ring members, which monospiro or dispiro 5- to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1 , 2, 3 or 4 identical or different radicals R k ;
  • R 2 is halogen, Ci-C6-alkyl, C3-C7-cycloalkyl, Ci-C6-alkoxy, C3-C7-cycloalkoxy,
  • R 3 is Z or Ci-C6-alkylene-Z, where an ethandiyl diradical within the alkylene moiety may be replaced by a C3-C7-cycloalkanediyl diradical, wherein Z is selected from Z1 , Z2, Z3 Z6 and Z7,
  • Z5 Z6 (Z7) where # denotes the point of attachment to the remainder of the molecule, or Z is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from N-Ri, O, and S(0)m as ring members, which monospiro or dispiro 5- to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1 , 2, 3 or 4 radicals R k ;
  • W is CH or N
  • X, Y are independently of each other selected from O and S; m is 0, 1 or 2;
  • R a , R b , R c are independently of each other selected from hydrogen, Ci-C4-alkyl,
  • Ci-C4-haloalkyl C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, Ci-C4-alkoxy-Ci- C4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, heterocyclyl, heterocyclyl-Ci- C4-alkyl, phenyl, hetaryl, phenyl-Ci-C4-alkyl and hetaryl-Ci-C4-alkyl, wherein the ring in the eight last mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents which, independently of each other, are selected from halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and C1-C4- haloalkoxy;
  • R d is selected from Ci-C4-alkyl, Ci-C4-haloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, phenyl, hetaryl, phenyl-Ci-C4-alkyl and hetaryl-Ci-C4-alkyl, wherein the ring in the eight last mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents which are independently of each other selected from halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl, Ci- C4-alkoxy and Ci-C4-halo
  • R e , R f are independently of each other selected from hydrogen, Ci-C4-alkyl,
  • Ci-C4-haloalkyl C3-C6-cycloalkyl, C3-C6-cycloalkylmethyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl, C2-C4-alkynyl, Ci-C4-alkoxy-Ci-C4-alkyl, C1-C4- alkylcarbonyl, Ci-C4-haloalkylcarbonyl, Ci-C4-alkylsulfonyl, C1-C4- haloalkylsulfonyl, heterocyclyl, heterocyclyl-Ci-C4-alkyl, heterocyclylcarbonyl, heterocyclyl-Ci-C4-sulfonyl, phenyl, phenylcarbonyl, phenylsulfonyl, hetaryl, hetarylcarbonyl, hetarylsul
  • R e and R f together with the nitrogen atom to which they are bound form a 5- or
  • 6-membered, saturated or unsaturated heterocycle which may carry a further heteroatom being selected from O, S and N as a ring member atom and wherein the heterocycle may be unsubstituted or may carry 1 , 2, 3, 4 or 5 substituents which are independently of each other selected from halogen, cyano, nitro, Ci- C4-alkyl, Ci-C4-haloalkyl, Ci-C4-alkoxy and Ci-C4-haloalkoxy; Re, R' 1 are independently of each other selected from hydrogen, Ci-C4-alkyl,
  • Ci-C4-haloalkyl C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl,
  • R i is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl,
  • R j is hydrogen, Ci-C2-alkyl, Ci-C2-haloalkyl, Ci-C2-alkylcarbonyl and Ci-C2-alkoxy- carbonyl;
  • R k is selected from halogen, CN, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C2-alkoxy-Ci-C2-alkyl, Ci-C2-alkylidene, wherein the four last mentioned radicals may be unsubstituted, or may be partially or fully halogenated,
  • R k is selected from N0 2 , C(0)NH 2 , C(S)NH 2 , Ci-C 2 -alkylcarbonyloxy,
  • R x is selected from cyano, nitro, Ci-C4-alkoxy, Ci-C4-haloalkoxy, S(0) m R d ,
  • Ci-Cio-alkylcarbonyl Ci-C 4 -haloalkylcarbonyl, C1-C4- alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C3-C6-cycloalkyl, 3- to 7-membered heterocyclyl, 5- or 6-membered hetaryl, phenyl, C3-C6-cycloalkoxy, 3- to 6- membered heterocyclyloxy and phenoxy, wherein the last 7 mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 radicals R ,
  • Ry is selected from halogen, cyano, nitro, Ci-C4-alkyl, Ci-C4-haloalkyl,
  • Ci-C4-haloalkylcarbonyl Ci-C4-alkoxycarbonyl, Ci-C4-haloalkoxycarbonyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C2-C4-alkenyl, C2-C4-haloalkenyl,
  • R kk , R xx , RYY independently of each other and from each appearance are selected from Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C6-cycloalkyl and C3-C6-halocycloalkyl; T is O or S;
  • R 3a , R 3b are independently of each other selected from R 31 , OR 31 and NR 31 R 32 , wherein R 31 and R 32 are independently of each other selected from Ci-C6-alkyl, C3-Cio-cycloalkyl and C3-Cio-cycloalkyl-Ci-C6-alkyl, wherein the three last mentioned radicals may be unsubstituted, or may be partially or fully halogenated;
  • R 3c , R 3d , R 3e are independently of each other selected from Ci-C6-alkyl, C3-C10- cycloalkyl and C3-Cio-cycloalkyl-Ci-C6-alkyl, wherein the three last mentioned radicals may be unsubstituted, or may be partially or fully halogenated;
  • U is an N-bound 5- to 10-membered saturated heterocyclyl which may or may not contain one further heteroatom moiety selected from O, S, Ci-C4-alkyl-N and R 3f - C(Y)-N as ring member, wherein R 3f is hydrogen or Ci-Cs-alkyl; and the stereoisomers, tautomers, N-oxides and agriculturally or veterinarily acceptable salts thereof.
  • the invention relates to acrylamide compounds of formula ⁇
  • Ci-C6-alkyl is hydrogen, Ci-C6-alkyl, C3-C7-cycloalkyl or C3-C7-cycloalkyl-Ci-C4-alkyl, wherein the three last mentioned radicals may be unsubstituted, or may be partially or fully halogenated,
  • R 3 is Ci-C6-alkoxy-Ci-C3-alkyl or C3-C7-cycloalkoxy-Ci-C3-alkyl;
  • Ci-C6-alkylene where an ethandiyl diradical within the Ci-C6-alkylene moiety may be replaced by a C3-C7-cycloalkandiyl diradical;
  • Z2, Z3, Z4, Z5, Z6 and Z7 which are as defined herein; is either CR'R m -(Ci-C4)-alkylene,
  • G' may also be a direct bond or a diradical CR'R m ,
  • R' and R m are independently of each other selected from hydrogen and Ci-C4-alkyl
  • a monospiro or dispiro 5- to 10-membered carbo- or heterocycle which may contain 1 or 2 heteroatom moieties independently selected from N-Ri, 0, and S(0)m as ring members, which monospiro or dispiro 5- to 10- membered carbo- or heterocycle is unsubstitued or may be substituted by
  • R 3 is not selected from hydrogen, Ci-C2-alkyl and Ci-C2-alkoxy-Ci-C2-alkyl,
  • R 1 may also be G"-Z1 , where Z1 is as defined herein and G" is Ci-Cs- alkylene;
  • R 2 , X and W are as defined herein; and the stereoisomers, tautomers, N-oxides and agriculturally or veterinarily acceptable salts thereof.
  • the present invention also relates to a method for combating or controlling invertebrate pests, which method comprises treating or contacting the pests, their food supply, their habitat or their breeding grounds with a pesticidally effective amount of a pyrazole compound of formulae I or ⁇ , or a salt thereof as defined herein.
  • the present invention also relates to a method for protecting growing plants or plant propagation materials (such as seed) from attack or infestation by invertebrate pests, which method comprises treating or contacting a plant, plant propagation material (such as seed), soil or water in which the plant is growing, with a pesticidally effective amount of a pyrazole compound of formulae I or ⁇ , or a salt thereof as defined herein.
  • the present invention also relates to plant propagation material, in particular seed, comprising at least one compound of formulae I or l'and/or an agriculturally acceptable salt thereof as defined herein.
  • the present invention also relates to the use of a compound of the formulae I or ⁇ , or an agriculturally acceptable salt thereof as defined herein, for protecting growing plants or plant propagation material from attack or infestation by invertebrate pests.
  • the present invention further relates to a method for treating or protecting animals from infestation or infection by parasites which comprises administering to the animals a parasiticidally effective amount of a compound of the formulae I or ⁇ , or a veterinarily acceptable salt thereof as defined herein.
  • the present invention further relates to the use of a compound of the formulae I or ⁇ , or a veterinarily acceptable salt thereof as defined herein, for combating parasites in and on animals.
  • the present invention further relates to a compound I or ⁇ , or a veterinarily acceptable salt thereof as defined herein, for preparing a medicament for treating animals infested or infected by parasites.
  • the present invention also relates to an agricultural or veterinary composition for com- bating animal pests comprising a pyrazole compound of formulae I or ⁇ , or a salt thereof as defined herein, and at least one inert liquid and/or solid agriculturally or veterinarily acceptable carrier and optionally at least one surfactant.
  • invertebrate pest also referred to as animal pests
  • animal pests encom- passes animal populations, such as insects, arachnids and nematodes, which may attack plants, thereby causing substantial damage to the plants attacked, as well as ectoparasites which may infest animals, in particular warm blooded animals such as e.g. mammals or birds, or other higher animals such as reptiles, amphibians or fish, thereby causing substantial damage to the animals infested.
  • compound(s) according to the invention or “compound(s) of formulae I or ⁇ ” 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.
  • stereoisomers encompasses both optical isomers, such as enantiomers or diastereomers, the latter existing due to more than one center of chirality in the molecule, as well as geometrical isomers (cis/trans isomers).
  • the compounds of formulae I or ⁇ may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • One center of chirality is the carbon atom carrying radicals R 3 , R 4 and R 5 .
  • the invention provides both the pure enantiomers or diastereomers and their mixtures and the use according to the invention of the pure enantiomers or diastereomers of the compound I or ⁇ or their mixtures.
  • Suitable compounds of the formulae I or ⁇ also include all possible geometrical stereoisomers (cis/trans isomers) and mixtures thereof.
  • N-oxide relates to a form of compounds I or ⁇ in which at least one nitrogen atom is present in oxidized form (as NO).
  • the compounds of the present invention may be amorphous or may exist in one ore more different crystalline states (polymorphs) which may have a different macroscopic properties such as stability or show different biological properties such as activities.
  • the present invention includes both amorphous and crystalline compounds of the formulae I or ⁇ , mixtures of different crystalline states of the respective compound I or ⁇ , as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formulae I or ⁇ are preferably agriculturally and veterinary acceptable salts. They can be formed in a customary method, e.g. by reacting the compound with an acid of the anion in question if the compound of formulae I or ⁇ has a basic functionality or by reacting an acidic compound of formulae I or ⁇ with a suitable base.
  • Suitable agriculturally acceptable salts are especially the salts of those cations or the acid addition salts of those acids whose cations and anions, respectively, do not have any adverse effect on the action of the compounds according to the present invention.
  • Suitable cations are in particular the ions of the alkali metals, preferably lithium, sodium and potassium, of the alkaline earth metals, preferably calcium, magnesium and barium, and of the transition metals, preferably manganese, copper, zinc and iron, and also ammonium (NH 4+ ) and substituted ammonium in which one to four of the hydrogen atoms are replaced by Ci-C4-alkyl, Ci-C4-hydroxyalkyl, Ci-C4-alkoxy, Ci-C4-alkoxy-
  • substituted ammonium ions comprise methylammonium, isopropylammonium, dimethylammo- nium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetrae- thylammonium, tetrabutylammonium, 2-hydroxyethylammonium, 2-(2-hydroxy- ethoxy)ethylammonium, bis(2-hydroxyethyl)ammonium, benzyltrimethylammonium and benzl-triethylammonium, furthermore phosphonium ions, sulfonium ions, preferably tri(Ci-C4-alkyl)sulfonium, and sulfoxonium ions, preferably tri(Ci-C4-alkyl)sul
  • Anions of useful acid addition salts are primarily chloride, bromide, fluoride, hydrogen sulfate, sulfate, dihydrogen phosphate, hydrogen phosphate, phosphate, nitrate, hydrogen carbonate, carbonate, hexafluorosilicate, hexafluorophosphate, benzoate, and the anions of Ci-C4-alkanoic acids, preferably formate, acetate, propionate and butyr- ate. They can be formed by reacting a compound of formulae I or ⁇ with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
  • Suitable acid addition salts e.g. formed by compounds of formulae I or ⁇ containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochlorids, sulphates, phosphates, and nitrates and salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • inorganic acids for example hydrochlorids, sulphates, phosphates, and nitrates
  • salts of organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • plant propagation material is to be understood to denote all the generative parts of the plant such as seeds and vegetative plant material such as cuttings and tubers (e. g. potatoes), which can be used for the multiplication of the plant. This in- eludes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants, including seedlings and young plants, which are to be transplanted after germination or after emergence from soil.
  • the plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting. Said young plants may also be protected before transplantation by a total or partial treatment by immersion or pouring.
  • plants comprises any types of plants including “non-cultivated plants” and in particular "cultivated plants”.
  • non-cultivated plants refers to any wild type species or related species or related genera of a cultivated plant.
  • cultiva plants is to be understood as including plants which have been modified by breeding, mutagenesis or genetic engineering including but not limiting to agricultural biotech products on the market or in development (cf.
  • Genetically modified plants are plants, whose genetic material has been modified by the use of recombinant DNA techniques in a way that is impossible under natural circumstances such as breeding, mutations or natural recombination.
  • one or more genes have been integrated into the genetic material of a genetically modified plant in order to improve certain properties of the plant.
  • Such genetic modifications also include but are not limited to targeted post-translational modification of protein(s), oligo- or polypeptides e. g. by gly- cosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties.
  • auxin herbicides
  • herbicides e. bromoxynil or ioxynil herbicides as a result of conventional methods of breeding or genetic engineering. Furthermore, plants have been made resistant to multiple classes of herbicides through multiple genetic modifications, such as resistance to both glyphosate and glufosinate or to both glyphosate and a herbicide from another class such as ALS inhibitors, HPPD inhibitors, auxin herbicides, or ACCase inhibitors.
  • ALS inhibitors e.g. described in Pest Managem. Sci.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more insecticidal proteins, especially those known from the bacterial genus Bacillus, particularly from Bacillus thuringiensis, such as ⁇ - endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), CryllA(b), CrylllA, CrylllB(bl ) or Cry9c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecti- cidal proteins of bacteria colonizing nematodes, e. g. Photorhabdus spp.
  • VIP1 , VIP2, VIP3 or VIP3A vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • toxins produced by fungi such Streptomy- cetes toxins, plant lectins, such as pea or barley lectins; agglutinins
  • proteinase inhibi- tors such as trypsin inhibitors, serine protease inhibitors, patatin, cystatin or papain inhibitors
  • ribosome-inactivating proteins (RIP) such as ricin, maize-RIP, abrin, luffin, saporin or bryodin
  • steroid metabolism enzymes such as 3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase, cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase
  • ion channel blockers such as block
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or otherwise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, e. g. WO 02/015701 ).
  • Further examples of such toxins or genetically modified plants capable of synthesizing such toxins are disclosed, e. g., in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/18810 und WO 03/52073.
  • the methods for producing such genetically modified plants are generally known to the per- son skilled in the art and are described, e. g.
  • insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins tolerance to harmful pests from all taxonomic groups of athropods, especially to beetles (Coeloptera), two-winged insects (Diptera), and moths (Lepidoptera) and to nematodes (Nematoda).
  • Genetically modified plants capable to synthesize one or more insecticidal proteins are, e.
  • WO 03/018810 MON 863 from Monsanto Europe S.A., Belgium (corn cultivars producing the Cry3Bb1 toxin), IPC 531 from Monsanto Europe S.A., Belgium (cotton cultivars producing a modified version of the CrylAc toxin) and 1507 from Pioneer Overseas Corporation, Belgium (corn cultivars producing the Cry1 F toxin and PAT enzyme).
  • plants are also covered that are by the use of recombinant DNA tech- niques capable to synthesize one or more proteins to increase the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called “ pathogenesis-related proteins” (PR proteins, see, e. g.
  • EP-A 392 225 plant disease resistance genes (e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum) or T4-lysozym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • plant disease resistance genes e. g. potato cultivars, which express resistance genes acting against Phytophthora infestans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lysozym e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora.
  • the methods for producing such genetically modified plants are generally known to the person skilled in the art and are described, e. g. in the publications men- tioned above.
  • plants are also covered that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to increase the productivity (e. g. bio mass production, grain yield, starch content, oil content or protein content), toler- ance to drought, salinity or other growth-limiting environmental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • productivity e. g. bio mass production, grain yield, starch content, oil content or protein content
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve human or animal nutrition, e. g. oil crops that produce health- promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape, DOW Agro Sciences, Canada).
  • plants are also covered that contain by the use of recombinant DNA techniques a modified amount of substances of content or new substances of content, specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • a modified amount of substances of content or new substances of content specifically to improve raw material production, e. g. potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato, BASF SE, Germany).
  • 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 -C m indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in par- ticular fluorine, chlorine or bromine.
  • alkyl as used herein and in the alkyl moieties of alkylthio (also referred to as alkylsulfanyl), alkylsulfinyl, and alkylsulfonyl 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, isopropyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1 - methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1 -ethyl propyl, n-hexyl, 1 ,1 -dimethylpropyl, 1 ,2-dimethylpropyl, 1 -methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1 ,1 -dimethylbutyl, 1 ,2-dimethylbutyl, 1 ,3-dimethylbutyl, 2,2- dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1 -ethylbutyl, 2-ethylbutyl, 1
  • alkylene (or alkanediyl) as used herein in each case denotes an alkyl radical as defined above, wherein one hydrogen atom at any position of the carbon backbone is replaced by one further binding site, thus forming a bivalent moiety.
  • haloalkyl as used herein and in the haloalkyl moieties of haloalkoxy, haloal- kylthio, haloalkylcarbonyl, haloalkylsulfinyl and haloalkylsulfonyl, denotes in each case a straight-chain or branched alkyl group having usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably from 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms.
  • Pre- ferred haloalkyl moieties are selected from Ci-C4-haloalkyl, more preferably from
  • Ci-C2-haloalkyl in particular from Ci-C2-fluoroalkyl such as fluoromethyl, difluorome- thyl, 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 at any position in the alkyl group and has usually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.
  • alkoxy group examples include methoxy, ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy, tert.-butyloxy and the like.
  • haloalkoxy denotes in each case a straight-chain or branched alkoxy group having from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms, wherein the hydrogen atoms of this group are partially or totally replaced with halogen atoms, in particular fluorine atoms.
  • Ci-C4-haloalkoxy moieties include Ci-C4-haloalkoxy, in particular Ci-C2-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy, 2-chloro-2,2-difluoro- ethoxy, 2,2dichloro-2-fluorethoxy, 2,2,2-trichloroethoxy, pentafluoroethoxy and the like.
  • Ci-C4-haloalkoxy such as fluoromethoxy, difluoromethoxy, trifluoromethoxy, 1 -fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy, 2,2,2-trifluoroethoxy, 2-chloro-2-fluoroeth
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkyl-alkyl, e.g. cycloalkyl-methyl, denotes in each case a mono- or bicyclic saturated carbocyclic radical having usually from 3 to 10, or preferably or 3 to 6 carbon atoms, such as cy- clopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, bicy- clo[2.1.1]hexyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.1 ]heptyl, and bicyclo[2.2.2]octyl and the like.
  • cycloalkenyl denotes in each case a partially unsaturated mono- or bicyclic carbocyclic radical having usually from 5 to 10, or preferably 5 to 8 carbon atoms, such as cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, bicy- clo[2.2.2]octenyl and the like.
  • halocycloalkyl as used herein and in the halocycloalkyl moieties of
  • C3-Cio-halocycloalkyl-methyl denotes in each case a mono- or bicyclic cycloaliphatic radical having usually from 3 to 10 carbon atoms or 3 to 6 carbon atoms, wherein at least one, e.g. 1 , 2, 3, 4 or 5 of the hydrogen atoms are replaced by halogen, in particular by fluorine or chlorine.
  • Examples are 1 - and 2-fluorocyclopropyl, 1 ,2-, 2,2- and 2,3-difluorocyclopropyl, 1 ,2,2-trifluorocyclopropyl, 2,2,3,3-tetrafluorocyclpropyl, 1 - and 2-chlorocyclopropyl, 1 ,2-, 2,2- and 2,3-dichlorocyclopropyl, 1 ,2,2-trichlorocyclopropyl, 2,2,3,3-tetrachlorocyclpropyl, 1 -,2- and 3-fluorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1 -,2- and 3-chlorocyclopentyl, 1 ,2-, 2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl and the like.
  • 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, propar- gyl (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 linear or branched alkyl having usually 1 to 4 carbon atoms, wherein 1 of those carbon atoms carries an alkoxy radical usually having 1 to 10, preferably 1 to 4 carbon atoms. Examples are CH2OCH3, CH2-OC2H5, n-propoxymethyl, CH2-OCH(CH3)2, n-butoxymethyl, (l -methylpropoxy)-methyl, (2-methylpropoxy)methyl, CH 2 -OC(CH 3 )3, 2-(methoxy)ethyl, 2-(ethoxy)ethyl,
  • haloalkylcarbonyl refers to an alkylcarbonyl group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • haloalkylthio refers to an alkylthio group as mentioned above, wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • di-(Ci-C4-alkyl)amino is a group -N(Ci-C4-alkyl)2. Examples are dimethyla- mino, diethylamino, ethylmethylamino, dipropylamino, diisopropylamino, methylpropyl- amino, methylisopropylamino, ethylpropylamino, ethylisopropylamino, dibutylamino and the like.
  • Ci-Cio-alkylsulfinyl preferably 1 to 4 carbon atoms
  • Ci-C4-alkylsulfinyl which is attached via the sulfur atom of a sulfinyl group at any position in the alkyl group.
  • haloalkylsulfinyl refers to a alkylsulfinyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • Ci-Cio-alkylsulfonyl preferably 1 to 4 carbon atoms
  • Ci-C4-alkylsulfonyl which is attached via the sulfur atom of a sulfonyl group at any position in the alkyl group.
  • haloalkylsulfonyl refers to an alkylsulfonyl group as mentioned above wherein the hydrogen atoms are partially or fully substituted by fluorine, chlorine, bromine and/or iodine.
  • heterocyclyl includes in general 3- to 8-membered, in particular 5- to 7- membered monocyclic heterocyclic non-aromatic radicals.
  • the heterocyclic non- aromatic radicals usually comprise 1 or 2 heteroatoms selected from N, O and S as ring members, where S-atoms as ring members may be present as S, SO or SO2.
  • the heterocyclic non-aromatic radicals may also comprise 1 or 2 carbonyl groups as ring members.
  • 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-oxothietanyl), thietanyl-S-dioxid (S-dioxothiethanyl), pyrrolidinyl, pyrrolinyl, py- razolinyl, tetrahydrofuranyl, dihydrofuranyl, 1 ,3-dioxolanyl, thiolanyl, S-oxothiolanyl, S-dioxothiolanyl, dihydrothienyl, S-oxodihydrothienyl, S-dioxodihydrothienyl, oxazoli- dinyl, oxazolinyl, thiazoliny
  • heterocyclic ring also comprising 1 or 2 carbonyl groups as ring members comprise pyrrolidin-2-only, pyrrolidin- 2,5-dionyl, imidazolidin-2-only, oxazolidin-2-only, thiazolidin-2-only and the like.
  • heteroaryl includes monocyclic 5- or 6-membered heteroaromatic radicals comprising as ring members 1 , 2, 3 or 4 heteroatoms selected from N, O and S. Examples of 5- or 6-membered heteroaromatic radicals include pyridyl, i.e. 2-, 3-, or
  • heteroaryl also includes bicyclic 8- to 10-membered heteroaromatic radicals comprising as ring members 1 , 2 or 3 heteroatoms selected from N, O and S, wherein a 5- or 6-membered heteroaromatic ring is fused to a phenyl ring or to a 5- or
  • 6- membered heteroaromatic radical examples include benzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl, benzoxathiazolyl, ben- zoxadiazolyl, benzothiadiazolyl, benzoxazinyl, chinolinyl, isochinolinyl, purinyl,
  • fused hetaryl radicals may be bonded to the remainder of the molecule via any ring atom of 5- or 6-membered heteroaromatic ring or via a carbon atom of the fused phenyl moiety.
  • cycloalkyl as used herein and in the cycloalkyl moieties of cycloalkoxy and cycloalkylmethyl denotes in each case a monocyclic cycloaliphatic radical having usu- ally from 3 to 6 carbon atom. Examples are cyclopropyl, cyclobutyl, cyclopentyl, and cyclohexyl.
  • cycloalkenyl denotes in each case a monocyclic monoun- saturated hydrocarbon groups having 5 or 6 carbon ring members. Examples are cy- clopenten-1 -yl, cyclopenten-3-yl, cyclohexen-1 -yl, cyclohexen-3-yl and cyclohexen-4-yl.
  • diispiro 5- to 10-membered carbocycle refers to a tricyclic ring system of 5-
  • dispiro[2.0.2.1 ]heptyl dispiro[2.0.3.1]octyl, dispiro[3.0.3.1]nonyl, dispiro[2.0.4.1 ]nonyl, dispiro[2.1.2.1 ]octyl, dispiro[2.1 .3.1]nonyl and dispiro[3.1 .3.1]decyl.
  • the term "monospiro or dispiro 5- to 10-membered heterocycle” refers to a bicyclic or tricyclic ring system of 5-, 6-, 7-, 8-, 9- or 10 ring atoms which has one or two spiroatoms.
  • the heterocyclic ring system usually comprise 1 or 2 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 are:
  • # denotes the attachment point to the remainder of the molecule.
  • the attachment point is not restricted to the ring on which is shown, but can be on either of the spiro rings, and may be on a carbon or on a nitrogen ring atom. If the rings carry one or more substituents, these may be bound to carbon and/or to nitrogen ring atoms.
  • R 2 is selected from halogen, Ci-C6-alkyl, Ci-C6-haloalkyl, C3-C7- cycloalkyl, C3-C7-halocycloalkyl, Ci-C6-alkoxy, Ci-C6-haloalkoxy, C3-C7-cycloalkyl-Ci- C 4 -alkyl and C3-C7-halocycloalkyl-Ci-C 4 -alkyl.
  • R 2 is selected from Ci-C 4 -alkyl, Ci-C 4 -haloalkyl, C3-C7-cycloalkyl and C3-C7-halocycloalkyl.
  • R 2 is selected from Ci-C2-alkyl, fluorinated C1-C2- alkyl and C3-C6-cycloalkyl, and specifically from methyl, cyclopropyl, CHF2 and CF3.
  • a particularly preferred embodiment of the invention relates to pyrazole compounds of the formula I, to their stereoisomers, salts, tautomers and N-oxides, and to the methods and uses of such compounds.
  • R 1 is selected from hydrogen, Ci-Cio-alkyl and C2-Cio-alkenyl, wherein the two last mentioned radicals may be unsubstituted, may be partially or fully halogenated or may carry 1 , 2 or 3 identical or different substituents selected from CN, Ci-C4-alkoxy, Ci-C 4 -haloalkoxy, Ci-C 4 -alkyl-S(0) m , Ci-C 4 -haloalkyl-S(0) m , C 3 -C 6 -cycloalkyl, 3- to 7- membered heterocyclyl, 5- or 6-membered hetaryl, phenyl and phenoxy, wherein the last five mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 radicals selected from halogen, CN, Ci-C 4 -alkyl, Ci-C 4 -haloalkyl
  • R 1 is further selected from C3-C6-cycloalkyl, 3- to 7-membered heterocyclyl, 5- to 6- membered hetaryl and phenyl, wherein the four last mentioned radicals may be unsubstituted or may carry 1 , 2, 3, 4 or 5 identical or different substituents selected from hal- ogen, N0 2 , CN, Ci-C 4 -alkyl, C 3 -C 6 -cycloalkyl, Ci-C 4 -haloalkyl, Ci-C 4 -alkoxy, Ci-C 4 - haloalkoxy, Ci-C 4 -alkylthio, Ci-C 4 -haloalkylthio, Ci-C 4 -alkylsulfonyl and Ci-C 4 - haloalkylsulfonyl,
  • R 1 is further selected from R 1a and d-Cs-alkylene-R 13 , wherein R 1a is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from NH, N-Ci-C2-alkyl, N-Ci-C2-haloalkyl, O, and S(0)m as ring members, which monospiro or dispiro 5- to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1 or 2 radicals selected from halogen, CN, Ci-C2-alkyl, Ci-C2-haloalkyl and Ci-C2-alkoxy.
  • R 1a is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from NH, N-Ci-C2-alkyl, N-Ci-C2-haloalkyl, O, and S
  • R 1 is selected from hydrogen, d-Cs-alkyl and C2-C6-alkenyl, wherein the two last mentioned radicals may be unsubstituted, may be partially or fully halogenated or may carry 1 or 2 identical or different substituents selected from CN, Ci-C 4 - alkoxy, Ci-C 4 -alkyl-S(0) m , Ci-C 4 -haloalkyl-S(0) m , C3-C6-cycloalkyl, 5- to 6-membered heterocyclyl, 5- or 6-membered hetaryl and phenyl, wherein the last four mentioned radicals may be unsubstituted or may carry 1 , 2, or 3 radicals selected from halogen, CN, Ci-C 2 -alkyl and Ci-C 2 -haloalkyl,
  • R 1 is further selected from C3-C6-cycloalkyl, 5- to 6-membered heterocyclyl, 5- to 6- membered hetaryl and phenyl, wherein the four last mentioned radicals may be unsubstituted or may carry 1 or 2 identical or different substituents selected from halogen, CN, Ci-C 2 -alkyl, Ci-C 2 -haloalkyl, Ci-C 2 -alkoxy and Ci-C 4 -haloalkoxy,
  • R 1 is further selected from R 1a and Ci-C3-alkylene-R 1a , wherein R 1a is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from NH and O as ring members, which monospiro or dispiro 5- to 10-membered carbo- or heterocycle is unsubstitued or may be substituted by 1 or 2 radicals selected from halogen, CN, Ci-C2-alkyl and Ci-C2-haloalkyl.
  • R 1 is selected from hydrogen, d-Cs-alkyl and C2-C6-alkenyl, wherein the two last mentioned radicals may be unsubstituted, may carry 1 , 2 or 3 sub- stituents selected from chlorine and fluorine or may carry 1 or 2 identical or different substituents selected from CN, methoxy, methyl-S(0) m , CHF 2 -S(0) m , CF 3 -S(0) m , C3- C6-cycloalkyl, 5- to 6-membered heterocyclyl, 5- or 6-membered hetaryl and phenyl, wherein the last four mentioned radicals may be unsubstituted or may carry 1 , 2, or 3 radicals selected from chlorine, CN and methyl,
  • R 1 is further selected from C3-C6-cycloalkyl, 5- to 6-membered heterocyclyl, 5- to 6- membered hetaryl and phenyl, wherein the four last mentioned radicals may be unsubstituted or may carry 1 or 2 identical or different substituents selected from chlorine, CN, methyl, OCHF 2 and OCF 3 .
  • R 1 is further selected from R 1a and Ci-C3-alkylene-R 1a , wherein R 1a is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 O atoms as ring members.
  • variable R 1 are selected from the radicals R 1 -1 , R 1 -2, R -3, R 1 -4, R -5, R 1 -6, R 1 -7, R -8, R 1 -9, R 1 -10, R 1 , R 1 -12, R -13, R 1 -14, R -15, R -16, R 1 -17, R -18, R 1 -19, R 1 -20, R 1 -21 , R -22, R -23, R 1 -24, R -25, R 1 -26, R 1 -27, R - 28, R 1 -29, R 1 -30, R 1 -31 , R 1 -32, R -33, R 1 -34, R -35, R 1 -36, R 1 -37, R -38, R 1 -39, R 1 -40, R 1 -4 1 -42 shown below:
  • R 3 is selected from Z, Ci-C4-alkylene-Z and C3-C6-cycloalkylene-Z, wherein Z is either a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from NH, N-Ci- C2-alkyl and O as ring members,
  • Z is selected from Z1 , Z2, Z3, Z4, Z5, Z6 and Z7, as defined herein,
  • R 3a , R 3b are independently of each other selected from Ci-C4-alkyl, Ci-C4-haloalkyl, C3- C7-cycloalkyl, C3-C7-halocycloalkyl, C3-C7-cycloalkyl-Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkoxy and di-(Ci-C4-alkyl)amino, and in particular selected from Ci- C 2 -alkyl, Ci-C 2 -haloalkyl, C 3 -C 6 -cycloalkyl, Ci-C 2 -alkoxy and di-(Ci-C 2 - alkyl)amino;
  • R 3c , R 3d , R 3e are independently of each other selected from Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C7-cycloalkyl, C3-C7-halocycloalkyl and C3-C7-cycloalkyl-Ci-C4-alkyl, and in particular selected from Ci-C 2 -alkyl, Ci-C 2 -haloalkyl and C3-C6-cycloalkyl;
  • U is an N-bound 5- to 7-membered saturated heterocyclyl which may or may not contain one further heteroatom moiety selected from O, S, Ci-C 2 -alkyl-N, formyl- N and Ci-C 2 -alkylcarbonyl-N as ring member, and in particular U is an N-bound 5-, 6- or 7-membered saturated heterocyclyl which may or may not contain one further heteroatom moiety selected from O, methyl-N and acyl-N as ring member; T is O or S.
  • R 3 is selected from Z' or Ci-C 2 -alkylene-Z', wherein Z' is selected from Z1 ', ⁇ 2', ⁇ 3', ⁇ 4', ⁇ 5', ⁇ 6', ⁇ 7', ⁇ 8, ⁇ 9 or Z10,
  • R 3a , R 3b are independently of each other selected from Ci-C2-alkyl, Ci-C2-haloalkyl, Ci- C2-alkoxy and di-(Ci-C2-alkyl)amino, and in particular selected from methyl, methoxy and di(methyl)N;
  • U 1 is CH 2 or CH 2 CH 2 and U 2 is selected from CH 2 , CH 2 CH 2 , O, methyl-N, ethyl-N and acetyl-N, and in particular U 1 is Chb provided that U 2 is CH2, or U 1 is CH2CH2 provided that U 2 is selected from CH2, O, methyl-N and acetyl-N; and
  • T is O or S.
  • Particularly preferred meanings of the variable R 3 are selected from the radicals Z-A.1 , Z-A.2, Z-A.3, Z-A.4, Z-A.5, Z-A.6, Z-A.7, Z-A.8, Z-A.9, Z-A.10, Z-A.1 1 , Z-A.12, Z-A.13, Z-A.14, Z-A.15, Z-A.16, Z-A.17, Z-A.18, Z-A.19, Z-A.20, Z-A.21 , Z-A.22, Z-A.23, Z-
  • radicals of formula A are A.1 to A.168, where the radicals R 1 and R 2 are as defined in any one of the 168 lines of table A.
  • cycPr in the above table A represents a cylcopropyl radical.
  • a particularly preferred embodiment of the present invention relates to compounds of the formula I and to their stereoisomers, salts, tautomers and N-oxides, wherein is selected from the radicals R 1 -1, R 1 -2, R 1 -3, R 1 -4, R 1 -5, R 1 -6, R 1 -7, R 1 -8, R 1 -9, R-10, R 1, R 1 -12, R-13, R 1 -14, R-15, R 1 -16, R 1 -17, R-18, R 1 -19, R 1 -20, R 1 - 21, R-22, R-23, R 1 -24, R-25, R 1 -26, R 1 -27, R-28, R 1 -29, R 1 -30, R 1 -31, R 1 -32, R 1 -33, R 1 -34, R-35, R 1 -36, R 1 -37, R-38, R 1 -39, R 1 -40, R 1 -41 and R 1 -42; is selected from Ci-
  • W is CH or N; and X is O or S.
  • Examples of compounds of this particularly preferred embodiment are the compounds as defined in the following tables 1 to 372.
  • Table 1 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.1 .
  • Table 2 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.2.
  • Table 3 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.3.
  • Table 4 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.4.
  • Table 5 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.5.
  • Table 6 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.6.
  • Table 7 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.7.
  • Table 8 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.8.
  • Table 9 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.9.
  • Table 10 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.10.
  • Table 1 1 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.1 1 .
  • Table 12 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.12.
  • Table 13 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.13.
  • Table 14 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.14.
  • Table 15 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.15.
  • Table 16 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.16.
  • Table 17 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.17.
  • Table 18 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.18.
  • Table 19 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.19.
  • Table 20 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.20.
  • Table 21 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.21 .
  • Table 22 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.22.
  • Table 23 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.23.
  • Table 24 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.24.
  • Table 25 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.25.
  • Table 26 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.26.
  • Table 27 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.27.
  • Table 28 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.28.
  • Table 29 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.29.
  • Table 30 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.30.
  • Table 31 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.31 .
  • Table 32 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.1.
  • Table 33 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.2.
  • Table 34 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.3.
  • Table 35 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.4.
  • Table 36 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.5.
  • Table 37 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.6.
  • Table 38 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.7.
  • Table 39 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.8.
  • Table 40 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.9.
  • Table 41 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.10.
  • Table 42 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.1 1 .
  • Table 43 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.12.
  • Table 44 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.13.
  • Table 45 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.14.
  • Table 46 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.15.
  • Table 47 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.16.
  • Table 48 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.17.
  • Table 49 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.18.
  • Table 50 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.19.
  • Table 51 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.20.
  • Table 52 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.21 .
  • Table 53 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.22.
  • Table 54 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.23.
  • Table 55 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.24.
  • Table 56 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.25.
  • Table 57 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.26.
  • Table 58 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.27.
  • Table 59 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.28.
  • Table 60 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.29.
  • Table 61 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.30.
  • Table 62 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.31 .
  • Table 63 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.1.
  • Table 64 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.2.
  • Table65 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.3.
  • Table 66 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.4.
  • Table 67 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.5.
  • Table 68 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.6.
  • Table 69 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.7.
  • Table 70 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.8.
  • Table 71 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.9.
  • Table 72 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C10.
  • Table 73 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.1 1.
  • Table 74 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.12.
  • Table 75 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.13.
  • Table 76 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.14.
  • Table 77 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.15.
  • Table 78 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C16.
  • Table 79 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.17.
  • Table 80 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.18.
  • Table 81 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.19.
  • Table 82 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.20.
  • Table 83 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.21.
  • Table 84 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.22.
  • Table 85 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.23.
  • Table 86 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.24.
  • Table 87 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.25.
  • Table 88 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.26.
  • Table 89 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.27.
  • Table 90 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.28.
  • Table 91 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.29.
  • Table 92 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.30.
  • Table 93 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.31.
  • Tables 94 to 186 Compounds of the formula I corresponding to compounds according to tables 1 to 93, with the exception that X is S.
  • Table 187 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.1 .
  • Table 188 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.2.
  • Table 189 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.3.
  • Table 190 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.4.
  • Table 191 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.5.
  • Table 192 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.6.
  • Table 193 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.7.
  • Table 194 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.8.
  • Table 195 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.9.
  • Table 196 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.10.
  • Table 197 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.1 1.
  • Table 198 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.12.
  • Table 199 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.13.
  • Table 200 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.14.
  • Table 201 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.15.
  • Table 202 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.16.
  • Table 203 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.17.
  • Table 204 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.18.
  • Table 205 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.19.
  • Table 206 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.20.
  • Table 207 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.21.
  • Table 208 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.22.
  • Table 209 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.23.
  • Table 210 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.24.
  • Table 21 1 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.25.
  • Table 212 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.26.
  • Table 213 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.27.
  • Table 214 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.28.
  • Table 215 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.29.
  • Table 216 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.30.
  • Table 217 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-A.31.
  • Table 218 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.1 .
  • Table 219 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.2.
  • Table 220 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.3.
  • Table 221 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.4.
  • Table 222 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.5.
  • Table 223 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.6.
  • Table 224 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.7.
  • Table 225 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.8.
  • Table 226 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.9.
  • Table 227 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.10.
  • Table 228 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.1 1.
  • Table 229 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.12.
  • Table 230 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.13.
  • Table 231 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.14.
  • Table 232 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.15.
  • Table 233 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.16.
  • Table 234 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.17.
  • Table 235 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.18.
  • Table 236 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.19.
  • Table 237 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.20.
  • Table 238 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.21.
  • Table 239 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.22.
  • Table 240 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.23.
  • Table 241 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.24.
  • Table 242 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.25.
  • Table 243 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.26.
  • Table 244 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.27.
  • Table 245 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.28.
  • Table 246 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.29.
  • Table 247 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.30.
  • Table 248 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-B.31.
  • Table 249 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.1.
  • Table 250 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.2.
  • Table 251 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.3.
  • Table 252 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.4.
  • Table 253 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.5.
  • Table 254 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.6.
  • Table 255 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.7.
  • Table 256 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.8.
  • Table 257 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.9.
  • Table 258 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.10.
  • Table 259 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.1 1 .
  • Table 260 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.12.
  • Table 261 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.13.
  • Table 262 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.14.
  • Table 263 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.15.
  • Table 264 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C16.
  • Table 265 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.17.
  • Table 266 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.18.
  • Table 267 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.19.
  • Table 268 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.20.
  • Table 269 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C21 .
  • Table 270 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.22.
  • Table 271 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.23.
  • Table 272 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.24.
  • Table 273 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.25.
  • Table 274 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.26.
  • Table 275 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.27.
  • Table 276 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.28.
  • Table 277 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.29.
  • Table 278 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.30.
  • Table 279 Compounds of the formula I and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A is a radical selected from radicals A.1 to A.168 and R 3 is Z-C.31 .
  • Tables 280 to 372 Compounds of the formula I corresponding to compounds according to tables 187 to 279, with the exception that X is S.
  • a further embodiment of the invention relates to pyrazole compounds of the formula ⁇ , to their stereoisomers, salts, tautomers and N-oxides, and to the methods and uses of such compounds.
  • R 3 is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6-cycloalkyl, C3-C6-halocycloalkyl, C3-C6-cycloalkyl-Ci-C3-alkyl, Ci-C4-alkoxy-Ci-C3-alkyl and C3-C6- cycloalkoxy-Ci-C2-alkyl.
  • R 3 is selected from hydrogen, Ci-C4-alkyl, Ci-C4-haloalkyl, C3-C6- cycloalkyl, Ci-C4-alkoxy-Ci-C3-alkyl and C3-C6-cycloalkoxy-Ci-C2-alkyl.
  • R 3 is selected from hydrogen, Ci-C4-alkyl and Ci-C3-alkoxy-Ci-C3-alkyl, and specifically from hydrogen, methyl, ethyl, methoxymethyl and ethoxymethyl.
  • G is Ci-C4-alkylene or C3-C6-cycloalkylene
  • Z a is selected from Z2, Z3, Z4, Z5, Z6 and Z7 which are as defined herein, wherein the variables R 3a , R 3c , R 3d , R 3e , U and T have the meanings given herein and in particular the meanings given as being preferred;
  • G' is either CR'R m -(Ci-C2)-alkylene, or, if R 3 is not selected from hydrogen, C1-C2- alkyl and Ci-C2-alkoxy-Ci-C2-alkyl, G' may also be a direct bond or a diradical CR'R m ,
  • R' and R m are independently of each other selected from hydrogen and Ci-C 2 -alkyl
  • Z b is a monospiro or dispiro 5- to 10-membered carbo- or heterocycle, which may contain 1 or 2 heteroatom moieties independently selected from NH, N-C1-C2- alkyl and O as ring members;
  • R 1 may also be G"-Z1 ,
  • G" is Ci-C 7 -alkylene and in particular is CR'R m -(Ci-C 2 )-alkylene or CR'R m with R' and R m being as defined herein, and wherein Z1 is as defined herein, wherein the variables R 3a and R 3b have the meanings given herein and in particular the meanings given as being preferred.
  • R 1' is Z a , CH n (CH 3 )2-n-Z a or CHn(CH 3 )2-n-CH2-Z c , or, if R 3' is not selected from hydrogen, Ci-C2-alkyl and Ci-C2-alkoxy-Ci-C2-alkyl, R 1 may also be CH n (CH 3 )2-n-Z1 or CHn(CH 3 )2-n-CH2-Z1 , where n is 0, 1 or 2, Z c is Z a or Z b , wherein the variables Z a , Z b and Z1 have the meanings given herein and in particular the meanings given as being preferred.
  • Z a is preferably selected from Z2', Z3 ⁇ Z4', Z5 ⁇ Z6' and Z7' which are as defined herein
  • Z b is preferably selected from Z8, Z9 and Z10 which are as defined herein
  • Z1 is preferably Z1 ' which is as defined herein.
  • 1' is selected from Z a , CH n (CH 3 )2-n-Z a and CHn(CH 3 )2-n-CH2-Z c , where n is 0, 1 or 2, and Z c is Z a or Z b , wherein Z a is selected from Z2', Z3', Z4', Z5', Z6' and Z7' which have the meanings given herein, in particular the meanings given as being preferred, and Z b is selected from Z8, Z9 and Z10 which are as defined herein.
  • variable R 1 are selected from the radicals Z- A.10, Z-A.1 1 , Z-A.12, Z-A.13, Z-A.14, Z-A.15, Z-A.16, Z-A.17, Z-A.18, Z-A.19, Z-A.20, Z-A.21 , Z-A.22, Z-A.23, Z-A.24, Z-A.25, Z-A.26, Z-A.27, Z-A.28, Z-B.10, Z-B.1 1 , Z- B.12, Z-B.13, Z-B.14, Z-B.15, Z-B.16, Z-B.17, Z-B.18, Z-B.19, Z-B.20, Z-B.21 , Z-B.22, Z-B.23, Z-B.24, Z-B.25, Z-B.26, Z-B.27, Z-B.28, Z-C.10
  • radicals of formula A' are AM to A'.568, where the radicals R 1 and R 2 are as defined in any one of the 568 lines of table A'.
  • a preferred embodiment of the present invention relates to compounds of the formula ⁇ and to their stereoisomers, salts, tautomers and N-oxides, wherein is selected from Z a , CH n (CH 3 ) 2 -n-Z a and CH n (CH 3 ) 2 -n-CH 2 -Z c , wherein n is 0, 1 or 2, and Z c is Z a or Z b , where Z a and Z b have the herein defined meanings, preferably Z a is Z2', Z3', Z4', Z5', Z6' or Z7' which are as defined herein, and Z b is Z8, Z9 or Z10 which are as defined herein; and in particular R 1 is selected from the radicals Z-A.10, Z-A.1 1 , Z-A.12, Z-A.13, Z-A.14, Z-A.15, Z-A.16, Z-A.17, Z-A.18, Z- A.19,
  • R 2 is selected from Ci-C2-alkyl, fluorinated Ci-C2-alkyl and C3-C6-cycloalkyl, and in particular R 2 is methyl, cyclopropyl, CHF2 or CF3;
  • R 3' is selected from selected from hydrogen, Ci-C 4 -alkyl and Ci-C3-alkoxy-Ci-C3- alkyl, and in particular R 3 is hydrogen, methyl, ethyl, methoxymethyl or ethoxymethyl;
  • W is CH or N
  • X is O or S.
  • Examples of compounds of this preferred embodiment are the compounds as defined in the following tables 373 to 387.
  • Table 373 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A' is a radical selected from radicals AM to A'.568 and R 3 is hydrogen.
  • Table 374 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A' is a radical selected from radicals AM to A'.568 and R 3' is methyl.
  • Table 375 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A' is a radical selected from radicals AM to A'.568 and R 3' is ethyl.
  • Table 376 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is CH, A' is a radical selected from radicals AM to A'.568 and R 3 is methoxymethyl.
  • Tables 378 to 382 Compounds of the formula ⁇ corresponding to compounds according to tables 373 to 377, with the exception that X is S.
  • Table 383 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A' is a radical selected from radicals AM to A'.568 and R 3 is hydrogen.
  • Table 384 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A' is a radical selected from radicals AM to A'.568 and R 3' is methyl.
  • Table 385 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A' is a radical selected from radicals AM to A'.568 and R 3' is ethyl.
  • Table 386 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A' is a radical selected from radicals AM to A'.568 and R 3 is methoxymethyl.
  • Table 387 Compounds of the formula ⁇ and the stereoisomers, salts, tautomers or N- oxide thereof, wherein X is O, W is N, A' is a radical selected from radicals AM to A'.568 and R 3 is ethoxymethyl.
  • Tables 383 to 387 Compounds of the formula ⁇ corresponding to compounds according to tables 378 to 382, with the exception that X is S.
  • the compounds of the formulae I or ⁇ 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 routes:
  • the compounds of the formulae I or ⁇ , wherein X is O can be prepared e.g. according to the method depicted in scheme 1 by reacting activated pyrazole carboxylic acid derivative III or III' with a 3-aminopyridine or 3-aminopyridazine compound II or ⁇ (see e.g. Houben-Weyl: "Methoden der organ. Chemie” [Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, New York 1985, Volume E5, pp.
  • Activated pyrazole carboxylic acid derivatives III or III' are, for example, halides, activated esters, anhydrides, azides, for example chlorides, fluorides, bromides, para-nitrophenyl esters, pentafluorophenyl esters, N-hydroxysuccinimides, hydroxybenzotriazol-1 -yl esters.
  • the radicals W, R 1 , R 1 , R 2 , R 3 and R 3 have the meanings given herein and in particular the meanings given as being preferred
  • L is a suitable leaving group such as halogen, N3, para-nitrophenoxy or pentafluorophenoxy etc.
  • the active compounds of the formulae I or ⁇ , wherein X is O can also be prepared, for example, by reacting the pyrazole carboxylic acid IV or IV with a 3-aminopyridine or 3-aminopyridazine compound II or II' in the presence of a coupling agent according to scheme 2.
  • a coupling agent according to scheme 2
  • the radicals W, R 1 , R 1 , R 2 , R 3 and R 3 have the meanings given above and in particular the meanings given as being preferred.
  • Suitable coupling agents are, for example:
  • N,N'-dicyclohexyl- carbodiimide for example N,N'-dicyclohexyl- carbodiimide [J.C. Sheehan, G.P. Hess, J. Am. Chem. Soc. 1955, 77, 1067], N-(3-dimethylaminopropyl)-N'-ethylcarbodiimide;
  • coupling agents which form mixed anhydrides with carbonic esters, for example 2- ethoxy-1 -ethoxycarbonyl-1 ,2-dihydroquinoline [B. Belleau, G. Malek, J. Amer. Chem. Soc. 1968, 90, 1651 ], 2-isobutyloxy-1 -isobutyloxycarbonyl-1 ,2- dihydroquinoline [Y. Kiso, H. Yajima, J. Chem. Soc, Chem. Commun. 1972, 942]; coupling agents based on phosphonium salts, for example (benzotriazol-1 - yloxy)tris(dimethylamino)phosphonium hexafluorophosphate [B. Castro, J.R.
  • the pyrazole carboxylic acids IV and IV and their activated derivatives III and III' as well as 3-aminopyridine or 3-aminopyridazine compounds II and ⁇ are known in the art or are commercially available or can be prepared by methods known from the literature.
  • a compound of the formulae I or ⁇ , wherein X is S can be prepared e.g. by reacting the corresponding compound of formulae I or ⁇ , wherein X is oxygen with 2,4-bis(4- methoxyphenyl)-1 ,3,2,4-dithiadiphosphetane-2,4-disulfide or phorphorus pentasulfide according to the method described by M.
  • the N-oxides of compounds of the formulae I or ⁇ can be prepared by oxidation of compounds I or ⁇ , respectively, according to standard methods of preparing pyridine N- oxides, e.g. by the method described by C. Botteghi et al. in Journal of Organometallic Chemistry 1989, 370, 17-31 .
  • the compounds of the formulae I or ⁇ can be prepared by the methods described above. If individual compounds can not be prepared via the above-described routes, they can be prepared by derivatization of other compounds of formulae I or ⁇ , or by customary modifications of the synthesis routes described.
  • certain compounds of formulae I or ⁇ can advantageously be prepared from other compounds of formulae I or ⁇ , e.g. by ester hydrolysis, amidation, esterification, ether cleavage, olefination, reduction, oxidation and the like.
  • 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 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 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, accord- ing 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 nem- atodes, and even more preferably from insects, acarids and nematodes. In the sense of the present invention, “invertebrate pests” are most preferably insects.
  • the invention further provides an agricultural composition for combating invertebrate pests, which comprises such an amount of at least one compound according to the invention and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
  • compositions may comprise a single active compound of the present invention or a mixture of several active compounds of the present invention.
  • the composition ac- cording to the present invention may comprise an individual isomer or mixtures of isomers or a salt as well as individual tautomers or mixtures of tautomers.
  • 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. 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, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Chei- matobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosel- la, Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta,
  • Cordylobia anthropophaga Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inornata, Culiseta melanura, Dacus cucurbi- tae, Dacus oleae, Dasineura brassicae, Delia antique, Delia coarctata, Delia platura, Delia radicum, Dermatobia hominis, Fannia canicularis, Geomyza Tripunctata, Gaster- ophilus intestinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hylemyia platura, Hypoderma lineata, Leptoconops torrens, Lirio
  • Dichromothrips corbetti Dichromothrips ssp., Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci, termites (Isoptera), e.g.
  • Calotermes flavicollis Leucotermes flavipes, Heterotermes aureus, Reticulitermes flavipes, Reticulitermes virginicus, Reticulitermes lucifugus, Re- ticulitermes santonensis, Reticulitermes grassei, Termes natalensis, and Coptotermes formosanus; cockroaches (Blattaria - Blattodea), e.g.
  • Blattella germanica Blattella asahinae, Peri- planeta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blatta orientalis; bugs, aphids, leafhoppers, whiteflies, scale insects, cicadas (Hemiptera), e.g.
  • Rhopalosiphum insertum Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Trialeurodes vaporariorum, Toxoptera au- rantiiand, Viteus vitifolii, Cimex lectularius, Cimex hemipterus, Reduvius senilis, Tria- toma spp., and Arilus critatus; ants, bees, wasps, sawflies (Hymenoptera), e.g.
  • 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, So- lenopsis xyloni, Pogonomyrmex barbatus, Pogonomyrmex californicus, Pheidole meg- acephala, Dasymutilla occidentalis, Bombus spp., Vespula squamosa, Paravespula vulgaris, Paravespula pennsylvanica, Paravespula germanica, Dolichovespula macula- ta, Vespa crabro
  • Argasidae Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Ambryomma maculatum, Argas persicus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Dermacentor andersoni, Dermacentor variabilis, Hy- alomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ixodes scapularis, Ixodes holo- cyclus, Ixodes pacificus, Ornithodorus moubata, Ornithodorus hermsi, Ornithodorus turicata, Ornithonyssus bacoti, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus sanguineus, Rhipicephal
  • Tarsonemidae spp. such as Phytonemus pallidus and Polyphagotarsonemus latus
  • Tenuipalpidae spp. such as Brevipalpus phoenicis
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ul- mi, Panonychus citri, and Oligonychus pratensis; Araneida, e.g. Latrodectus mactans, and Loxosceles reclusa; fleas (Siphonaptera), e.g.
  • Earwigs e.g. forficula auricularia, lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bo- vicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • collembola (springtails), e.g. Onychiurus ssp.
  • the compounds of the present invention are also suitable for controlling nematodes , especially 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; Sting nematodes, Belonolaimus longicaudat
  • the compounds of the present invention are particularly useful for controlling insects, preferably sucking or piercing and chewing and biting insects such as insects from the genera Ixodida, Si- phonaptera, Lepidoptera, Coleoptera and Hemiptera.
  • the invention also relates to agrochemical compositions comprising an auxiliary and at least one compound I or ⁇ according to the invention.
  • An agrochemical composition comprises a pesticidally effective amount of a compound I or ⁇ .
  • the term "effective amount” denotes an amount of the composition or of the compounds I or ⁇ , 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 or material. Such an amount can vary in a broad range and is dependent on various factors, such as the invertebrate (e.g. insect) species to be controlled, the treated cultivated plant or material, the climatic conditions and the specific compound I or ⁇ used.
  • invertebrate e.g. insect
  • 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 In- forma, London, 2005.
  • auxiliaries are solvents, liquid carriers, solid carriers or fillers, surfactants, dispersants, emulsifiers, wetters, adjuvants, solubilizers, penetration enhancers, protective colloids, adhesion agents, thickeners, humectants, repellents, at- tractants, 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, tetra- hydronaphthalene, 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, tetra- hydronaphthalene, alky
  • lactates carbonates, fatty acid esters, gamma-butyrolactone; fatty acids; phospho- nates; amines; amides, e.g. N-methylpyrrolidone, fatty acid dimethylamides; and mix- tures 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 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 alkylarylsulfonates, 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, sulfosuccin- ates or sulfosuccinamates.
  • Examples of sulfates are sulfates of fatty acids and oils, of ethoxylated alkylphenols, of alcohols, of ethoxylated 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, am- ides, 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 alkylpolyglucosides.
  • polymeric surfactants are home- or copolymers of vinylpyrrolidone, vinyl- alcohols, or vinylacetate.
  • Suitable cationic surfactants are quaternary surfactants, for example quaternary am- monium 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 pol- ybases. 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 activity themselves, and which improve the biological performance of the compound I or ⁇ on the target.
  • examples are surfactants, mineral or vegetable oils, and other auxi- laries. 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 hexacyanoferrate) 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 or ⁇ according to the invention 5-25 wt% of a compound I or ⁇ according to the invention and 1 -10 wt% dispersant (e. g. polyvinylpyrrolidone) are dissolved in up to 100 wt% organic solvent (e.g. cyclohexa- none). Dilution with water gives a dispersion.
  • dispersant e. g. polyvinylpyrrolidone
  • emulsifiers e.g. calcium dodecylbenzenesulfonate and castor oil ethoxylate
  • 20- 40 wt% water-insoluble organic solvent e.g. aromatic hydrocarbon
  • a compound I or ⁇ 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 or ⁇ 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 or ⁇ 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 or ⁇ 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 or ⁇ 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 %.
  • 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 or ⁇ 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 or ⁇ according to the invention, 0-40 wt% water insoluble organic solvent (e.g.
  • an isocyanate monomer e.g. diphenylmethene-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 or ⁇ 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 or ⁇ according to the invention is ground finely and associated with up to 100 wt% solid carrier (e.g. silicate).
  • Granulation is achieved by extru- sion, spray-drying or the fluidized bed.
  • compositions types i) to xiii) 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 in particular 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 or ⁇ 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 ⁇ 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.
  • amounts of active substance 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 seeds) 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 further 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 device, 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 e. g. components comprising compounds I or ⁇ and/or active substances from the groups M) or F) (see below), 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 or ⁇ and/or active substances from the groups M) or F) (see below), can be applied jointly (e.g. after tank mix) or consecutively.
  • the following categorized list M of pesticides represents insecticidal mixture partners, which are, whenever possible, classified according to the Insecticide Resistance Action Committee (IRAC), and together with which the compounds according to the present invention may be used.
  • IRAC Insecticide Resistance Action Committee
  • the combined use of the compounds of the present invention with the following pesticides may result in potential synergistic effects.
  • the following examples of insecticidal mixing partners are provided with the intention to illustrate the possible combinations, but not to impose any limitation to the obtainable mixtures:
  • Acetylcholine esterase (AChE) inhibitors from the class of
  • M.1 A carbamates for example aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pi- rimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb and triazamate; or from the class of
  • M.1 B organophosphates for example acephate, azamethiphos, azinphos-ethyl, az- inphosmethyl, cadusafos, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethopro- phos, famphur, fenamiphos, fenitrothion, fenthion, fosthiazate, heptenophos, imicyafos, isofenphos, isopropyl O- (methoxyaminothio-phosphoryl) salicylate, isoxathion, mala- thion, mecarbam, me
  • M.2A cyclodiene organochlorine compounds as for example endosulfan or chlordane; or
  • M.2B fiproles phenylpyrazoles
  • fipronil phenylpyrazoles
  • flufiprole pyra- fluprole
  • pyriprole phenylpyrazoles
  • M.3A pyrethroids for example acrinathrin, allethrin, d-cis-trans allethrin, d-trans alle- thrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyper- methrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta- cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fenvalerate
  • Nicotinic acetylcholine receptor agonists from the class of
  • M.4A neonicotinoids for example acteamiprid, chlothianidin, dinotefuran, imidacloprid, nitenpyram, thiacloprid and thiamethoxam; or
  • M.7A juvenile hormone analogues as hydroprene, kinoprene and methoprene; or oth- ers as
  • M.8A alkyl halides as methyl bromide and other alkyl halides, or
  • M.1 1 Microbial disruptors of insect midgut membranes, for example bacillus thurin- giensis 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. tenebri- onis, or the Bt crop proteins: CrylAb, CrylAc, Cryl Fa, Cry2Ab, mCry3A, Cry3Ab, Cry3Bb and Cry34/35Ab1 ;
  • M.12 Inhibitors of mitochondrial ATP synthase for example
  • 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, for example chlorfenapyr, DNOC or sulfluramid;
  • Nicotinic acetylcholine receptor (nAChR) channel blockers for example nereis- toxin analogues as bensultap, cartap hydrochloride, thiocyclam or thiosultap sodium;
  • Ecdyson receptor agonists such as diacylhydrazines, for example methoxyfeno- zide, tebufenozide, halofenozide, fufenozide or chromafenozide;
  • Octopamin receptor agonists as for example amitraz
  • M.21A METI acaricides and insecticides such as fenazaquin, fenpyroximate, pyrimidif- en, pyridaben, tebufenpyrad or tolfenpyrad, or
  • M.22B metaflumizone M.23 Inhibitors of the of acetyl CoA carboxylase, such as Tetronic and Tetramic acid derivatives, for example spirodiclofen, spiromesifen or spirotetramat;
  • M.24A phosphine such as aluminium phosphide, calcium phosphide, phosphine or zinc phosphide, or
  • Mitochondrial complex II electron transport inhibitors such as beta-ketonitrile derivatives, for example cyenopyrafen or cyflumetofen;
  • flubendiamide for example flubendiamide, chloranthraniliprole (rynaxypyr®), cyanthraniliprole
  • M.26.4 methyl-2-[3,5-dibromo-2-( ⁇ [3-bromo-1 -(3-chlorpyridin-2-yl)-1 H-pyrazol-5- yl]carbonyl ⁇ amino)benzoyl]-1 ,2-dimethylhydrazinecarboxylate;
  • M.X insecticidal active compounds of unknown or uncertain mode of action as for example azadirachtin, amidoflumet, benzoximate, bifenazate, bromopropylate, chinome- thionat, cryolite, dicofol, flufenerim, flometoquin, fluensulfone, flupyradifurone, piperonyl butoxide, pyridalyl, pyrifluquinazon, sulfoxaflor, or the compound
  • M.X.2 cyclopropaneacetic acid, l .l'- S ⁇ R ⁇ aR.eS.eaS. ⁇ R. ⁇ aS. ⁇ bSH-I ⁇ - cyclopropylacetyl)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, or the compound
  • M.X.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).
  • the commercially available compounds of the group M listed above may be found in The Pesticide Manual, 15th Edition, C. D. S. Tomlin, British Crop Protection Council (201 1 ) among other publications.
  • the phthalamides M.26.1 and M.26.2 are both known from WO 2007/101540.
  • the an- thranilamide M.26.3 has been described in WO2005/077943.
  • the hydrazide compound M.26.4 has been described in WO 2007/043677.
  • the quinoline derivative flometoquin is shown in WO2006/013896.
  • the aminofuranone compounds flupyradifurone is known from WO 2007/1 15644.
  • the sulfoximine compound sulfoxaflor is known from
  • Inhibitors of complex III at Qo site e.g. strobilurins
  • strobilurins azoxystrobin, coumethoxystrobin, coumoxystrobin, dimoxystrobin, ene- stroburin, fluoxastrobin, kresoxim-methyl, metominostrobin, orysastrobin, picoxystrobin, pyraclostrobin, pyrametostrobin, pyraoxystrobin, pyribencarb, triclopyricarb/chlorodin- carb, 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;
  • Inhibitors of complex II e.g. carboxamides
  • carboxanilides benodanil, bixafen, boscalid, carboxin, fenfuram, fenhexamid, fluopy- ram, flutolanil, furametpyr, isopyrazam, isotianil, mepronil, 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 pyra- zole-4-carboxamide and N-(2-(1 ,3,3-trimethyl-butyl)-phenyl)-1
  • Inhibitors of complex III at Qi site cyazofamid, amisulbrom;
  • nitrophenyl derivates binapacryl, dinobuton, dinocap, fluazinam, nitrthal-isopropyl, organometal compounds: fentin salts, such as fentin-acetate, fentin chloride or fentin hydroxide;
  • F.II-1 C14 demethylase inhibitors (DMI fungicides, e.g. triazoles, imidazoles) triazoles: azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, diniconazole, diniconazole-M, epoxiconazole, fenbuconazole, fluquinconazole, flusi- lazole, flutriafol, hexaconazole, imibenconazole, ipconazole, metconazole, myclobu- tanil, paclobutrazole, penconazole, propiconazole, prothioconazole, simeconazole, tebuconazole, tetraconazole, triadimefon, triadimenol, triticonazole, uniconazole; imidazoles: imazalil, pefurazoate,
  • pyrimidines, pyridines and piperazines fenarimol, nuarimol, pyrifenox, triforine;
  • morpholines aldimorph, dodemorph, dodemorph-acetate, fenpropimorph, tridemorph;
  • piperidines fenpropidin, piperalin;
  • spiroketalamines spiroxamine
  • phenylamides or acyl amino acid fungicides benalaxyl, benalaxyl-M, kiralaxyl, met- alaxyl, metalaxyl-M (mefenoxam), ofurace, oxadixyl;
  • isoxazoles and iosothiazolones hymexazole, octhilinone;
  • 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
  • benzamides and phenyl acetamides diethofencarb, ethaboxam, pencycuron, fluopico- lide, zoxamide;
  • Actin inhibitors benzophenones: metrafenone;
  • anilino-pyrimidines cyprodinil, mepanipyrim, nitrapyrin, pyrimethanil;
  • F.V-2 Protein synthesis inhibitors (anilino-pyrimidines)
  • antibiotics blasticidin-S, kasugamycin, kasugamycin hydrochloride-hydrate, mildiomy- cin, streptomycin, oxytetracyclin, polyoxine, validamycin A; F.VI) Signal transduction inhibitors
  • MAP / Histidine kinase inhibitors e.g. anilino-pyrimidines
  • dicarboximides fluoroimid, iprodione, procymidone, vinclozolin;
  • phenylpyrroles fenpiclonil, fludioxonil;
  • F.VI-2 G protein inhibitors: quinolines: quinoxyfen;
  • organophosphorus compounds edifenphos, iprobenfos, pyrazophos;

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Abstract

Cette invention concerne un composé de pyrazole de formules (I) ou (I'), ou un stéréoisomère, un sel, un tautomère ou un N-oxyde de celui-ci. Cette invention concerne également des méthodes et des utilisations de ces nouveaux composés 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. Des méthodes et des utilisations de ces nouveaux composés pour lutter contre les parasites dans ou sur les animaux, et pour empêcher ces animaux d'être infestés ou infectés par des parasites sont en outre décrites.
PCT/EP2013/072113 2012-10-24 2013-10-23 Composés de pyrazole pour lutter contre les ravageurs invertébrés WO2014064129A1 (fr)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015169734A1 (fr) * 2014-05-05 2015-11-12 Basf Se Pyrazoles pour la lutte contre les invertébrés nuisibles
WO2015189080A1 (fr) * 2014-06-12 2015-12-17 Basf Se Mélanges à activité pesticide
JP2016204599A (ja) * 2015-04-28 2016-12-08 旭化成株式会社 熱可塑性樹脂組成物及びその成形体
WO2018041665A1 (fr) * 2016-08-30 2018-03-08 Basf Se Méthode de lutte contre des ravageurs dans les plantes modifiées
WO2018165227A1 (fr) * 2017-03-10 2018-09-13 Wto Investments, Llc Stations d'appât pour mouches piqueuses à la recherche de sang et procédés associés

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009027393A2 (fr) * 2007-08-27 2009-03-05 Basf Se Composés de pyrazole permettant de lutter contre les nuisibles invertébrés
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009027393A2 (fr) * 2007-08-27 2009-03-05 Basf Se Composés de pyrazole permettant de lutter contre les nuisibles invertébrés
WO2010034737A1 (fr) * 2008-09-24 2010-04-01 Basf Se Composés de pyrazole pour la lutte contre des parasites invertébrés

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2015169734A1 (fr) * 2014-05-05 2015-11-12 Basf Se Pyrazoles pour la lutte contre les invertébrés nuisibles
WO2015189080A1 (fr) * 2014-06-12 2015-12-17 Basf Se Mélanges à activité pesticide
JP2016204599A (ja) * 2015-04-28 2016-12-08 旭化成株式会社 熱可塑性樹脂組成物及びその成形体
WO2018041665A1 (fr) * 2016-08-30 2018-03-08 Basf Se Méthode de lutte contre des ravageurs dans les plantes modifiées
CN109640663A (zh) * 2016-08-30 2019-04-16 巴斯夫欧洲公司 防治修饰植物中的害虫的方法
WO2018165227A1 (fr) * 2017-03-10 2018-09-13 Wto Investments, Llc Stations d'appât pour mouches piqueuses à la recherche de sang et procédés associés

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