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WO2010070035A1 - Thiourea compounds for combating invertebrate pests - Google Patents

Thiourea compounds for combating invertebrate pests Download PDF

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Publication number
WO2010070035A1
WO2010070035A1 PCT/EP2009/067382 EP2009067382W WO2010070035A1 WO 2010070035 A1 WO2010070035 A1 WO 2010070035A1 EP 2009067382 W EP2009067382 W EP 2009067382W WO 2010070035 A1 WO2010070035 A1 WO 2010070035A1
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Prior art keywords
alkyl
phenyl
alkoxy
membered
halogen
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French (fr)
Inventor
Markus Kordes
Ronan Le Vezouet
Ralph Paulini
Deborah L. Culbertson
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BASF SE
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BASF SE
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C335/00—Thioureas, i.e. compounds containing any of the groups, the nitrogen atoms not being part of nitro or nitroso groups
    • C07C335/04—Derivatives of thiourea
    • C07C335/06—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms
    • C07C335/10—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton
    • C07C335/12—Derivatives of thiourea having nitrogen atoms of thiourea groups bound to acyclic carbon atoms of an unsaturated carbon skeleton the carbon skeleton containing six-membered aromatic rings
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/78—Carbon atoms having three bonds to hetero atoms, with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D213/79—Acids; Esters
    • C07D213/80—Acids; Esters in position 3

Definitions

  • the present invention relates to thiourea compounds which can be used for combating or controlling invertebrate pests, in particular arthropod pests and nematodes.
  • the invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural composition comprising said compounds.
  • Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, 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, in particular insects, arachnids and nematodes.
  • the WO 2005/063724 describes 1-(azolin-2-yl)amino-1 ,2-diphenylethane compounds of the general formulae B.1 and B.2,
  • WO 2006/125745 describes 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests, in particular insects, arachnids or nematodes. However, there activity is not always satisfactory.
  • the invention relates to the use of compounds of formula I
  • n 0, 1 , 2, 3, 4 or 5;
  • n 0, 1 , 2, 3, 4 or 5;
  • X is a single bond, -C(O)- or -C(S)-;
  • Y is Ci-Cio-alkyl, C2-Cio-alkenyl, C4-Cio-alkadienyl, C2-Cio-alkynyl, where the four last-mentioned groups may be unsubstituted, partially or fully halogenated or may carry 1 , 2 or 3 radicals R y , where R y is CN, OR y1 , -SR y2 , -S(O) 2 R y2 , -NR y3 R y4 , -C(O)R y5 , C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl, where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or
  • Y may be further C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-C12- cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R
  • Y may be further NR y6 R y7 , P(O)R y8 R y9 , P(S)R y10 R y11 , SO 2 R y12 or SiR y13 R y14 R y15 ,
  • R y1 is hydrogen, Ci-C 8 -alkyl, Ci-C 8 -haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C2-C 8 -alkynyl, C2-C8-haloalkynyl, Ci-Cs-alkylcarbonyl, Ci-Cs- haloalkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-haloalkenylcarbonyl, C2-C8- alkynylcarbonyl, C2-C8-haloalkynylcarbonyl,
  • R y2 hydrogen, Ci-C 8 -alkyl, d-Cs-haloalkyl, C 2 -C 8 -alkenyl, C 2 -C 8 -haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl, or 5- to 10-membered hetaryl, wherein the six last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R yy and where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members
  • R y3 has one of the meanings given for R y1 and may also be d-Cs-alkoxy or
  • R y4 has one of the meanings given for R y1 , or
  • R y3 and R y4 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-C ⁇ -alkyl, Ci-C6-alkoxy,Ci- C ⁇ -haloalkyl, C-i-C ⁇ -haloalkoxy;
  • R y5 has one of the meanings given for R y2 , and may also be hydroxy, Ci-Cs- alkoxy, Ci-Cs-haloalkoxy, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8- alkynyloxy, C2-C8-haloalkynyloxy, C3-Ci2-cycloalkyloxy, C3-C12- cycloalkenyloxy, phenyloxy, naphthyloxy, 5- to 10-membered heterocyclyl- oxy or 5- to 10-membered hetaryloxy, wherein the six last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals R yy and where 5- to 10-membered heterocyclyloxy and 5- to 10- membered hetaryloxy contain 1 , 2, 3 or 4 heteroatoms selected independ- ently from one another from O, S
  • R y6 has one of the meanings given for R y3 ;
  • R y7 has one of the meanings given for R y1 or
  • R y6 and R y7 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-C ⁇ -alkyl, Ci-C6-alkoxy,Ci- C ⁇ -haloalkyl and Ci-C ⁇ -haloalkoxy;
  • R y8 and R y9 are in each case independently of one another selected from hydrogen, hydroxy, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Ci-C ⁇ -alkyl, Ci-C ⁇ - alkoxy, d-C ⁇ -alkylthio, C3-Ci2-cycloalkyl, phenyl, phenyl-Ci-C4-alkyl,
  • R y10 and R y11 have in each case independently of one another one of the mean- ings given for Rv 8 and R y9 ;
  • R y12 is hydroxy, d-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, d-C ⁇ -haloalkyl, phenyl, phenoxy and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moiety of phenoxy and phenyl-Ci-C4-alkyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy;
  • R y13 , R y14 and R y15 are in each case independently of one another selected from Ci-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, phenyl and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moiety of phenyl-Ci-C4-alkyl may be unsubstituted or substi- tuted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl and C1-C4- alkoxy;
  • R yy is selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-C ⁇ -alkyl, d-Ce-alkoxy, d-C 6 -haloalkoxy, Ci-C 6 -haloalkyl, Ci-C 6 -alkylthio, Ci-C 6 - haloalkylthio, d-C ⁇ -alkylsulfonyl, Ci-C6-haloalkylsulfonyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy, carboxyl, Ci-C6-alkoxycarbonyl and Cs-Cs-cycloalkyl;
  • R yyy is selected from the group consisting of halogen, cyano, nitro, OR y1 , -SR y2 , -S(O) 2 R y2 , -NR y3 R y4 , -C(O)R y5 , Ci-C 6 -alkyl, d-C ⁇ -haloalkyl, C 2 -C 6 -alkenyl,
  • R 1 and R 2 are each independently halogen, OH, SH, NH 2 , SO 3 H, COOH, cyano, nitro, d-C ⁇ -alkyl, Ci-C ⁇ -alkoxy, Ci-C ⁇ -alkylamino, di(Ci-C6-alkyl)amino, d-Cs-alkylthio, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6- alkynyl, C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, Ci-C ⁇ - alkylsulfonyl, d-C ⁇ -alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, formyl
  • R a1 and R a2 are each independently hydrogen, d-C ⁇ -alkyl, C2-C6-alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkoxy and d-C ⁇ -alkylthio,
  • Z is a single bond, oxygen, sulfur, d-C ⁇ -alkanediyl or d-C ⁇ -alkanediyloxy,
  • Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered heteroaro- matic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d- C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkyl, C-i-C ⁇ -haloalkoxy, Ci-C6-alkylthio and d-C ⁇ -haloalkylthio; and
  • Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkyl, d-C ⁇ -haloalkoxy, d-Ce-alkylthio and d-C 6 -haloalkylthio;
  • R 1 or R 2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-C ⁇ -alkyl, d-C ⁇ -alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-C ⁇ -haloalkoxy, d-Ce-alkylthio, d-C 6 -haloalkyl and (
  • invertebrate pests in particular arthropod pests and/or nematodes.
  • Another object of the present invention is the use of the compounds of formula I as defined above and/or a veterinarily acceptable salt thereof for treating or protecting an animal from infestation or infection by invertebrate parasites.
  • the present invention also provides an agricultural composition comprising at least one thiourea compound of the formula I as defined herein and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
  • 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, cul- tivated 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 thiourea compound of formula I 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 formula I and/or an agriculturally acceptable salt thereof as defined herein.
  • the present invention further relates to a method for treating or protecting an animal from infestation or infection by invertebrate parasites which comprises bringing the ani- mal in contact with a parasiticidally effective amount of a thiourea compound of the formula I or a veterinarily acceptable salt thereof as defined herein. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal.
  • the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers.
  • 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 its mixtures.
  • Suitable compounds of the formula I also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.
  • 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 formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
  • Salts of the compounds of the formula I are preferably agriculturally and veterinarily 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 formula I has a basic functionality or by reacting an acidic compound of formula I 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- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl.
  • substi- tuted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammonium, 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)sulfoxonium.
  • 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 bu- tyrate. They can be formed by reacting a compound of formulae I 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 formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochloride, 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 hydrochloride, sulphates, phosphates, and nitrates
  • organic acids for example acetic acid, maleic acid, dimaleic acid, fumaric acid, difumaric acid, methane sulfenic acid, methane sulfonic acid, and succinic acid.
  • invertebrate pest encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants thereby causing substan- tial 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.
  • plant propagation material as used herein includes 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.
  • seed- lings and young plants which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
  • 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 as used herein includes plants which have been modified by breeding, mutagenesis or genetic engineering.
  • Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross 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-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g.
  • cultiva plants as used herein further includes plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g.
  • HPPD hy- droxy-phenylpyruvate dioxygenase
  • ALS acetolactate synthase
  • sulfonyl ureas see e. g.
  • EP-A-0242236, EP-A-242246) or oxynil herbicides see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering.
  • mutagenesis for example Clearfield ® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox.
  • cultiva plants as used herein further includes plants 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 bacil- lus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), Cry- IIA(b), CrylllA, CrylllB(bi ) or Cry ⁇ c; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp.
  • VIP vegetative insecticidal proteins
  • toxins produced by animals such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins
  • tox- ins produced by fungi such Streptomycetes toxins, plant lectins, such as pea or barley lectins
  • proteinase inhibitors 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 blockers of sodium
  • these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or other- wise modified proteins.
  • Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ).
  • Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073.
  • cultivars as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to in- crease the resistance or tolerance of those plants to bacterial, viral or fungal pathogens.
  • proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (e. g. potato cultivars capable of synthesizing these proteins with increased resistance against bacteria such as Erwinia amylvora).
  • PR proteins pathogenesis-related proteins
  • plant disease resistance genes for example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum
  • T4-lyso-zym e.
  • cultivadas plants as used herein further includes plants 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), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
  • cultivadas plants as used herein further includes plants 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, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera ® rape).
  • cultiva plants as used herein further includes plants 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, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora ® potato).
  • the organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members.
  • the prefix C n -Cm indicates in each case the possible number of carbon atoms in the group.
  • halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine.
  • Ci-Cio-alkyl as used herein and in the alkyl moieties of alkoxy, alkylamino, dialkylamino, alkylthio, alkylcarbonyl, alkoxycarbonyl and the like refers to saturated straight-chain or branched hydrocarbon radicals having 1 to 2, 1 to 4, 1 to 6, 1 to 8 or 1 to 10 carbon atoms.
  • Ci-C2-Alkyl is methyl or ethyl.
  • Ci-C 4 -AIkVl is additionally also, for example, propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 ,1-dimethylethyl (tert-butyl).
  • Ci-C ⁇ -Alkyl is additionally also, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 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 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2- methylpropyl.
  • d-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2-ethylhexyl and positional isomers thereof.
  • Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl and positional isomers thereof.
  • Ci-Cio-haloalkyl refers to straight-chain or branched alkyl groups having 1 to 2, 1 to 4, 1 to 6, 1 to 8 or 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloro- methyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl,
  • C2-Cio-alkenyl refers to monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 3 to 8, 2 to 10 or 3 to 10 carbon atoms and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1- methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1- propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1- methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-1-butenyl, 1- methyl-2-butenyl, 2-methyl-2-buteny
  • C4-Cio-alkadienyl refers to doubly unsaturated straight-chain or branched hydrocarbon radicals having 4 to 6, 4 to 8 or 4 to 10 carbon atoms and two double bonds in any position, but preferably not cumulated, for example 1 ,3- butadienyl, 1-methyl-1 ,3-butadienyl, 2-methyl-1 ,3-butadienyl, penta-1 ,3-dien-1-yl, hexa- 1 ,4-dien-1-yl, hexa-1 ,4-dien-3-yl, hexa-1 ,4-dien-6-yl, hexa-1 ,5-dien-1-yl, hexa-1 ,5-dien- 3-yl, hexa-1 ,5-dien-4-yl, hepta-1 ,4-dien-1-yl, hepta-1 ,4-dien-3-yl,
  • C2-Cio-haloalkenyl as used herein and the haloalkenyl moieties in haloal- kenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
  • C2-Cio-alkynyl as used herein and the alkynyl moieties in alkynyloxy, al- kynylcarbonyl and the like refers to straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6, 2 to 8, 3 to 8, 2 to 10 or 3 to 10 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3- methyl-1-butynyl, 1 ,1-dimethyl-2-propynyl, 1-
  • C2-Cio-haloalkynyl as used herein and the haloalkynyl moieties in haloal- kynyloxy, haloalkynylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms, frequently 3 to 4, 3 to 6, 3 to 8 or 3 to 10 carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl.
  • Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
  • C3-Ci2-halocycloalkyl as used herein and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like refers to mono- or bi- or polycyclic saturated hydrocarbon groups having 3 to 6, 3 to 8 or 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
  • aryl refers to carbocyclic aromatic radicals having 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracenyl and phenanthrenyl.
  • aryl is phenyl.
  • the term "5- to 10-membered heterocyclyl ( 5-, 6-, 7-, 8-, 9- or 10- membered heterocyclyl)" as used herein includes in general 5-, 6-, 7- or 8-membered monocyclic heterocyclic radicals and 8- , 9- or 10- membered bicyclic heterocyclic radicals, the mono- and bicyclic radicals may be saturated or unsaturated.
  • the mono- and bicyclic heterocyclic radicals usually comprise 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally 1 or 2 carbonyl groups as ring members.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member:
  • Examples of 5- to 10-membered heterocyclyl include: five- or six-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen (as N or NR) and sulfur and: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms and optionally 1 or 2 carbonyl groups, for example 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 3-tetrahydrofuran-2-onyl, 4-tetrahydrofuran-2-onyl, 5-tetrahydrofuran- 2-onyl, 2-tetrahydrofuran-3-onyl, 4-tetrahydrofuran-3-onyl, 5-tetrahydrofuran-3-onyl, 2-tetrahydrothienyl, 3-tetrahydrothieny
  • seven-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur as ring members: for example mono- and bicyclic heterocycles having 7 ring members which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -A-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl,
  • the term "mono- or bicyclic 5- to 10-membered heteroaromatic ring” as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, wich may comprise a fused 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4 of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • the fused ring comprises Cs- C7-cycloalkyl, Cs-Cz-cycloalkenyl, or 5 to 7 membered heterocyclyl and phenyl.
  • hetaryl "heteroaryl"
  • hetaryl refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a a benzene ring, a saturated or partially unsaturated 5-, 6-, or 7-membered carbo- cycle or a 5-, 6-, or 7-membered heterocycle thus having a total number of ring members from 8, 9 or 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur.
  • the hetaryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
  • Examples for monocyclic 5-membered hetaryl which contains one oxygen atom, or one sulfur atome, or one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and one sulfur or oxygen atom include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2- pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5- oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1 ,3,4-triazol- 2-yl.
  • Examples for monocyclic 6-membered hetaryl which contains one, two or three or one, two, three or four nitrogen atoms in addition to carbon atoms as ring members are 2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4- pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
  • Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, ben- zo[b]thiazolyl, benzoxazolyl, and benzimidazolyl.
  • fused 5- to 7- membered heterocycle which contains 1 , 2, 3 or 4 heteroa- toms selected from O, S and N as ring members
  • fused 5- to 7- membered heterocycle which contains 1 , 2, 3 or 4 heteroa- toms selected from O, S and N as ring members
  • monocyclic heteroaromatic rings having 5 or 6 ring members and nonaromatic saturated or partially unsaturated heterocyclic rings having 5, 6 or 7 ring members.
  • non-aromatic rings include saturated 5-, 6-, or 7-membered heterocycles such as tetrahydrofuran, tetrahydropyran, piperidine, pyrrolidine, oxazolidine, isoxazolidine, thiazolidine, diox- ane, morpholine, dithiane, pyrazolidine, thiomorpholine, piperazine, imidazolidine, di- oxolane, thrithiane, pyrroline, oxazoline, imidazoline, pyrazoline, thiazoline, pyran, di- hydropyran, tetrahydropyridine, dihydropyridine, thiopyran, dihydrothiopyran, dihy- drothiine, tetrahydroazepine, dihydroazepine, tetrahydrooxepine, dihydrooxepine, tet- rahydo
  • 5-or 6- membered heteroaromatic rings examples include pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, isothiazole, thiodiazole, furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazole and tetrazine.
  • linear d-C ⁇ -alkanediyl examples include methanediyl, ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl.
  • Examples for branched d-C ⁇ -alkanediyl comprise ethyl-1 ,1-diyl, propyl-1 ,1-diyl, butyl-1 ,1-diyl, 1- methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1-ethylethane-1 ,2 diyl, 1- methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.
  • Preferred are thiourea compounds of formula I, wherein X is -C( O)-.
  • thiourea compounds of formula I wherein Y is Ci-C ⁇ - alkyl, Ci-Ce-alkoxy-Ci-C ⁇ -alkyl, Ci-C4-alkoxycarbonyl-Ci-C6-alkyl, C1-C4- alkylcarbonyloxy-Ci-C ⁇ -alkyl or phenoxy-Ci-C ⁇ -alkyl, wherein the phenyl moiety of phenoxy-Ci-C ⁇ -alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, d-C 6 -haloalkylthio, Ci-C 6 - alkoxy or Ci-C6-haloalkoxy groups.
  • Y is d-d-alkyl, such as methyl, ethyl or propyl
  • Ci-C2-alkoxy-Ci-C4-alkyl such as methoxymethyl, methoxyethyl, ethoxymethyl or ethoxyethyl
  • C1-C2- alkoxycarbonyl-Ci-d-alkyl such as methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl or ethoxycarbonyl- propyl
  • Ci-C2-alkylcarbonyloxy-Ci-C4-alkyl such as methylcarbonyloxymethyl, methyl- carbonyloxyethyl, methylcarbonyloxypropyl, CH3C(O)OC(CH3)2, ethylcarbonyloxy- methyl, ethylcarbonyloxye
  • Y is methyl, methoxymethyl, methoxycarbonylethyl, CH3C(O)OC(CH3)2, pheonoxymethyl or pentafluorophenoxy- methyl. Most preferably, Y is methyl.
  • thiourea compounds of formula I wherein Y is a 5- or 6-membered hetaryl containing 1 or 2 heteroatoms selected independently from one another from O, S and N as ring members which is unsubstituted or substituted with any combination of 1 , 2, or 3 radicals R yyy , especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or C1-C3- haloalkyl.
  • Y is a 6- membered hetaryl containing 1 or 2 nitrogen atoms as ring members, which is unsubstituted or substituted with any combination of 1 , 2 or 3 radicals R yyy , especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or Ci-C3-haloalkyl.
  • Y is pyridyl which is unsubstituted or substituted with any combination of 1 , 2 or 3 radicals R yyy , especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, C1-C3- haloalkoxy or Ci-C3-haloalkyl.
  • R yyy radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, C1-C3- haloalkoxy or Ci-C3-haloalkyl.
  • Y is unsubstituted pyridyl such as 2- pyridyl, 3-pyridyl or 4-pyridyl.
  • thiourea compounds of formula I wherein Y is phenyl which is unsubstituted or substituted with any combination of 1 , 2, 3, 4, or 5 radicals R yyy , especially with any combination of 1 , 2 or 3 radicals R yyy .
  • R yyy is as defined above or has one of the preferred meanings as defined below.
  • R yyy are halogen, Ci-C3-alkoxy, Ci-C3-haloalkyl, C1-C3- haloalkoxy, Ci-C3-alkylthio, Ci-C3-haloalkylthio, or two adjacent radicals R yyy together with the carbon atoms of the phenyl ring to which they are attached form a fused 5-, 6-, or 7-membered heterocycle, which contains 1 or 2 heteroatoms selected from oxygen or sulfur as ring members, such as 1 ,4-dioxane, 1 ,3-dioxolane, tetrahydrofuran or tet- rahydrothiophen.
  • thiourea compounds of formula I wherein n in formula I is 0, 1 , 2 or 3.
  • a particular preferred embodiment relates to compounds of formula I, wherein n is 1 or 2.
  • Another preferred embodiment relates to compounds of formula I, wherein, n is 3.
  • a particular preferred embodiment relates to compounds of formula I, wherein m is 1 or 2.
  • Another preferred embodiment relates to compounds of formula I, wherein m is 3.
  • n+m is an integer from 1 , 2, 3, 4 or 5, in particular 3, 4 or 5.
  • n is preferably 1 or 2 and m is preferably 2 or 3.
  • each R 1 is selected from halogen, Ci-C 4 -alkyl, Ci-C4-alkoxy, Ci-C 4 -haloalkyl, Ci-C4-haloalkoxy and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkylthio, d-Ce-haloalkylthio, Ci-C 6 -alkoxy or Ci-C ⁇ -haloalkoxy groups.
  • each R 1 is selected from fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylthio or phenyl, which may be unsubstituted or may carry 1 , 2 or 3 radicals selected from halogen or methyl.
  • R 1 is selected from chloro, fluoro, bromo, CH3, CH3O or CF3.
  • R 1 may be same or different.
  • the radical(s) R 1 can be located in any position on the phenyl ring.
  • at least one radical R 1 is attached at the carbon atom in one of the meta-positions of the phenyl ring relative to the bonding position of the phenyl to the remainder of the compound of formula I.
  • each R 2 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-C ⁇ -alkyl, Ci-C ⁇ -haloalkyl, C-i-C ⁇ -alkylthio, C-i-C ⁇ -haloalkylthio, C-i-C ⁇ -alkoxy or Ci-C ⁇ -haloalkoxy groups.
  • each R 2 is selected from fluoro, chloro, bromo, methyl, ethyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylthio or phenyl, which may be unsubstituted or may carry 1 , 2 or 3 radicals selected from halogen or methyl.
  • R 2 is selected from chloro, fluoro, bromo, CH 3 , CH 3 O or CF 3 .
  • R 2 may be same or different.
  • the radical(s) R 2 can be located in any position on the phenyl ring.
  • one radical R 2 is attached at the carbon atom in one of the meta-positions of the phenyl ring relative to the bonding position of the phenyl to the remainder of the compound of formula I.
  • thiourea compounds of the formula I wherein two adjacent radicals R 2 together with the carbon atoms of the phenyl ring to which they are attached form a ring which is depicted as a benzene ring, a saturated 5-, 6-, or 7-membered carbocycle, a partially unsaturated 5-, 6-, or 7-membered carbocycle, a 5-, 6-, or 7-membered saturated heterocycle, a partially unsaturated 5-, 6-, or 7-membered heterocycle, which heterocycles contain 1 , 2, or 3 heteroatoms selected from O, S and N as ring members, and a 5- or 6-membered heteroaromatic ring which contains 1 , 2, or 3 heteroatoms selected from O, S and N as ring members
  • ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and cyano.
  • radicals R 2 form a bivalent radical selected from -(CH 2 J 4 -, -(CH 2 )S-, -O-CH2-O-, -0-(CH 2 J 2 -O-, -0-(CH 2 J 3 -OTO-CF 2 -O- ,-0-(CF 2 J 2 -O- , -0(CH 2 J 2 -, -0-(CH 2 J 3 -, -CH(CHs)-CH(CHs)-O-, -CH 2 -C(CHs) 2 -O-, -CH 2 -CHCH 3 -O-, -CHCH 3 -CH 2 O-, -S(CH 2 J 2 -, -S-(CH 2 J 3 -, -CH(CH 3 )-CH(CH)
  • the radical R ⁇ 1 is preferably C-i-C ⁇ -alky, Ci-C4-alkylcarbonyl or phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 CT Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkylthio, d-Ce-haloalkylthio, Ci-C 6 -alkoxy or CrC 6 - haloalkoxy groups.
  • the radical R ⁇ 2 is preferably C-i-C ⁇ -alkyl or phenyl which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, C-i-C ⁇ - alkylthio, C-i-C ⁇ -haloalkylthio, d-C ⁇ -alkoxy or Ci-C ⁇ -haloalkoxy groups.
  • the radicals R y3 and R y4 are, independently of each other, preferably selected from Ci-C ⁇ -alkyl or hydrogen or may form together with the nitrogen atom to which they are attached may also form a saturated 5- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, or 4 substituents selected from the group consisting of halogen, d-C ⁇ -alkyl, d-C ⁇ -alkoxy and C-i-C ⁇ -haloalkyl.
  • the radical R y5 is preferably Ci-C4-alkoxy.
  • the radicals R y6 and R y7 are preferably selected, independently of each other, from the group consisting of hydrogen, d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, Ci-C ⁇ -alkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl and C2-C4-alkynyl.
  • R y6 and R y7 together with the nitrogen atom to which they are at- tached may also form a saturated 5- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-alkoxy,Ci-C4-haloalkyl, C1-C4- haloalkoxy.
  • R y8 and R y9 independently of each other, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy, Cs-C ⁇ -cycloalkyl which is un- substituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, phenyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, benzyl, phenoxy and phenoxy-Ci-C4-alkyl, wherein phenoxy and the phenyl moiety of benzyl and phenoxy-Ci-C4-alkyl is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and C1-C4- alkoxy.
  • the radicals R y1 ° and R y11 independently of each other, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, C3-C6-cycloalkyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, phenyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, benzyl, phenoxy and phenoxy-Ci-C4-alkyl, wherein phenoxy and the phenyl moiety of benzyl and phenoxy-Ci-C4-alkyl is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-
  • R y1 ° and R y11 independently of each other are Ci-C4-alkoxy, especially methoxy or ethoxy.
  • the radical R y12 is preferably selected from hydroxy, Ci-C4-alkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, phenyl, phenoxy and phenyl-Ci-C4-alkyl, wherein phenyl , phenoxy and phenyl-Ci-C4-alkyl may be unsubstituted or substituted with 1 or 2 substituents selected from Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy.
  • the radicals R y13 , R y14 and R y15 are preferably selected from the group consisting of Ci-C4-alkyl and Ci-C4-alkoxy.
  • radicals R a1 and R a2 preferably are hydrogen or C-i-C ⁇ -alkyl.
  • the radical Ar is preferably phenyl, naphthyl or a 5- or 6-membered hetaryl containing 1 or 2 heteroatoms selected from oxygen, sulphur and nitrogen as ring members, wherein Ar is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, Ci-C 6 -haloalkyl, Ci-C 6 -alkylthio, Ci-C 6 -haloalkylthio, Ci-C 6 -alkoxy or Ci- C ⁇ -haloalkoxy groups.
  • the radical Cy is preferably Cs-Cs-cycloalkyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-C ⁇ -alkyl, C-i-C ⁇ -haloalkyl, C-i-C ⁇ -alkylthio, Ci-C ⁇ -haloalkylthio, Ci-C6-alkoxy or Ci-C ⁇ -haloalkoxy groups.
  • the radical R yy is preferably halogen such as chlorine, fluorine or bromine, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, amino, Ci-C4-alkylamino and di(Ci-C4-alkyl)amino,
  • a preferred embodiment of the invention relates to the compounds I of formula I',
  • X and Y have one of the meanings given above, especially one of the preferred meanings;
  • R 1a and R 1b are, independently of one another, hydrogen or have one of the meanings given above for R 1 ;
  • R 2a , R 2b and R 2c are, independently of one another other, hydrogen or have one of the meanings given above for R 2 .
  • the invention relates to compounds of formula I', wherein R 1a and R 1b are, independently from one another, selected from halogen, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy and phenyl, which is unsubsti- tuted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-C ⁇ -alkyl, Ci-C ⁇ - haloalkyl, d-C ⁇ -alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy or Ci-C ⁇ -haloalkoxy groups, provided that one of the radicals R 1a or R 1b may also be hydrogen.
  • a further more preferred embodiment of the present invention relates to compounds of the formula I', wherein both radicals R 1a and R 1b are different from hydrogen.
  • R 1a and R 1b are, independently of one another, selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy. More preferably R 1a and R 1b , independently of each other, are selected from fluoro, chloro, bromo, methyl, methoxy, difluoromethyl, trifluoromethyl, difluoromethoxy and trifluoromethoxy. Most preferably R 1a and R 1b are, independently of each other, selected from chloro, methyl and methoxy, especially methyl.
  • the invention relates to compounds of formula I', wherein R 2a and R 2b are, independently from one another, halogen, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-C ⁇ -alkyl, d-C ⁇ -haloalkyl, C-i-C ⁇ -alkylthio, Ci- C ⁇ -haloalkylthio, Ci-C6-alkoxy or Ci-C ⁇ -haloalkoxy groups.
  • R 2a and R 2b are, independently of one another, are selected from the group consisting of fluoro, chloro, bromo, methyl, methoxy, difluoromethyl, trifluoromethyl, difluoromethoxy and trifluoromethoxy, especially methyl or chloro.
  • the invention relates to compounds of formula I', wherein R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via 1 or 2 oxygen atoms, 1 or 2 sulphur atoms or 1 nitrogen atom.
  • the invention relates to compounds of formula I', wherein R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via an oxygen atom in the Re position.
  • the invention relates to compounds of formula I', wherein R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via a sulfur atom in the Re position. In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via a nitrogen atom in the Re position.
  • the invention relates to compounds of formula I', wherein R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via an oxygen atom in the Re position.
  • R 2a and R 2b together form a bivalent radical which is bonded to the phenyl ring via an oxygen atom in the Re position.
  • the first atom is meant to be bound to the phenyl ring at the R 2a position.
  • R 2a and R 2b are selected from -(CH 2 ) 4 -, -(CH 2 ) 3 -, -0-CH 2 -O-, -O-(CH 2 ) 2 -O-, -O-(CH 2 ) 3 -O- ,-0-CF 2 -O- ,-O-(CF 2 ) 2 -O- , -O(CH 2 ) 2 -, -O-(CH 2 ) 3 -, -(CH 2 ) 2 -O-, -(CH 2 ) 3 -O-, -CH(CH 3 )- CH(CHs)-O-, -O-CH(CH 3 )-CH(CH 3 )-, -CH 2 -C(CHs) 2 -O-, -CH 2 -CHCH 3 -O-, -CHCH 3 - CH 2 O-, -0-CH 2 -C
  • the invention relates to compounds of formula I', wherein R 2c is hydrogen, fluoro, chloro, CF 3 or CH 3 , preferably hydrogen.
  • Y is Ci-C 4 -alkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -alkoxycarbonyl-Ci-C 4 -alkyl, Ci-C 4 - alkylcarbonyloxy-Ci-C 4 -alkyl or phenoxy-Ci-C 4 -alkyl, wherein the phenyl moiety of phenoxy-Ci-C ⁇ -alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, Ci-C 6 - haloalkylthio, Ci-C6-alkoxy or Ci-C ⁇ -haloalkoxy groups, or pyridyl which is unsubstituted or substituted with any combination of 1 , 2 or 3 halogen atoms, Ci-C 3
  • R 1a and R 1b are, independently from one another, halogen, Ci-C 4 -alkyl, Ci-C 4 -alkoxy, Ci-C 4 -haloalkyl and Ci-C 4 -haloalkoxy, where one of the radicals R 1a or R 1b may also be hydrogen, in particular R 1a and R 1b are methyl;
  • R 2a and R 2b are, independently from one another halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R 2a or R 2b may also be hydrogen, in particular R 2a and R 2b are halogen or methyl, especially chloro or methyl; and R 2c is hydrogen.
  • Y is Ci-C 4 -alkyl, Ci-C 4 -alkoxy-Ci-C 4 -alkyl, Ci-C 4 -alkoxycarbonyl-Ci-C 4 -alkyl, Ci-C 4 - alkylcarbonyloxy-Ci-C4-alkyl or phenoxy-Ci-C4-alkyl, wherein the phenyl moiety of phenoxy-Ci-C ⁇ -alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, CrC 6 - haloalkylthio, Ci-C6-alkoxy or C-i-C ⁇ -haloalkoxy groups, or pyridyl which is unsub- stituted or substituted with any combination of 1
  • Examples of especially preferred embodiments of the compounds of the formula I' are illustrated by the following formulae (IM ), (l'.2), (l'.3), (l'.4), (l'.5), (l'.6), (l'.7), (l'.8), (l'.9), (IMO), (IM 1 ), (IM2) and (IM 3), wherein X is C(O) and R 1a , R 1b and Y have one of the meanings given above, in particular one of the preferred meanings:
  • the first atom is meant to be bound to the phenyl ring at the R 2a position
  • the compounds of formula I wherein X is C(O), can for instance be prepared according to the method depicted in scheme 1 by esterification reaction or alcoholysis reaction.
  • n, m, R 1 , R 2 , and Y have one of the meanings given above and LG denotes a leaving group such as halogen, Ci-C ⁇ -alkoxy or hydroxy.
  • a 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il is reacted with carboxylic acids, esters or carboxylic acid halogenides, especially chlorides, by methods familiar to an organic chemist and well known in the art to give compounds of formula I.
  • the compounds of formula I wherein X is C(O), can for instance also be prepared according to the method depicted in scheme 3 by reacting the isothiocyanate (V) with an appropriate carboxylic acid 2-aminoethyl ester of formula (Vl) or its salt.
  • n, m, R 1 , R 2 , and Y have one of the meanings given above. It may be advantageous to carry out the reaction in the presence of a base.
  • the compounds of formula I wherein X is C(S) can for instance be prepared by thiona- tion of the corresponding compound I wherein X is C(O) using phosphorus pentasulfide or Lawesson's reagent.
  • the compounds of formula I wherein X a single bond and Y is SiR y13 R y14 R y15 can be prepared according to the method depicted in scheme 3 by reacting H 2 N-CH 2 -CH 2 -O-SiR y13 R y14 R y15 . with the isothiocyanate (V)
  • the compounds of formula I wherein X a single bond and Y is SO 2 R y12 can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea com- pound Il with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur triox- ide/water to give compounds I with R y12 being OH.
  • Compounds of formula I with R y12 being OH may be modified by etherifcation to give compounds I with R y12 being alkoxy or optionally substituted phenoxy.
  • the compounds of formula I wherein X a single bond and Y is P(O)R y8 R y9 can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il with phosphoric acid or phosphoroxychloride/water or with an ortho- phosphate ester.
  • the compounds of formula I wherein X a single bond and Y is P(S)R y10 R y11 can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il with a thiophosphate salt or an appropriate 0,0-dialkyl thiophosphoric acid or diphenyl thiophosphoric acid.
  • the compounds of formula I wherein X a single bond and Y is NR y6 R y7 can be prepared according to scheme 4 by reacting a compound of formula V with an appropriate amine of formula Vl I or salt thereof.
  • n, m, R 1 , R 2 , R y6 , and R y7 have one of the meanings given above.
  • suitable amine salts are e.g. the acid addition salts formed by treating the amine with an inorganic or organic acid.
  • Anions of useful acids are e.g. sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, chloride, bromide, p-toluene sulfonate, and the anions of Ci-C4-alkanoic acids such as acetate, propionate, and the like.
  • Compounds of the formulae Il and V are known, e.g. from WO 2005/063724 and WO 2006/125745 or can be prepared in analogy to the methods described there. For example, they can be prepared as outlined in scheme 5 below.
  • n, m, R 1 and R 2 have one of the meanings given above.
  • a 1 ,2-diphenylaminoethane III is converted into the corresponding isothiocyanate V by conventional means, e.g. by reacting III with thiophosgene (see e.g. Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter INc, pp. 837-842.
  • the isothiocyanate V is then reacted with 2- aminoethanol of the formula VIII, thereby obtaining the thiourea compound of the formula II.
  • the reaction of aminoethanol VIII with isothiocyanate V can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Bio- chem. 1992, 56 (7), 1062-1065 (cf. eg WO 2005/063724).
  • Diphenylethylamines of the formula III are known in the art (e.g. 1 ,2- diphenylethylamine, CAS-Nr.[ 3082-58-4] ) or they can be prepared by methods familiar to an Organic chemist and well known in the art. Suitable methods for preparing diphenylethylamines III comprise inter alia the reductive amination of the corresponding phenylbenzylketones or the reduction of the corresponding phenylbenzyloximes (see e.g. J. Med. Chem. 1995, 38, 1600-1607; J. Med. Chem 1994, 37 (7), 913-923). 2-Aminoethanol VIII is commercially available.
  • lsothiocyanates of the general formula IV can for instance be prepared according to the procedures described in Coll. Czech. Chem. Comm. 1986, 51 , 112 - 1 17.
  • Carboxylic acid 2-aminoethyl ester of formula (Vl) and amine compounds of formula (VII) are commercially available or they can be prepared according to routine methods, which are familiar to an organic chemist.
  • the compounds of formula I can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds of formula I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefi- nation, reduction, metal catalyzed coupling reactions, 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 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 digestion.
  • the compounds of formula I 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 formula I or a salt thereof 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 animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesti- cidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below.
  • the method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
  • invertebrate pests are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
  • the invention further provides an agricultural composition for combating such invertebrate pests, which comprises such an amount of at least one compound of formula I or at least one agriculturally useful salt thereof 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 contain a single active compound of formula I or a salt thereof or a mixture of several active compounds of formula I or their salts according to the present invention.
  • the composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers.
  • the compounds of the formula I and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes.
  • Invertebrate pests controlled by the compounds of formula I include for example:
  • 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, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipunc- ta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Ea- rias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta
  • beetles Coldoptera
  • Agrilus sinuatus for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtip
  • dipterans dipterans
  • Aedes aegypti Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Cu- lex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria
  • thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Eu- schistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Ne- zara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
  • Heteroptera e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Eu- schistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis
  • homopterans e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae,
  • Isoptera e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
  • orthopterans e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
  • Orthoptera e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melan
  • Arachnoidea such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp.
  • Arachnids Acarina
  • Argasidae e.g. of the families Argas
  • Tetranychidae spp. such as Tetranychus cinnabarinus, Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius and Tetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychus pratensis;
  • Siphonatera e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
  • compositions and compounds of formula I are useful for the control of 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
  • Het- erodera 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 longicaudatus and other Belonolaimus species
  • Pine nematodes Bursaphelenchus xylophilus and other Bursaphelenchus species
  • Ring nematodes Criconema species, Criconemella species, Criconemoides species, Mesocriconema species
  • Stem and bulb nematodes Ditylen- chus destructor, Ditylenchus dipsaci and other Ditylenchus species
  • AwI nema-todes
  • the compounds of formula I are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina.
  • the com- pounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
  • the compounds of formula I or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by invertebrate pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pes- ticidally effective amount of compounds of formula I.
  • crop refers both to growing and harvested crops.
  • the compounds of formula I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules.
  • the use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
  • the formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq.
  • auxiliaries suitable for the formulation of agrochemicals such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti-foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
  • solvents examples include water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gam- ma-butyrolactone), pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
  • aromatic solvents for example Solvesso products, xylene
  • paraffins for example mineral oil fractions
  • alcohols for example methanol, butanol, pentanol, benzyl alcohol
  • ketones for example cyclohexanone, gam- ma-butyrolactone
  • pyrrolidones N
  • Suitable emulsifiers are non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates).
  • examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
  • Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, poly- oxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphen
  • Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
  • mineral oil fractions of medium to high boiling point such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, x
  • anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
  • Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
  • a suitable preservative is e.g. dichlorophen.
  • Seed treatment formulations may additionally comprise binders and optionally colorants.
  • Binders can be added to improve the adhesion of the active materials on the seeds after treatment.
  • Suitable binders are block copolymers EO/PO surfactants but also po- lyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol ® , Polymin ® ), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
  • colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
  • Examples of a gelling agent is carrageen (Satiagel ® ).
  • Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
  • Granules for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
  • solid carriers examples include mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium ni- trate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
  • mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium
  • the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s).
  • the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
  • respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
  • the compounds of formula I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusta- ble products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring.
  • the use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.
  • Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water.
  • emulsions, pastes or oil dispersions the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Ho- wever, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
  • the active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
  • the active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
  • UUV ultra-low-volume process
  • the active compound(s) 10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.
  • Emulsions EW, EO, ES
  • 25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight).
  • This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
  • an emulsifier machine e.g. Ultraturrax
  • 50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active compound ⁇ ), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
  • Products to be applied undiluted for foliar applications may be applied to the seed diluted or undiluted.
  • 0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound ⁇ ) is obtained.
  • Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
  • the compounds of formula I are also suitable for the treatment of plant propagation materials (such as seed).
  • Conventional seed treatment formulations include for exam- pie flowable concentrates FS, solutions LS, powders for dry treatment DS, water dis- persible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having preger-minated the latter In a preferred embodiment a FS formulation is used for seed treatment.
  • a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
  • compositions of compounds of formula I for seed treatment comprise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
  • oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
  • the compounds of formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
  • compounds of formula I are preferably used in a bait composition.
  • the bait can be a liquid, a solid or a semisolid preparation (e.g. a gel).
  • Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks.
  • Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources.
  • Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickyness, moisture retention or aging characteristics.
  • the bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it.
  • the attractiveness can be manipulated by using feeding stimulants or sex pheromones.
  • Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey.
  • Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant.
  • Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
  • Formulations of compounds of formula I as aerosols are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches.
  • Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g.
  • kerosenes having boiling ranges of approximately 50 to 250 0 C, dimethyl- fomaamide, N methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol mo- nooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
  • emulsifiers such as sorbitol mo- nooleate, oleyl ethoxylate
  • the oil spray formulations differ from the aerosol recipes in that no propellants are used.
  • the compounds of formula I and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vapor- izers and also in moth papers, moth pads or other heat-independent vaporizer systems.
  • Methods to control infectious diseases transmitted by insects e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis
  • compounds of formula I and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwov- ens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder.
  • Suitable repellents for exam- pie are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3- cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as ⁇ (+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant ex- tracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants
  • Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic ac- ids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and diethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
  • vinyl esters of aliphatic ac- ids such as such as vinyl acetate and vinyl versatate
  • acrylic and methacrylic esters of alcohols such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate
  • mono- and diethylenically unsaturated hydrocarbons such as styrene
  • aliphatic diens such as butadiene.
  • the impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the active compounds of formula I or spraying them onto the nets.
  • seed treatment refers to all methods that bring seeds and the compounds of formula I into contact with each other
  • seed dressing to methods of seed treatment which provide the seeds with an amount of the compounds of formula I, i.e. which generate a seed comprising the compound of formula I.
  • the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed.
  • the seed can be treated immediately before, or during, the planting of the seed, for example using the "planter's box” method.
  • the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
  • the treatment is applied to unsown seed.
  • the term "unsown seed” is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
  • a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If appropriate, this is followed by a drying step.
  • a suitable device for example a mixing device for solid or solid/liquid mixing partners
  • seed treatment formulations either as such or after previous dilution with water
  • a further object of the present invention is therefore to provide new methods for con- trolling parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
  • the invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
  • the present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula I or veterinarily ac-ceptable salts thereof or a composition comprising it.
  • the invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula I or the veterinarily acceptable salts thereof or a composition comprising it.
  • Compounds of formula I or veterinarily acceptable salts thereof and compositions com- prising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
  • mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer
  • fur-bearing animals such as mink, chin
  • Compounds of formula I or veterinarily acceptable salts thereof and compositions com- prising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
  • Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
  • the compounds of formula I or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
  • the compounds of formula I are especially useful for combating ectoparasites.
  • the compounds of formula I are especially useful for combating parasites of the following orders and species, respectively:
  • fleas e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
  • cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
  • insects e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Cul
  • Pediculus humanus capitis e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
  • ticks and parasitic mites ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,
  • actinedida Prostigmata
  • Acaridida e.g. Acarapis spp., Cheyletiella spp., Ornitrocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
  • Heteropterida Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
  • Anoplurida e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trimenopon spp. Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Tricho- dectes spp., and Felicola spp
  • Mallophagida suborders Arnblycerina and Ischnocerina
  • Trichinosis Trichosyringida
  • Trichinellidae Trichinella spp.
  • T ri- churidae Trichuris spp.
  • Capillaria spp Trichinosis
  • Rhabditida e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
  • Strongylida e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp.,
  • Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
  • Camallanida e.g. Dracunculus medinensis (guinea worm)
  • Spirurida e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
  • Thorny headed worms e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,
  • Planarians (Plathelminthes):
  • Flukes e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
  • Cercomeromorpha in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
  • the compounds of formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
  • the compounds of formula I also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
  • Administration can be carried out both prophylactically and therapeutically.
  • Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
  • the compounds of formula I may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules.
  • the compounds of formulae I may be administered to the animals in their drinking water.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula I, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
  • the compounds of formula I may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection.
  • the compounds of formula I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection.
  • the compounds of formula I may be formulated into an implant for subcutaneous administration.
  • the compounds of formula I may be transdermally administered to animals.
  • the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula I.
  • the compounds of formula I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on for- mulations and in ointments or oil-in-water or water-in-oil emulsions.
  • dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of formula I.
  • the compounds of formula I may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep. Suitable preparations are:
  • Solutions such as oral solutions, concentrates for oral administration after dilution, solu- tions for use on the skin or in body cavities, pouring-on formulations, gels;
  • Emulsions and suspensions for oral or dermal administration for oral or dermal administration; semi-solid preparations;
  • Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
  • compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers.
  • the solutions are filtered and filled sterile.
  • Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.
  • the active compounds can optionally be dissolved in physiologically tolerable vegeta- ble or synthetic oils which are suitable for injection.
  • Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation.
  • examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
  • Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
  • Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
  • Solutions for use on the skin are prepared according to the state of the art and accord- ing to what is described above for injection solutions, sterile procedures not being necessary.
  • solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
  • alkyleneglycol alkylether e.g. dipropylenglycol monomethylether
  • ketons such as acetone, me- thylethylketone
  • aromatic hydrocarbons such as acetone, me- thylethylketone
  • vegetable and synthetic oils dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate,
  • thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
  • Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results.
  • the thickeners employed are the thickeners given above.
  • Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
  • pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
  • Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N methylpyrroli- done
  • Suitable colorants are all colorants permitted for use on animals and which can be dis- solved or suspended.
  • Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
  • Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
  • Suitable light stabilizers are, for example, novantisolic acid.
  • Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
  • Emulsions can be administered orally, dermally or as injections.
  • Emulsions are either of the water-in-oil type or of the oil-in-water type.
  • Suitable hydrophobic phases are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, is
  • Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
  • Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mo- no/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
  • non-ionic surfactants e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol
  • Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
  • Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
  • auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
  • Liquid suspending agents are all homogeneous solvents and solvent mixtures.
  • Suitable wetting agents are the emulsifiers given above.
  • Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
  • the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form.
  • suitable excipients are all physiologically tolerable solid inert substances.
  • Those used are inorganic and organic substances.
  • Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium ox- ides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates.
  • Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
  • Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
  • auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyr- rolidone, and dry binders such as microcrystalline cellulose.
  • lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyr- rolidone, and dry binders such as microcrystalline cellulose.
  • parasiticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the parasiticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
  • compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compounds of formula I.
  • the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
  • Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most prefera- bly from 5 to 40 percent by weight.
  • Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight. Furthermore, the preparations comprise the compounds of formula I against endopara- sites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
  • compositions comprising the compounds of formula I are applied dermally / topically.
  • the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
  • solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
  • thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used.
  • Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula I.
  • a detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
  • compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides.
  • additional ingredients may be used sequentially or in combination with the abo- ve-described compositions, if appropriate also added only immediately prior to use (tank mix).
  • the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
  • agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds of formula I or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action.
  • Organo(thio)phosphate compounds acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fam- phur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton
  • Carbamate compounds aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
  • Pyrethroid compounds acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyflu- thrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyperme- thrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fen- valerate, fluc
  • Juvenile hormone mimics hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
  • Nicotinic receptor agonists/antagonists compounds acetamiprid, bensultap, car- tap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thio- cyclam, thiosultap-sodium and AKD1022.
  • GABA gated chloride channel antagonist compounds chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole M.7.
  • Chloride channel activators abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
  • METI I compounds fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
  • METI Il and III compounds acequinocyl, fluacyprim, hydramethylnon;
  • M.1 Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
  • Moulting disruptors cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
  • Mite growth inhibitors clofentezine, hexythiazox, etoxazole;
  • Lipid biosynthesis inhibitors spirodiclofen, spiromesifen, spirotetramat
  • Anthranilamide compounds chloranthraniliprole,cyantraniliprole,
  • M.25. Microbial disruptors Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
  • the isoxazoline compounds M 22.1 to M 22.8 have been described in e.g. WO2005/085216, WO 2007/079162, WO 2007/026965, WO 2009/126668 and WO2009/051956.
  • the aminofuranone compounds M 26.1 to M 26.10 have been described eg. in WO 2007/1 15644.
  • the pyripy- ropene derivative M 27.2 has been described in WO 2008/66153 and WO
  • the pyridazin compound M 27.3 has been described in JP 2008/1 15155.
  • Malononitrile compounds as those (M24.1 ) and (M24.2) have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.
  • Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole
  • the invertebrate pest i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) of formula I or composition(s) containing them by any application method known in the art.
  • "contacting” includes both direct contact (applying the compounds/compositions di- rectly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
  • invertebrate pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula I.
  • the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
  • “Locus” means a habitat, breeding ground, cultivated plants, plant propagation material (such as seed), soil, area, material or environ-ment in which a pest or parasite is growing or may grow.
  • pesticidally effective amount means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism.
  • the pesticidally effective amount can vary for the various compounds/compositions used in the invention.
  • a pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
  • the compounds of formula I and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities).
  • the compounds of are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywood, furniture, etc., wooden articles such as particle boards, half boards, etc.
  • the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
  • the compounds of formula I can also be applied preventively to places at which occurrence of the pests is expected.
  • the compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I.
  • "contacting” includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
  • the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m 2 , preferably from 0.001 to 2O g per 100 m 2 .
  • Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m 2 treated material, desirably from 0.1 g to 50 g per m 2 .
  • lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and/or insecticide.
  • the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound.
  • the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
  • the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
  • the application rates of the active ingredients are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
  • Example 1 Compound of formula I, wherein (R 1 ) n is 3,5-di-CH3, (R 2 ) m is 2-CH3, 3-CF3, X is (CO) and Y is 2-pyridyl)
  • the active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica ® surfactant.
  • Cotton plants in the cotyledon stage (variety 'Delta Pine') are infested with approximately 100 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The cotyledons of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
  • the active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica ® surfactant.
  • Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') are infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The leaves of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
  • the active compounds were formulated in 50:50 (vohvol) acetone:water and 100 ppm Kinetica ® surfactant.
  • Nasturtium plants grown in Metro mix in the 1 st leaf-pair stage were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days. In this test, the compounds of examples 25, 26, 27, 31 , 38 and 39 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.
  • Cowpea aphid (Aphis craccivora)
  • the active compounds were formulated in 50:50 (vohvol) acetone : water and 100 ppm Kinetica ® surfactant.
  • Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population has been recorded. Population reduction was recorded after 24, 72, and 120 hours.
  • the active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica® surfactant.
  • Selected cotton plants were grown to the cotyledon state (one plant per pot).
  • the coty- ledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry.
  • Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced.
  • the insects were colleted using an aspirator and a 0.6 cm, non-toxic Tygon® tubing (R- 3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding.
  • the cups were covered with a re-usable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 oC and 20-40% relative humid-ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to pre- vent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.

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Abstract

The present invention relates to the use of a thiourea compound of the formula (I) and the salts thereof (I) wherein X is a single bond, C(O) or C(S); Y is optionally substituted alkyl, alkenyl, alkadienyl, alkynyl, cycloalkyl, cycloalkenyl, cycloalkynyl, phenyl, naphthyl, heterocyclyl or hetaryl and may be further NRy6Ry7, P(O)Ry8Ry9, P(S)Ry10Ry11, SO2Ry12 Or SiRy13Ry14Ry15, if X is a single bond; m is 0 to 5; n is 0 to 5; and the variables R1, R2, Ry6, Ry7, Ry8, Ry9, Ry10, Ry11, Ry12, Ry13, Ry14 and Ry15 are as defined in the claims. The invention also relates to novel compounds of formula (I) and to a method for controlling invertebrate pests. The invention also relates to plant propagation material and to an agricultural composition comprising a thiourea compound of formula (I).

Description

Thiourea compounds for combating invertebrate pests
The present invention relates to thiourea compounds which can be used for combating or controlling invertebrate pests, in particular arthropod pests and nematodes. The invention also relates to a method for controlling invertebrate pests by using these compounds and to plant propagation material and to an agricultural composition comprising said compounds.
Invertebrate pests and in particular arthropods and nematodes destroy growing and harvested crops and attack wooden dwelling and commercial structures, 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, in particular insects, arachnids and nematodes.
The WO 2005/063724 describes 1-(azolin-2-yl)amino-1 ,2-diphenylethane compounds of the general formulae B.1 and B.2,
Figure imgf000002_0001
(B.1 ) (B.2) wherein X is sulphur or oxygen, which are useful for combating insects, arachnids and nematodes. Compounds of the formula I as defined below wherein X is -C(=O)-, if Y is phenyl or methyl are described as intermediates. However, the thiourea compounds described therein have not been reported to be useful for combating invertebrate pests.
WO 2006/125745 describes 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests, in particular insects, arachnids or nematodes. However, there activity is not always satisfactory.
Therefore it is an object of the present invention to provide compounds that have a good pesticidal activity, in particular insecticidal activity, and show a broad activity spectrum against a large number of different invertebrate pests, especially against difficult to control arthropod pests and/or nematodes.
It has been found that these objectives can be achieved by compounds of the formulae I below and by their salts, in particular their agriculturally or veterinarily acceptable salts.
Therefore, in a first aspect, the invention relates to the use of compounds of formula I
Figure imgf000003_0001
wherein m is 0, 1 , 2, 3, 4 or 5;
n is 0, 1 , 2, 3, 4 or 5;
X is a single bond, -C(O)- or -C(S)-;
Y is Ci-Cio-alkyl, C2-Cio-alkenyl, C4-Cio-alkadienyl, C2-Cio-alkynyl, where the four last-mentioned groups may be unsubstituted, partially or fully halogenated or may carry 1 , 2 or 3 radicals Ry, where Ry is CN, ORy1, -SRy2, -S(O)2Ry2, -NRy3Ry4, -C(O)Ry5, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl, where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-C12- cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy,
and Y may be further C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-C12- cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryyy,
and in the case that X is a single bond,
Y may be further NRy6Ry7, P(O)Ry8Ry9, P(S)Ry10Ry11, SO2Ry12 or SiRy13Ry14Ry15,
wherein
Ry1 is hydrogen, Ci-C8-alkyl, Ci-C8-haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, Ci-Cs-alkylcarbonyl, Ci-Cs- haloalkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8-haloalkenylcarbonyl, C2-C8- alkynylcarbonyl, C2-C8-haloalkynylcarbonyl,
C3-Ci2-cycloalkyl, C3-Ci2-cycloalkylcarbonyl, C3-Ci2-cycloalkenyl, C3-C12- cycloalkenylcarbonyl, phenyl, phenylcarbonyl, naphthyl, naphthylcarbonyl, 5- to 10-membered heterocyclyl, 5- to 10-membered heterocyclylcarbonyl, 5- to 10-membered hetaryl or 5- to 10-membered hetarylcarbonyl, wherein the twelve last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy, and where 5- to 10-membered heterocyclyl, the heterocyclyl moiety in 5- to 10-membered heterocyclylcarbonyl, the heataryl moiety in 5- to 10-membered hetarylcarbonyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independ- ently from one another from O, S and N as ring members and 5- to 10- membered heterocyclyl may furthermore contain one or two CO groups as ring members;
Ry2 hydrogen, Ci-C8-alkyl, d-Cs-haloalkyl, C2-C8-alkenyl, C2-C8-haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl, or 5- to 10-membered hetaryl, wherein the six last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy and where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members;
Ry3 has one of the meanings given for Ry1 and may also be d-Cs-alkoxy or
C2-C8-alkenyloxy;
Ry4 has one of the meanings given for Ry1, or
Ry3 and Ry4 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-Cβ-alkyl, Ci-C6-alkoxy,Ci- Cβ-haloalkyl, C-i-Cβ-haloalkoxy;
Ry5 has one of the meanings given for Ry2, and may also be hydroxy, Ci-Cs- alkoxy, Ci-Cs-haloalkoxy, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8- alkynyloxy, C2-C8-haloalkynyloxy, C3-Ci2-cycloalkyloxy, C3-C12- cycloalkenyloxy, phenyloxy, naphthyloxy, 5- to 10-membered heterocyclyl- oxy or 5- to 10-membered hetaryloxy, wherein the six last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy and where 5- to 10-membered heterocyclyloxy and 5- to 10- membered hetaryloxy contain 1 , 2, 3 or 4 heteroatoms selected independ- ently from one another from O, S and N as ring members and 5- to 10- membered heterocyclyloxy may furthermore contain one or two CO groups as ring members;
Ry6 has one of the meanings given for Ry3;
Ry7 has one of the meanings given for Ry1 or
Ry6 and Ry7 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-Cβ-alkyl, Ci-C6-alkoxy,Ci- Cβ-haloalkyl and Ci-Cβ-haloalkoxy; Ry8 and Ry9 are in each case independently of one another selected from hydrogen, hydroxy, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, Ci-Cβ-alkyl, Ci-Cβ- alkoxy, d-Cβ-alkylthio, C3-Ci2-cycloalkyl, phenyl, phenyl-Ci-C4-alkyl, phenoxy-Ci-C4-alkyl and phenoxy, wherein C3-Ci2-cycloalkyl, phenyl and the phenyl moiety of phenyl-Ci-C4-alkyl, phenoxy-Ci-C4-alkyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy;
Ry10 and Ry11 have in each case independently of one another one of the mean- ings given for Rv8 and Ry9;
Ry12 is hydroxy, d-Cε-alkyl, Ci-Cβ-alkoxy, d-Cβ-haloalkyl, phenyl, phenoxy and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moiety of phenoxy and phenyl-Ci-C4-alkyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy;
Ry13, Ry14 and Ry15 are in each case independently of one another selected from Ci-Cβ-alkyl, Ci-Cβ-alkoxy, phenyl and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moiety of phenyl-Ci-C4-alkyl may be unsubstituted or substi- tuted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl and C1-C4- alkoxy;
Ryy is selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, Ci-Cβ-alkyl, d-Ce-alkoxy, d-C6-haloalkoxy, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci-C6- haloalkylthio, d-Cβ-alkylsulfonyl, Ci-C6-haloalkylsulfonyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy, carboxyl, Ci-C6-alkoxycarbonyl and Cs-Cs-cycloalkyl;
Ryyy is selected from the group consisting of halogen, cyano, nitro, ORy1, -SRy2, -S(O)2Ry2, -NRy3Ry4, -C(O)Ry5, Ci-C6-alkyl, d-Cβ-haloalkyl, C2-C6-alkenyl,
C2-C6-alkynyl, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl, where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy, it being possible for two radicals Ryyy that are bound to adjacent carbon atoms of the phenyl ring to form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered hetero- cycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy, Ci-Cβ- alkylthio, Ci-C6-haloalkyl and (=0) (oxo);
R1 and R2 are each independently halogen, OH, SH, NH2, SO3H, COOH, cyano, nitro, d-Cβ-alkyl, Ci-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, d-Cs-alkylthio, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6-alkenylthio, C2-C6- alkynyl, C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6-alkynylthio, Ci-Cβ- alkylsulfonyl, d-Cβ-alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, formyl, d-Cβ-alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, Ci-Cβ- alkoxycarbonyl, C2-C6-alkenyloxycarbonyl, C2-C6-alkynyloxycarbonyl, Ci-Cβ-alkylcarbonyloxy, d-Cβ-alkylcarbonyloxy, C2-C6-alkenylcarbonyloxy, C2-C6- alkynylcarbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C-i-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ- haloalkoxy and d-Cβ-alkylthio,
C(O)NRa1Ra2, (SO2)NRa1Ra2, wherein Ra1 and Ra2 are each independently hydrogen, d-Cβ-alkyl, C2-C6-alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio,
a radical Z-Ar or a radical Z-Cy, wherein
Z is a single bond, oxygen, sulfur, d-Cβ-alkanediyl or d-Cβ-alkanediyloxy,
Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered heteroaro- matic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d- Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkyl, C-i-Cβ-haloalkoxy, Ci-C6-alkylthio and d-Cβ-haloalkylthio; and
Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkyl, d-Cβ-haloalkoxy, d-Ce-alkylthio and d-C6-haloalkylthio;
and wherein two radicals R1 or R2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, d-Ce-alkylthio, d-C6-haloalkyl and (=0) (oxo);
and/or the salts thereof, in particular the agriculturally acceptable salts thereof,
for combating invertebrate pests, in particular arthropod pests and/or nematodes.
Another object of the present invention is the use of the compounds of formula I as defined above and/or a veterinarily acceptable salt thereof for treating or protecting an animal from infestation or infection by invertebrate parasites.
So far, the thiourea compounds of the formula I and their salts have not yet been described, except for compounds of the formula I, wherein X is -C(=O)-, if Y is phenyl or methyl. Therefore, the novel thiourea compounds of formula I and their salts, in particular their agriculturally or veterinarily acceptable salts, are also part of the invention.
The present invention also provides an agricultural composition comprising at least one thiourea compound of the formula I as defined herein and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier. 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, cul- tivated 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 thiourea compound of formula I 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 formula I and/or an agriculturally acceptable salt thereof as defined herein.
The present invention further relates to a method for treating or protecting an animal from infestation or infection by invertebrate parasites which comprises bringing the ani- mal in contact with a parasiticidally effective amount of a thiourea compound of the formula I or a veterinarily acceptable salt thereof as defined herein. Bringing the animal in contact with the compound I, its salt or the veterinary composition of the invention means applying or administering it to the animal.
Depending on the substitution pattern, the compounds of the formula I may have one or more centers of chirality, in which case they are present as mixtures of enantiomers or diastereomers. 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 its mixtures. Suitable compounds of the formula I also include all possible stereoisomers (cis/trans isomers) and mixtures thereof.
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 formula I, mixtures of different crystalline states of the respective compound I, as well as amorphous or crystalline salts thereof.
Salts of the compounds of the formula I are preferably agriculturally and veterinarily 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 formula I has a basic functionality or by reacting an acidic compound of formula I 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 (NH4+) 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- Ci-C4-alkyl, hydroxy-Ci-C4-alkoxy-Ci-C4-alkyl, phenyl or benzyl. Examples of substi- tuted ammonium ions comprise methylammonium, isopropylammonium, dimethylam- monium, diisopropylammonium, trimethylammonium, tetramethylammonium, tetra- ethylammonium, 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)sulfoxonium.
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 bu- tyrate. They can be formed by reacting a compound of formulae I with an acid of the corresponding anion, preferably of hydrochloric acid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.
By the term "veterinarily acceptable salts" is meant salts of those cations or anions which are known and accepted in the art for the formation of salts for veterinary use. Suitable acid addition salts, e.g. formed by compounds of formula I containing a basic nitrogen atom, e.g. an amino group, include salts with inorganic acids, for example hydrochloride, 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.
The term "invertebrate pest" as used herein encompasses animal populations, such as insects, arachnids and nematodes, which may attack plants thereby causing substan- tial 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. The term "plant propagation material" as used herein includes 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 includes seeds, roots, fruits, tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants. Seed- lings and young plants, which are to be transplanted after germination or after emergence from soil, may also be included. These plant propagation materials may be treated prophylactically with a plant protection compound either at or before planting or transplanting.
The term "plants" comprises any types of plants including "non-cultivated plants" and in particular "cultivated plants".
The term "non-cultivated plants" refers to any wild type species or related species or related genera of a cultivated plant.
The term "cultivated plants" as used herein includes plants which have been modified by breeding, mutagenesis or genetic engineering. Genetically modified plants are plants, which genetic material has been so modified by the use of recombinant DNA techniques that under natural circumstances cannot readily be obtained by cross breeding, mutations or natural recombination. Typically, 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-transtional modification of protein(s) (oligo- or polypeptides) poly for example by glycosylation or polymer additions such as prenylated, acetylated or farnesylated moieties or PEG moieties(e.g. as disclosed in Biotechnol Prog. 2001 JuI- Aug;17(4):720-8., Protein Eng Des SeI. 2004 Jan;17(1 ):57-66, Nat. Protoc. 2007;2(5):1225-35., Curr. Opin. Chem. Biol. 2006 Oct; 10(5):487-91. Epub 2006 Aug 28., Biomaterials. 2001 Mar; 22(5):405-17, Bioconjug Chem. 2005 Jan-Feb;16(1):1 13- 21).
The term "cultivated plants" as used herein further includes plants that have been rendered tolerant to applications of specific classes of herbicides, such as hy- droxy-phenylpyruvate dioxygenase (HPPD) inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonyl ureas (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (see e. g. US 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO 03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphate synthase (EPSPS) inhibitors, such as glyphosate (see e. g. WO 92/00377); glutamine synthetase (GS) inhibitors, such as glufosinate (see e. g. EP-A-0242236, EP-A-242246) or oxynil herbicides (see e. g. US 5,559,024) as a result of conventional methods of breeding or genetic engineering. Several cultivated plants have been rendered tolerant to herbicides by conventional methods of breeding (mutagenesis), for example Clearfield® summer rape (Canola) being tolerant to imidazolinones, e. g. imazamox. Genetic engineering methods have been used to render cultivated plants, such as soybean, cotton, corn, beets and rape, tolerant to herbicides, such as glyphosate and glufosinate, some of which are commercially available under the trade names RoundupReady® (glyphosate) and LibertyLink® (glufosinate).
The term "cultivated plants" as used herein further includes plants 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 bacil- lus thuringiensis, such as a-endotoxins, e. g. CrylA(b), CrylA(c), CrylF, CrylF(a2), Cry- IIA(b), CrylllA, CrylllB(bi ) or Cryθc; vegetative insecticidal proteins (VIP), e. g. VIP1 , VIP2, VIP3 or VIP3A; insecticidal proteins of bacteria colonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.; toxins produced by animals, such as scorpion toxins, arachnid toxins, wasp toxins, or other insect-specific neurotoxins; tox- ins produced by fungi, such Streptomycetes toxins, plant lectins, such as pea or barley lectins; agglutinins; proteinase inhibitors, 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 blockers of sodium or calcium channels; juvenile hormone esterase; diuretic hormone receptors (helicokinin receptors); stilben synthase, bibenzyl synthase, chitinases or glucanases. In the context of the present invention these insecticidal proteins or toxins are to be understood expressly also as pre-toxins, hybrid proteins, truncated or other- wise modified proteins. Hybrid proteins are characterized by a new combination of protein domains, (see, for example WO 02/015701 ). Further examples of such toxins or genetically-modified plants capable of synthesizing such toxins are dis-closed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A 427 529, EP-A 451 878, WO 03/018810 und WO 03/052073. The methods for producing such genetically modi- fied plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above. These insecticidal proteins contained in the genetically modified plants impart to the plants producing these proteins protection from harmful pests from certain taxonomic groups of arthropods insects, particularly to beetles (Coleoptera), flies (Diptera), and butterflies and moths (Lepidoptera) and to plant parasitic nematodes (Nematoda).
The term "cultivated plants" as used herein further includes plants that are by the use of recombinant DNA techniques capable to synthesize one or more proteins to in- crease the resistance or tolerance of those plants to bacterial, viral or fungal pathogens. Examples of such proteins are the so-called "pathogenesis-related proteins" (PR proteins, see, for example EP-A 0 392 225), plant disease resistance genes (for example potato cultivars, which express resistance genes acting against Phytophthora in- festans derived from the mexican wild potato Solanum bulbocastanum) or T4-lyso-zym (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, for example, in the publications mentioned above.
The term "cultivated plants" as used herein further includes plants 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), tolerance to drought, salinity or other growth-limiting envi- ron-mental factors or tolerance to pests and fungal, bacterial or viral pathogens of those plants.
The term "cultivated plants" as used herein further includes plants 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, for ex-ample oil crops that produce health-promoting long-chain omega-3 fatty acids or unsaturated omega-9 fatty acids (e. g. Nexera® rape).
The term "cultivated plants" as used herein further includes plants 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, for example potatoes that produce increased amounts of amylopectin (e. g. Amflora® potato).
The organic moieties mentioned in the above definitions of the variables are - like the term halogen - collective terms for individual listings of the individual group members. The prefix Cn-Cm indicates in each case the possible number of carbon atoms in the group.
The term halogen denotes in each case fluorine, bromine, chlorine or iodine, in particular fluorine, chlorine or bromine. The term "Ci-Cio-alkyl" as used herein and in the alkyl moieties of alkoxy, alkylamino, dialkylamino, alkylthio, alkylcarbonyl, alkoxycarbonyl and the like refers to saturated straight-chain or branched hydrocarbon radicals having 1 to 2, 1 to 4, 1 to 6, 1 to 8 or 1 to 10 carbon atoms. Ci-C2-Alkyl is methyl or ethyl. Ci-C4-AIkVl is additionally also, for example, propyl, isopropyl, butyl, 1-methylpropyl (sec-butyl), 2-methylpropyl (isobutyl) or 1 ,1-dimethylethyl (tert-butyl). Ci-Cβ-Alkyl is additionally also, for example, pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl, 1 ,1-dimethylpropyl, 1 ,2-dimethylpropyl, hexyl, 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 ,1 ,2-trimethylpropyl, 1 ,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, or 1-ethyl-2- methylpropyl. d-Cs-Alkyl is additionally also, for example, heptyl, octyl, 2-ethylhexyl and positional isomers thereof. Ci-Cio-Alkyl is additionally also, for example, nonyl, decyl and positional isomers thereof.
The term "CiCio-haloalkyl" as used herein refers to straight-chain or branched alkyl groups having 1 to 2, 1 to 4, 1 to 6, 1 to 8 or 1 to 10 carbon atoms (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above: in particular Ci-C2-haloalkyl, such as chloro- methyl, bromomethyl, dichloromethyl, trichloromethyl, fluoromethyl, difluoromethyl, trifluoromethyl, chlorofluoromethyl, dichlorofluoromethyl, chlorodifluoromethyl, 1- chloroethyl, 1-bromoethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl, 2,2,2- trifluoroethyl, 2-chloro-2-fluoroethyl, 2-chloro-2,2-difluoroethyl, 2,2-dichloro-2- fluoroethyl, 2,2,2-trichloroethyl, pentafluoroethyl or 1 ,1 ,1 -trif I uoroprop-2-yl .
The term "C2-Cio-alkenyl" as used herein and in the alkenyl moiety of alkenyloxy and the like refers to monounsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8, 3 to 8, 2 to 10 or 3 to 10 carbon atoms and a double bond in any position, for example C2-C6-alkenyl, such as ethenyl, 1-propenyl, 2-propenyl, 1- methylethenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-methyl-1-propenyl, 2-methyl-1- propenyl, 1-methyl-2-propenyl, 2-methyl-2-propenyl, 1-pentenyl, 2-pentenyl, 3- pentenyl, 4-pentenyl, 1-methyl-1-butenyl, 2-methyl-1-butenyl, 3-methyl-1-butenyl, 1- methyl-2-butenyl, 2-methyl-2-butenyl, 3-methyl-2-butenyl, 1-methyl-3-butenyl, 2-methyl- 3-butenyl, 3-methyl-3-butenyl, 1 ,1-dimethyl-2-propenyl, 1 ,2-dimethyl-1-propenyl, 1 ,2- dimethyl-2-propenyl, 1-ethyl-1-propenyl, 1-ethyl-2-propenyl, 1-hexenyl, 2-hexenyl, 3- hexenyl, 4-hexenyl, 5-hexenyl, 1-methyl-1-pentenyl, 2-methyl-1-pentenyl, 3-methyl-1- pentenyl, 4-methyl-1-pentenyl, 1-methyl-2-pentenyl, 2-methyl-2-pentenyl, 3-methyl-2- pentenyl, 4-methyl-2-pentenyl, 1-methyl-3-pentenyl, 2-methyl-3-pentenyl, 3-methyl-3- pentenyl, 4-methyl-3-pentenyl, 1-methyl-4-pentenyl, 2-methyl-4-pentenyl, 3-methyl-4- pentenyl, 4-methyl-4-pentenyl, 1 ,1-dimethyl-2-butenyl, 1 ,1-dimethyl-3-butenyl, 1 ,2-dimethyl-1-butenyl, 1 ,2-dimethyl-2-butenyl, 1 ,2-dimethyl-3-butenyl, 1 ,3-dimethyl-1- butenyl, 1 ,3-dimethyl-2-butenyl, 1 ,3-dimethyl-3-butenyl, 2,2-dimethyl-3-butenyl, 2,3-dimethyl-1-butenyl, 2,3-dimethyl-2-butenyl, 2,3-dimethyl-3-butenyl, 3,3-dimethyl-1- butenyl, 3,3-dimethyl-2-butenyl, 1-ethyl-1-butenyl, 1-ethyl-2-butenyl, 1-ethyl-3-butenyl, 2-ethyl-1-butenyl, 2-ethyl-2-butenyl, 2-ethyl-3-butenyl, 1 ,1 ,2-trimethyl-2-propenyl, 1 -ethyl-1 -methyl-2-propenyl, 1 -ethyl-2-methyl-1 -propenyl, 1 -ethyl-2-methyl-2-propenyl and the like.
The term "C4-Cio-alkadienyl" as used herein refers to doubly unsaturated straight-chain or branched hydrocarbon radicals having 4 to 6, 4 to 8 or 4 to 10 carbon atoms and two double bonds in any position, but preferably not cumulated, for example 1 ,3- butadienyl, 1-methyl-1 ,3-butadienyl, 2-methyl-1 ,3-butadienyl, penta-1 ,3-dien-1-yl, hexa- 1 ,4-dien-1-yl, hexa-1 ,4-dien-3-yl, hexa-1 ,4-dien-6-yl, hexa-1 ,5-dien-1-yl, hexa-1 ,5-dien- 3-yl, hexa-1 ,5-dien-4-yl, hepta-1 ,4-dien-1-yl, hepta-1 ,4-dien-3-yl, hepta-1 ,4-dien-6-yl, hepta-1 ,4-dien-7-yl, hepta-1 ,5-dien-1-yl, hepta-1 ,5-dien-3-yl, hepta-1 ,5-dien-4-yl, hepta- 1 ,5-dien-7-yl, hepta-1 ,6-dien-1-yl, hepta-1 ,6-dien-3-yl, hepta-1 ,6-dien-4-yl, hepta-1 ,6- dien-5-yl, hepta-1 ,6-dien-2-yl, octa-1 ,4-dien-1-yl, octa-1 ,4-dien-2-yl, octa-1 ,4-dien-3-yl, octa-1 ,4-dien-6-yl, octa-1 ,4-dien-7-yl, octa-1 ,5-dien-1 -yl, octa-1 ,5-dien-3-yl, octa-1 ,5- dien-4-yl, octa-1 ,5-dien-7-yl, octa-1 ,6-dien-1-yl, octa-1 ,6-dien-3-yl, octa-1 ,6-dien-4-yl, octa-1 ,6-dien-5-yl, octa-1 ,6-dien-2-yl, deca-1 ,4-dienyl, deca-1 ,5-dienyl, deca-1 ,6-dienyl, deca-1 ,7-dienyl, deca-1 ,8-dienyl, deca-2,5-dienyl, deca-2,6-dienyl, deca-2,7-dienyl, deca-2,8-dienyl and the like.
The term "C2-Cio-haloalkenyl"as used herein and the haloalkenyl moieties in haloal- kenyloxy, haloalkenylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms and a double bond in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine, for example chlorovinyl, chloroallyl and the like.
The term "C2-Cio-alkynyl" as used herein and the alkynyl moieties in alkynyloxy, al- kynylcarbonyl and the like refers to straight-chain or branched hydrocarbon groups having 2 to 4, 2 to 6, 2 to 8, 3 to 8, 2 to 10 or 3 to 10 carbon atoms and one or two triple bonds in any position, for example C2-C6-alkynyl, such as ethynyl, 1-propynyl, 2- propynyl, 1-butynyl, 2-butynyl, 3-butynyl, 1-methyl-2-propynyl, 1-pentynyl, 2-pentynyl, 3-pentynyl, 4-pentynyl, 1-methyl-2-butynyl, 1-methyl-3-butynyl, 2-methyl-3-butynyl, 3- methyl-1-butynyl, 1 ,1-dimethyl-2-propynyl, 1-ethyl-2-propynyl, 1-hexynyl, 2-hexynyl, 3- hexynyl, 4-hexynyl, 5-hexynyl, 1-methyl-2-pentynyl, 1-methyl-3-pentynyl, 1-methyl-4- pentynyl, 2-methyl-3-pentynyl, 2-methyl-4-pentynyl, 3-methyl-1-pentynyl, 3-methyl-4- pentynyl, 4-methyl-1-pentynyl, 4-methyl-2-pentynyl, 1 ,1-dimethyl-2-butynyl, 1 ,1- dimethyl-3-butynyl, 1 ,2-dimethyl-3-butynyl, 2,2-dimethyl-3-butynyl, 3,3-dimethyl-1- butynyl, 1-ethyl-2-butynyl, 1-ethyl-3-butynyl, 2-ethyl-3-butynyl, 1-ethyl-1-methyl-2- propynyl and the like.
The term "C2-Cio-haloalkynyl" as used herein and the haloalkynyl moieties in haloal- kynyloxy, haloalkynylcarbonyl and the like refers to unsaturated straight-chain or branched hydrocarbon radicals having 2 to 4, 2 to 6, 2 to 8 or 2 to 10 carbon atoms, frequently 3 to 4, 3 to 6, 3 to 8 or 3 to 10 carbon atoms and one or two triple bonds in any position (as mentioned above), where some or all of the hydrogen atoms in these groups may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
The term "C3-Ci2-cycloalkyl" as used herein refers to mono- or bi- or polycyclic saturated hydrocarbon radicals having 3 to 12 (= C3-Ci2-cycloalkyl), frequently 3 to 8 carbon atoms (= Cs-Cs-cycloalkyl), in particular 3 to 6 carbon atoms (= C3-C6- cycloalkyl). Examples of monocyclic radicals comprise cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl and cyclodecyl. Examples of bicyclic radicals comprise bicyclo[2.2.1]heptyl, bicyclo[3.1.1]heptyl, bicyclo[2.2.2]octyl and bicyclo[3.2.1]octyl.
The term "C3-Ci2-halocycloalkyl" as used herein and the halocycloalkyl moieties in halocycloalkoxy, halocycloalkylcarbonyl and the like refers to mono- or bi- or polycyclic saturated hydrocarbon groups having 3 to 6, 3 to 8 or 3 to 10 carbon ring members (as mentioned above) in which some or all of the hydrogen atoms may be replaced by halogen atoms as mentioned above, in particular fluorine, chlorine and bromine.
The term "C3-Ci2-cycloalkenyl" as used herein refers to mono- or bicyclic monounsaturated hydrocarbon groups having 3 to 12 (= C3-Ci2-cycloalkenyl), preferably 5 to 8 (= Cs-Cs-cycloalkenyl), carbon ring members, such as cyclopenten-1- yl, cyclopenten-3-yl, cyclohexen-1-yl, cyclohexen-3-yl, cyclohexen-4-yl, cycloheptenyl, cyclooctenyl, bicyclo[2.2.2]octenyl and the like.
The term "aryl" as used herein refers to carbocyclic aromatic radicals having 6 to 14 carbon atoms, such as phenyl, naphthyl, anthracenyl and phenanthrenyl. Preferably, aryl is phenyl. Phenyl fused to a 5- or 6-membered non-aromatic (i.e. saturated or partially unsaturated) heterocyclic ring is for example 2,3-dihydrobenzofuranyl, benzoxolanyl, 2,3-dihydrobenzothienyl, indolinyl, chromanyl, chromenyl, benzodioxanyl and the like. Examples for phenyl fused to a 5- or 6-membered aromatic heterocyclic ring (= fused to a 5- or 6-membered heteroaromatic ring) are given below.
The term "5- to 10-membered heterocyclyl (= 5-, 6-, 7-, 8-, 9- or 10- membered heterocyclyl)" as used herein includes in general 5-, 6-, 7- or 8-membered monocyclic heterocyclic radicals and 8- , 9- or 10- membered bicyclic heterocyclic radicals, the mono- and bicyclic radicals may be saturated or unsaturated. The mono- and bicyclic heterocyclic radicals usually comprise 1 , 2, 3 or 4 heteroatoms selected from N, O and S as ring members and optionally 1 or 2 carbonyl groups as ring members. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member:
Examples of 5- to 10-membered heterocyclyl include: five- or six-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen (as N or NR) and sulfur and: for example monocyclic saturated or partially unsaturated heterocycles which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms and optionally 1 or 2 carbonyl groups, for example 2-tetrahydrofuranyl, 3- tetrahydrofuranyl, 3-tetrahydrofuran-2-onyl, 4-tetrahydrofuran-2-onyl, 5-tetrahydrofuran- 2-onyl, 2-tetrahydrofuran-3-onyl, 4-tetrahydrofuran-3-onyl, 5-tetrahydrofuran-3-onyl, 2-tetrahydrothienyl, 3-tetrahydrothienyl, 3-tetrahydrothien-2-onyl, 4-tetrahydrothien-2- onyl, 5-tetrahydrothien-2-onyl, 2-tetrahydrothien-3-onyl, 4-tetrahydrothien-3-onyl, 5-tetrahydrothien-3-onyl, 2-pyrrolidinyl, 3-pyrrolidinyl, 1 -pyrrolidin-2-onyl, 3-pyrrolidin-2- onyl, 4-pyrrolidin-2-onyl, 5-pyrrolidin-2-onyl, 1 -pyrrolidin-3-onyl, 2-pyrrolidin-3-onyl, 4- pyrrolidin-3-onyl, 5-pyrrolidin-3-onyl, 1-pyrrolidin-2,5-dionyl, 3-pyrrolidin-2,5-dionyl, 3- isoxazolidinyl, 4-isoxazolidinyl, 5-isoxazolidinyl, 3-isothiazolidinyl, 4-isothiazolidinyl, 5-isothiazolidinyl, 3-pyrazolidinyl, 4-pyrazolidinyl, 5-pyrazolidinyl, 2-oxazolidinyl, 4- oxazolidinyl, 5-oxazolidinyl, 2-thiazolidinyl, 4-thiazolidinyl, 5-thiazolidinyl, 2-imidazolidinyl, 4-imidazolidinyl, 1 ,2,4-oxadiazolidin-3-yl, 1 ,2,4-oxadiazolidin-5-yl, 1 ,2,4-thiadiazolidin-3-yl, 1 ,2,4-thiadiazolidin-5-yl, 1 ,2,4-triazolidin-3-yl, 1 ,3,4- oxadiazolidin-2-yl, 1 ,3,4-thiadiazolidin-2-yl, 1 ,3,4-triazolidin-2-yl, 2,3-dihydrofur-2-yl, 2,3-dihydrofur-3-yl, 2,4-dihydrofur-2-yl, 2,4-dihydrofur-3-yl, 2,3-dihydrothien-2-yl, 2,3-dihydrothien-3-yl, 2,4-dihydrothien-2-yl, 2,4-dihydrothien-3-yl, 2-pyrrolin-2-yl, 2- pyrrolin-3-yl, 3-pyrrolin-2-yl, 3-pyrrolin-3-yl, 2-isoxazolin-3-yl, 3-isoxazolin-3-yl, 4-isoxazolin-3-yl, 2-isoxazolin-4-yl, 3-isoxazolin-4-yl, 4-isoxazolin-4-yl, 2-isoxazolin-5-yl, 3-isoxazolin-5-yl, 4-isoxazolin-5-yl, 2-isothiazolin-3-yl, 3-isothiazolin-3-yl, 4-isothiazolin- 3-yl, 2-isothiazolin-4-yl, 3-isothiazolin-4-yl, 4-isothiazolin-4-yl, 2-isothiazolin-5-yl, 3- isothiazolin-5-yl, 4-isothiazolin-5-yl, 2,3-dihydropyrazol-1-yl, 2,3-dihydropyrazol-2-yl, 2,3-dihydropyrazol-3-yl, 2,3-dihydropyrazol-4-yl, 2,3-dihydropyrazol-5-yl, 3,4- dihydropyrazol-1-yl, 3,4-dihydropyrazol-3-yl, 3,4-dihydropyrazol-4-yl, 3,4- dihydropyrazol-5-yl, 4,5-dihydropyrazol-1-yl, 4,5-dihydropyrazol-3-yl, 4,5- dihydropyrazol-4-yl, 4,5-dihydropyrazol-5-yl, 2,3-dihydrooxazol-2-yl, 2,3-dihydrooxazol- 3-yl, 2,3-dihydrooxazol-4-yl, 2,3-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 3,4-dihydrooxazol-5-yl, 3,4-dihydrooxazol-2-yl, 3,4-dihydrooxazol-3-yl, 3,4-dihydrooxazol-4-yl, 2-piperidinyl, 3- piperidinyl, 4-piperidinyl, 1 ,3-dioxan-5-yl, 2-tetrahydropyranyl, 4-tetrahydropyranyl, 2- tetrahydrothienyl, 3-hexahydropyτidazinyl, 4-hexahydropyridazinyl, 2- hexahydropyrimidinyl, 4-hexahydropyτimidinyl, 5-hexahydropyrimidinyl, 2-piperazinyl, 1 ,3,5-hexahydrotriazin-2-yl and 1 ,2,4-hexahydrotriazin-3-yl and also the corresponding -ylidene radicals;
seven-membered saturated or partially unsaturated heterocycle which contains one, two, three or four heteroatoms from the group consisting of oxygen, nitrogen and sulfur as ring members: for example mono- and bicyclic heterocycles having 7 ring members which, in addition to carbon ring members, contain one to three nitrogen atoms and/or one oxygen or sulfur atom or one or two oxygen and/or sulfur atoms, for example tetra- and hexahydroazepinyl, such as 2,3,4,5-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, 3,4,5,6-tetrahydro[2H]azepin-2-, -3-, -A-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]azepin-1 -, -2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]azepin-1-, -2-, -3-, -4-, -5-, -6- or -7-yl, hexahydroazepin-1-, -2-, -3- or -4-yl, tetra- and hexahydrooxepinyl, such as 2,3,4,5- tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, 2,3,4,7-tetrahydro[1 H]oxepin-2-, -3-, - 4-, -5-, -6- or -7-yl, 2,3,6,7-tetrahydro[1 H]oxepin-2-, -3-, -4-, -5-, -6- or -7-yl, hexahydroazepin-1 -, -2-, -3- or -4-yl, tetra- and hexahydro-1 ,3-diazepinyl, tetra- and hexahydro-1 ,4-diazepinyl, tetra- and hexahydro-1 ,3-oxazepinyl, tetra- and hexahydro-1 ,4-oxazepinyl, tetra- and hexahydro-1 ,3-dioxepinyl, tetra- and hexahydro-1 ,4-dioxepinyl and the corresponding -ylidene radicals;
The term "mono- or bicyclic 5- to 10-membered heteroaromatic ring" as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, wich may comprise a fused 5, 6 or 7 membered ring thus having a total number of ring members from 8 to 10, wherein in each case 1 , 2, 3 or 4 of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The heterocyclic radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member. The fused ring comprises Cs- C7-cycloalkyl, Cs-Cz-cycloalkenyl, or 5 to 7 membered heterocyclyl and phenyl.
The term "5- to 10-membered hetaryl (hetaryl = "heteroaryl")" as used herein refers to a monocyclic heteroaromatic radical which has 5 or 6 ring members, which may be fused to a a benzene ring, a saturated or partially unsaturated 5-, 6-, or 7-membered carbo- cycle or a 5-, 6-, or 7-membered heterocycle thus having a total number of ring members from 8, 9 or 10, wherein in each case 1 , 2, 3 or 4, preferably 1 , 2 or 3, of these ring members are heteroatoms selected, independently from each other, from the group consisting of oxygen, nitrogen and sulfur. The hetaryl radical may be attached to the remainder of the molecule via a carbon ring member or via a nitrogen ring member.
Examples for monocyclic 5-membered hetaryl which contains one oxygen atom, or one sulfur atome, or one, two, three or four nitrogen atoms or one, two or three nitrogen atoms and one sulfur or oxygen atom include 2-furyl, 3-furyl, 2-thienyl, 3-thienyl, 2- pyrrolyl, 3-pyrrolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, 2-oxazolyl, 4-oxazolyl, 5- oxazolyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, 2-imidazolyl, 4-imidazolyl, and 1 ,3,4-triazol- 2-yl.
Examples for monocyclic 6-membered hetaryl which contains one, two or three or one, two, three or four nitrogen atoms in addition to carbon atoms as ring members, are 2- pyridinyl, 3-pyridinyl, 4-pyridinyl, 3-pyridazinyl, 4-pyridazinyl, 2-pyrimidinyl, 4- pyrimidinyl, 5-pyrimidinyl and 2-pyrazinyl.
Examples for 5- to 6-membered heteroaromatic rings being fused to a phenyl ring (or for benzene fused to a 5- to 6-membered heteroaromatic ring) are quinolinyl, iso- quinolinyl, indolyl, indolizinyl, isoindolyl, indazolyl, benzofuryl, benzthienyl, ben- zo[b]thiazolyl, benzoxazolyl, and benzimidazolyl. Ex-amples for 5- to 6-membered het- eroaromatic rings being fused to a cycloalkenyl ring are dihydroindolyl, dihydroindoliz- inyl, dihydroisoindolyl, dihydroquinolinyl, dihydroiso-quinolinyl, chromenyl, chromanyl and the like.
The term "fused 5- to 7- membered heterocycle, which contains 1 , 2, 3 or 4 heteroa- toms selected from O, S and N as ring members" comprises monocyclic heteroaromatic rings having 5 or 6 ring members and nonaromatic saturated or partially unsaturated heterocyclic rings having 5, 6 or 7 ring members. Examples for non-aromatic rings include saturated 5-, 6-, or 7-membered heterocycles such as tetrahydrofuran, tetrahydropyran, piperidine, pyrrolidine, oxazolidine, isoxazolidine, thiazolidine, diox- ane, morpholine, dithiane, pyrazolidine, thiomorpholine, piperazine, imidazolidine, di- oxolane, thrithiane, pyrroline, oxazoline, imidazoline, pyrazoline, thiazoline, pyran, di- hydropyran, tetrahydropyridine, dihydropyridine, thiopyran, dihydrothiopyran, dihy- drothiine, tetrahydroazepine, dihydroazepine, tetrahydrooxepine, dihydrooxepine, tet- rahydothiepine, tetrahydrodiazepiine, and tetrahydrotriazepine. Examples of 5-or 6- membered heteroaromatic rings include pyrrole, pyrazole, imidazole, triazole, oxazole, isoxazole, oxadiazole, thiazole, isothiazole, thiodiazole, furan, thiophene, pyridine, pyrazine, pyrimidine, pyridazine, triazine, tetrazole and tetrazine.
The term "Ci-Cβ-alkanediyl" as used herein and the d-Cβ-alkanediyl moiety in Ci-Cβ- alkanediyloxy refers to straight-chain or branched saturated alkyl groups having 1 to 6 carbon atoms (as mentioned above) in particular 1 to 4 carbon atoms (= C1-C4- alkanediyl), where one of the hydrogen atoms in these groups is replaced by a further bonding position. Examples for linear d-Cβ-alkanediyl comprise methanediyl, ethane- 1 ,2-diyl, propane-1 ,3-diyl, butane-1 ,4-diyl, pentane-1 ,5-diyl, hexane-1 ,6-diyl. Examples for branched d-Cβ-alkanediyl comprise ethyl-1 ,1-diyl, propyl-1 ,1-diyl, butyl-1 ,1-diyl, 1- methylethane-1 ,2 diyl, 1 ,2-dimethylethane-1 ,2-diyl, 1-ethylethane-1 ,2 diyl, 1- methylpropane-1 ,3-diyl, 2-methylpropan-1 ,3-diyl and the like.
The remarks made below concerning preferred embodiments of the variables of the compounds of formula I, of the features of the use and method according to the invention and of the composition of the invention are valid on their own as well as preferably in combination with each other.
Preferred are thiourea compounds of formula I, wherein X is -C(=O)-.
Preference is further given to thiourea compounds of formula I, wherein Y is Ci-Cβ- alkyl, Ci-Ce-alkoxy-Ci-Cβ-alkyl, Ci-C4-alkoxycarbonyl-Ci-C6-alkyl, C1-C4- alkylcarbonyloxy-Ci-Cβ-alkyl or phenoxy-Ci-Cβ-alkyl, wherein the phenyl moiety of phenoxy-Ci-Cβ-alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, d-C6-haloalkylthio, Ci-C6- alkoxy or Ci-C6-haloalkoxy groups. More preference is given to compounds of formula I, wherein Y is d-d-alkyl, such as methyl, ethyl or propyl, Ci-C2-alkoxy-Ci-C4-alkyl such as methoxymethyl, methoxyethyl, ethoxymethyl or ethoxyethyl, C1-C2- alkoxycarbonyl-Ci-d-alkyl such as methoxycarbonylmethyl, methoxycarbonylethyl, methoxycarbonylpropyl, ethoxycarbonylmethyl, ethoxycarbonylethyl or ethoxycarbonyl- propyl, Ci-C2-alkylcarbonyloxy-Ci-C4-alkyl such as methylcarbonyloxymethyl, methyl- carbonyloxyethyl, methylcarbonyloxypropyl, CH3C(O)OC(CH3)2, ethylcarbonyloxy- methyl, ethylcarbonyloxyethyl, ethylcarbonyloxypropyl or C2H5C(O)OC(CH3)2, or phenoxy-Ci-C2-alkyl, wherein the phenyl moiety of phenoxy-Ci-C2-alkyl is unsubstituted or substituted with any combination of 1 to 5, e.g. 1 , 2, 3, 4, or 5 halogen atoms with fluorine or chlorine being most preferred. In particular, Y is methyl, methoxymethyl, methoxycarbonylethyl, CH3C(O)OC(CH3)2, pheonoxymethyl or pentafluorophenoxy- methyl. Most preferably, Y is methyl.
Likewise, preference is given to thiourea compounds of formula I, wherein Y is a 5- or 6-membered hetaryl containing 1 or 2 heteroatoms selected independently from one another from O, S and N as ring members which is unsubstituted or substituted with any combination of 1 , 2, or 3 radicals Ryyy, especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or C1-C3- haloalkyl. More preference is given to compounds of formula I, wherein Y is a 6- membered hetaryl containing 1 or 2 nitrogen atoms as ring members, which is unsubstituted or substituted with any combination of 1 , 2 or 3 radicals Ryyy, especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or Ci-C3-haloalkyl. In particular Y is pyridyl which is unsubstituted or substituted with any combination of 1 , 2 or 3 radicals Ryyy, especially with any combination of 1 , 2 or 3 radicals selected from halogen, Ci-C3-alkyl, Ci-C3-alkoxy, C1-C3- haloalkoxy or Ci-C3-haloalkyl. Most preferably, Y is unsubstituted pyridyl such as 2- pyridyl, 3-pyridyl or 4-pyridyl.
Likewise, preference is given to thiourea compounds of formula I, wherein Y is phenyl which is unsubstituted or substituted with any combination of 1 , 2, 3, 4, or 5 radicals Ryyy, especially with any combination of 1 , 2 or 3 radicals Ryyy. Ryyy is as defined above or has one of the preferred meanings as defined below.
Preferred meanings of Ryyy are halogen, Ci-C3-alkoxy, Ci-C3-haloalkyl, C1-C3- haloalkoxy, Ci-C3-alkylthio, Ci-C3-haloalkylthio, or two adjacent radicals Ryyy together with the carbon atoms of the phenyl ring to which they are attached form a fused 5-, 6-, or 7-membered heterocycle, which contains 1 or 2 heteroatoms selected from oxygen or sulfur as ring members, such as 1 ,4-dioxane, 1 ,3-dioxolane, tetrahydrofuran or tet- rahydrothiophen.
Preference is further given to thiourea compounds of formula I, wherein n in formula I is 0, 1 , 2 or 3. A particular preferred embodiment relates to compounds of formula I, wherein n is 1 or 2. Another preferred embodiment relates to compounds of formula I, wherein, n is 3. Preference is further given to thiourea compounds of formula I, wherein m in formula I is 0, 1 , 2 or 3, in particular 1 , 2 or 3. A particular preferred embodiment relates to compounds of formula I, wherein m is 1 or 2. Another preferred embodiment relates to compounds of formula I, wherein m is 3.
In particular preferred are compounds of formula I, wherein n+m is an integer from 1 , 2, 3, 4 or 5, in particular 3, 4 or 5. According to this embodiment, n is preferably 1 or 2 and m is preferably 2 or 3.
Preference is further given to thiourea compounds of formula I, wherein each R1 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, d-Ce-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups. More preferably, each R1 is selected from fluorine, chlorine, bromine, methyl, ethyl, propyl, isopropyl, tert-butyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylthio or phenyl, which may be unsubstituted or may carry 1 , 2 or 3 radicals selected from halogen or methyl. Most preferably, R1 is selected from chloro, fluoro, bromo, CH3, CH3O or CF3.
In case that n is equal to or greater than 2, R1 may be same or different. In principle, the radical(s) R1 can be located in any position on the phenyl ring. Preferably, at least one radical R1 is attached at the carbon atom in one of the meta-positions of the phenyl ring relative to the bonding position of the phenyl to the remainder of the compound of formula I.
Preference is further given to thiourea compounds of formula I, wherein each R2 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-Cβ-alkyl, Ci-Cβ-haloalkyl, C-i-Cβ-alkylthio, C-i-Cβ-haloalkylthio, C-i-Cβ-alkoxy or Ci-Cβ-haloalkoxy groups. More preferably, each R2 is selected from fluoro, chloro, bromo, methyl, ethyl, methoxy, ethoxy, difluoromethyl, trifluoromethyl, difluoromethoxy, trifluoromethoxy, methylthio or phenyl, which may be unsubstituted or may carry 1 , 2 or 3 radicals selected from halogen or methyl. Most preferably, R2 is selected from chloro, fluoro, bromo, CH3, CH3O or CF3.
In case that m is equal to or greater than 2, R2 may be same or different. In principle, the radical(s) R2 can be located in any position on the phenyl ring. Preferably, one radical R2 is attached at the carbon atom in one of the meta-positions of the phenyl ring relative to the bonding position of the phenyl to the remainder of the compound of formula I.
Also preferred are thiourea compounds of the formula I, wherein two adjacent radicals R2 together with the carbon atoms of the phenyl ring to which they are attached form a ring which is depicted as a benzene ring, a saturated 5-, 6-, or 7-membered carbocycle, a partially unsaturated 5-, 6-, or 7-membered carbocycle, a 5-, 6-, or 7-membered saturated heterocycle, a partially unsaturated 5-, 6-, or 7-membered heterocycle, which heterocycles contain 1 , 2, or 3 heteroatoms selected from O, S and N as ring members, and a 5- or 6-membered heteroaromatic ring which contains 1 , 2, or 3 heteroatoms selected from O, S and N as ring members
and wherein the ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, Ci-C4-alkyl, C1-C4- haloalkyl, Ci-C4-alkoxy and cyano.
Amongst compounds of formula I, wherein two adjacent radicals R2 together with the carbon atoms of the phenyl ring to which they are attached form a ring, those are in particular preferred wherein said radicals R2 form a bivalent radical selected from -(CH2J4-, -(CH2)S-, -O-CH2-O-, -0-(CH2J2-O-, -0-(CH2J3-OTO-CF2-O- ,-0-(CF2J2-O- , -0(CH2J2-, -0-(CH2J3-, -CH(CHs)-CH(CHs)-O-, -CH2-C(CHs)2-O-, -CH2-CHCH3-O-, -CHCH3-CH2O-, -S(CH2J2-, -S-(CH2J3-, -CH(CH3)-CH(CH3)-S-, -CH2-C(CHs)2-S-, -CH2-CHCH3-S-, -CHCH3-CH2S-, -0-CH=CH-, -S-CH=CH-, -CH=CH-CH=CH- and -CH=CH-CH=N-. In particular, two radicals R2 that are bound to adjacent carbon atoms together form a bivalent radical are selected from -0-CH2-O-, -0-CH2-CH2-O, -0-CH2-CH2-, -0-CH2-CH2-CH2-, -S-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH2-CH2-CH2-CH2-, -CH=CH-CH=CH- and -CH=CH-CH=N-.
Furthermore, the radical R^1 is preferably C-i-Cβ-alky, Ci-C4-alkylcarbonyl or phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 CT Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, d-Ce-haloalkylthio, Ci-C6-alkoxy or CrC6- haloalkoxy groups.
The radical R^2 is preferably C-i-Cβ-alkyl or phenyl which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-Cβ-alkyl, C-i-Cβ-haloalkyl, C-i-Cβ- alkylthio, C-i-Cβ-haloalkylthio, d-Cβ-alkoxy or Ci-Cβ-haloalkoxy groups. The radicals Ry3 and Ry4 are, independently of each other, preferably selected from Ci-Cβ-alkyl or hydrogen or may form together with the nitrogen atom to which they are attached may also form a saturated 5- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, or 4 substituents selected from the group consisting of halogen, d-Cε-alkyl, d-Cβ-alkoxy and C-i-Cε-haloalkyl.
The radical Ry5 is preferably Ci-C4-alkoxy.
The radicals Ry6 and Ry7 are preferably selected, independently of each other, from the group consisting of hydrogen, d-Cε-alkyl, d-Cε-haloalkyl, Ci-Cβ-alkoxy, C2-C4-alkenyl, C2-C4-haloalkenyl and C2-C4-alkynyl. Likewise, preference is given to compounds of formula I, wherein Ry6 and Ry7 together with the nitrogen atom to which they are at- tached may also form a saturated 5- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-C4-alkyl, Ci-C4-alkoxy,Ci-C4-haloalkyl, C1-C4- haloalkoxy.
The radicals Ry8 and Ry9 independently of each other, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy, Cs-Cβ-cycloalkyl which is un- substituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, phenyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, benzyl, phenoxy and phenoxy-Ci-C4-alkyl, wherein phenoxy and the phenyl moiety of benzyl and phenoxy-Ci-C4-alkyl is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and C1-C4- alkoxy. In particular, Ry8 and Ry9 independently of each other are Ci-C4-alkoxy, especially methoxy or ethoxy.
The radicals Ry1° and Ry11 independently of each other, are preferably selected from the group consisting of hydrogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-alkylthio, C3-C6-cycloalkyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, phenyl which is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy, benzyl, phenoxy and phenoxy-Ci-C4-alkyl, wherein phenoxy and the phenyl moiety of benzyl and phenoxy-Ci-C4-alkyl is unsubstituted or may carry 1 , 2 or 3 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy. In particular, Ry1° and Ry11 independently of each other are Ci-C4-alkoxy, especially methoxy or ethoxy. The radical Ry12 is preferably selected from hydroxy, Ci-C4-alkyl, Ci-C4-alkoxy, C1-C4- haloalkyl, phenyl, phenoxy and phenyl-Ci-C4-alkyl, wherein phenyl , phenoxy and phenyl-Ci-C4-alkyl may be unsubstituted or substituted with 1 or 2 substituents selected from Ci-C4-alkyl, Ci-C4-haloalkyl and Ci-C4-alkoxy.
The radicals Ry13, Ry14 and Ry15, independently of each other, are preferably selected from the group consisting of Ci-C4-alkyl and Ci-C4-alkoxy.
The radicals Ra1 and Ra2 preferably are hydrogen or C-i-Cε-alkyl.
The radical Ar is preferably phenyl, naphthyl or a 5- or 6-membered hetaryl containing 1 or 2 heteroatoms selected from oxygen, sulphur and nitrogen as ring members, wherein Ar is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy or Ci- Cβ-haloalkoxy groups.
The radical Cy is preferably Cs-Cs-cycloalkyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Cε-alkyl, C-i-Cε-haloalkyl, C-i-Cε-alkylthio, Ci-Cβ-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups.
The radical Ryy is preferably halogen such as chlorine, fluorine or bromine, hydroxy, cyano, Ci-C4-alkyl, Ci-C4-alkoxy, amino, Ci-C4-alkylamino and di(Ci-C4-alkyl)amino,
A preferred embodiment of the invention relates to the compounds I of formula I',
Figure imgf000025_0001
wherein
X and Y have one of the meanings given above, especially one of the preferred meanings; R1a and R1b, are, independently of one another, hydrogen or have one of the meanings given above for R1; and
R2a, R2b and R2c are, independently of one another other, hydrogen or have one of the meanings given above for R2. In a more preferred embodiment, the invention relates to compounds of formula I', wherein R1a and R1b are, independently from one another, selected from halogen, Ci- C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy and phenyl, which is unsubsti- tuted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Cε-alkyl, Ci-Cβ- haloalkyl, d-Cε-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups, provided that one of the radicals R1a or R1b may also be hydrogen.
A further more preferred embodiment of the present invention relates to compounds of the formula I', wherein both radicals R1a and R1b are different from hydrogen.
Amongst compounds of the formula I', particular preference is given to those compounds, wherein R1a and R1b are, independently of one another, selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy. More preferably R1a and R1b, independently of each other, are selected from fluoro, chloro, bromo, methyl, methoxy, difluoromethyl, trifluoromethyl, difluoromethoxy and trifluoromethoxy. Most preferably R1a and R1b are, independently of each other, selected from chloro, methyl and methoxy, especially methyl.
In a further more preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b are, independently from one another, halogen, Ci-C4-alkyl, Ci- C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Cε-alkyl, d-Cε-haloalkyl, C-i-Cε-alkylthio, Ci- Cβ-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups.
Amongst compounds of the formula I', particular preference is given to those compounds, wherein R2a and R2b are, independently of one another, are selected from the group consisting of fluoro, chloro, bromo, methyl, methoxy, difluoromethyl, trifluoromethyl, difluoromethoxy and trifluoromethoxy, especially methyl or chloro.
In a further more preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b together form a bivalent radical which is bonded to the phenyl ring via 1 or 2 oxygen atoms, 1 or 2 sulphur atoms or 1 nitrogen atom.
In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b together form a bivalent radical which is bonded to the phenyl ring via an oxygen atom in the Re position.
In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b together form a bivalent radical which is bonded to the phenyl ring via a sulfur atom in the Re position. In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b together form a bivalent radical which is bonded to the phenyl ring via a nitrogen atom in the Re position.
In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R2a and R2b together form a bivalent radical which is bonded to the phenyl ring via an oxygen atom in the Re position. For the bivalent radicals listed in the following, the first atom is meant to be bound to the phenyl ring at the R2a position. Amonst these preference is given to those compounds of formula I', wherein R2a and R2b are selected from -(CH2)4-, -(CH2)3-, -0-CH2-O-, -O-(CH2)2-O-, -O-(CH2)3-O- ,-0-CF2-O- ,-O-(CF2)2-O- , -O(CH2)2-, -O-(CH2)3-, -(CH2)2-O-, -(CH2)3-O-, -CH(CH3)- CH(CHs)-O-, -O-CH(CH3)-CH(CH3)-, -CH2-C(CHs)2-O-, -CH2-CHCH3-O-, -CHCH3- CH2O-, -0-CH2-C(CHs)2-, -0-CH2-CHCH3-, -0-CHCH3-CH2-, -S(CH2)2-, -S-(CH2)3-, -(CH2)2-S-, -(CH2)S-S-, -CH(CHs)-CH(CHs)-S-, -CH2-C(CHs)2-S-, -CH2-CHCH3-S-,
-CHCH3-CH2S-, -S-CH(CHs)-CH(CHs)-, -S-CH2-C(CHs)2-, -S-CH2-CHCH3-, -S-CHCH3- CH2-, -0-CH=CH-, -S-CH=CH-, -CH=CH-O-, -CH=CH-S-, -CH=CH-CH=CH-, -N=CH-CH=CH-and -CH=CH-CH=N-. In particular, R2a and R2b are selected from -CH2-CH2-CH2-CH2-,-O-CH2-O-, -0-CH2-CH2-O, -0-CH2-CH2-, -0-CH2-CH2-CH2-, -(CHz)2-O-, -S-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH=CH-CH=CH- and -N=CH-CH=CH-.
In a further particular preferred embodiment, the invention relates to compounds of formula I', wherein R2c is hydrogen, fluoro, chloro, CF3 or CH3, preferably hydrogen.
Especially preferred are compounds of formula I' having the following meanings:
X is -C(=0)-;
Y is Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl-Ci-C4-alkyl, Ci-C4- alkylcarbonyloxy-Ci-C4-alkyl or phenoxy-Ci-C4-alkyl, wherein the phenyl moiety of phenoxy-Ci-Cβ-alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, Ci-C6- haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups, or pyridyl which is unsubstituted or substituted with any combination of 1 , 2 or 3 halogen atoms, Ci-C3- alkyl, Ci-Cs-alkoxy, Ci-Cs-haloalkoxy or Ci-C3-haloalkyl groups, in particular pyridyl, methyl, methoxymethyl, methoxycarbonylethyl,
CH3C(O)OC(CHS)2, pheonoxymethyl or pentafluorophenoxymethyl; R1a and R1b are, independently from one another, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R1a or R1b may also be hydrogen, in particular R1a and R1b are methyl; R2a and R2b are, independently from one another halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R2a or R2b may also be hydrogen, in particular R2a and R2b are halogen or methyl, especially chloro or methyl; and R2c is hydrogen.
Likewise, especially preferred are compounds of formula I', having the following meanings:
X is -C(=O)-; Y is Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl-Ci-C4-alkyl, Ci-C4- alkylcarbonyloxy-Ci-C4-alkyl or phenoxy-Ci-C4-alkyl, wherein the phenyl moiety of phenoxy-Ci-Cβ-alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, CrC6- haloalkylthio, Ci-C6-alkoxy or C-i-Cβ-haloalkoxy groups, or pyridyl which is unsub- stituted or substituted with any combination of 1 , 2 or 3 halogen atoms, C1-C3- alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or Ci-C3-haloalkyl groups; in particular pyridyl, methyl, methoxymethyl, methoxycarbonylethyl, CH3C(O)OC(CH3)2, pheonoxymethyl or pentafluorophenoxymethyl; R1a and R1b are, independently from one another, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R1a or R1b may also be hydrogen, in particular R1a and R1b are methyl;
R2a together with R2b forms a bivalent radical selected from -CH2-CH2-CH2-CH2-, -O-CH2-O-, -O-CH2-CH2-O, -O-CH2-CH2-, -O-CH2-CH2-CH2-, -(CHz)2-O-, -S-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH=CH-CH=CH- and -N=CH-CH=CH- (in these radicals, the first atom is meant to be bound to the phenyl ring at the R2a position); R2c is hydrogen.
Examples of especially preferred embodiments of the compounds of the formula I' are illustrated by the following formulae (IM ), (l'.2), (l'.3), (l'.4), (l'.5), (l'.6), (l'.7), (l'.8), (l'.9), (IMO), (IM 1 ), (IM2) and (IM 3), wherein X is C(O) and R1a, R1b and Y have one of the meanings given above, in particular one of the preferred meanings:
Figure imgf000029_0001
(IM) (l\2)
Figure imgf000029_0002
(l'.3) (l\4)
Figure imgf000029_0003
(l'.7) (l'.8)
Figure imgf000030_0001
(l'.9) (IMO)
Figure imgf000030_0002
(IM 1 ) (IM2)
Figure imgf000030_0003
(IM 3)
In particular with a view to their use for combating invertebrate pests, preference is given to the individual compounds of the formula I '-A (compounds of formula I', where R2c is H, X is C(=O)) compiled in tables 1 to 4 below, where the variables R1a, R1b, R2a and R2b each have the meanings given in one row of table A
Figure imgf000030_0004
Table A:
Figure imgf000031_0001
*) the first atom is meant to be bound to the phenyl ring at the R2a position
Table 1 :
Compounds of the formula I'-A, in which Y is methyl, R1a, R1b, R2a and R2b for each individual compound correspond in each case to one row of table A.
Table 2:
Compounds of the formula I'-A, in which Y is 2-pyridyl, R1a, R1b, R2a and R2b for each individual compound correspond in each case to one row of table A. Table 3:
Compounds of the formula I '-A, in which Y is 3-pyridyl, R1a, R1b, R2a and R2b for each individual compound correspond in each case to one row of table A.
Table 4:
Compounds of the formula I '-A, in which Y is 4-pyridyl, R1a, R1b, R2a and R2b for each individual compound correspond in each case to one row of table A.
Preparation of the compounds of formula I can be accomplished according to standard methods of organic chemistry, e.g. by the methods described hereinafter or in the working examples but are not limited to the routes given below.
The compounds of formula I wherein X is C(O), can for instance be prepared according to the method depicted in scheme 1 by esterification reaction or alcoholysis reaction.
Figure imgf000032_0001
(I)
In scheme 1 , n, m, R1, R2, and Y have one of the meanings given above and LG denotes a leaving group such as halogen, Ci-Cβ-alkoxy or hydroxy.
According to scheme 1 , a 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il is reacted with carboxylic acids, esters or carboxylic acid halogenides, especially chlorides, by methods familiar to an organic chemist and well known in the art to give compounds of formula I.
The compounds of formula I wherein X is C(O), can for instance also be prepared according to the method depicted in scheme 2 by reacting primary amines of formula III or a salt thereof with appropriately substituted isothiocyanates of formula IV. Scheme 2:
Figure imgf000033_0001
(I) In scheme 2, n, m, R1, R2, and Y have one of the meanings given above.
The compounds of formula I wherein X is C(O), can for instance also be prepared according to the method depicted in scheme 3 by reacting the isothiocyanate (V) with an appropriate carboxylic acid 2-aminoethyl ester of formula (Vl) or its salt.
Scheme 3:
Figure imgf000033_0002
(V)
(I)
In scheme 3, n, m, R1, R2, and Y have one of the meanings given above. It may be advantageous to carry out the reaction in the presence of a base.
The compounds of formula I wherein X is C(S) can for instance be prepared by thiona- tion of the corresponding compound I wherein X is C(O) using phosphorus pentasulfide or Lawesson's reagent.
The compounds of formula I wherein X a single bond and Y is SiRy13Ry14Ry15, can for instance be prepared according to the method depicted in scheme 2 by reacting primary amines of formula III with an appropriately substituted isothiocyanate S=C=N-CH2-CH2-O-SiRy13Ry14Ry15. Alternatively, the compounds of formula I wherein X a single bond and Y is SiRy13Ry14Ry15, can be prepared according to the method depicted in scheme 3 by reacting H2N-CH2-CH2-O-SiRy13Ry14Ry15. with the isothiocyanate (V)
The compounds of formula I wherein X a single bond and Y is SO2Ry12 can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea com- pound Il with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur triox- ide/water to give compounds I with Ry12 being OH. Compounds of formula I with Ry12 being OH may be modified by etherifcation to give compounds I with Ry12 being alkoxy or optionally substituted phenoxy. The reaction of compounds of formula Il with an appropriate sulfonic acid Ry12Sθ2-OH gives compounds of formula I with Ry12 being alkyl, haloalkyl, optionally substituted phenyl or phenyl-Ci-C4-alkyl.
The compounds of formula I wherein X a single bond and Y is P(O)Ry8Ry9 can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il with phosphoric acid or phosphoroxychloride/water or with an ortho- phosphate ester.
The compounds of formula I wherein X a single bond and Y is P(S)Ry10Ry11, can for instance be prepared by reacting the 1-(1 ,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compound Il with a thiophosphate salt or an appropriate 0,0-dialkyl thiophosphoric acid or diphenyl thiophosphoric acid.
The compounds of formula I wherein X a single bond and Y is NRy6Ry7 can be prepared according to scheme 4 by reacting a compound of formula V with an appropriate amine of formula Vl I or salt thereof.
Scheme 4:
Figure imgf000034_0001
(V)
(i)
In scheme 4, n, m, R1, R2, Ry6, and Ry7 have one of the meanings given above.
In the schemes above, suitable amine salts are e.g. the acid addition salts formed by treating the amine with an inorganic or organic acid. Anions of useful acids are e.g. sulfate, hydrogen sulfate, phosphate, dihydrogen phosphate, hydrogen phosphate, nitrate, bicarbonate, carbonate, chloride, bromide, p-toluene sulfonate, and the anions of Ci-C4-alkanoic acids such as acetate, propionate, and the like. Compounds of the formulae Il and V are known, e.g. from WO 2005/063724 and WO 2006/125745 or can be prepared in analogy to the methods described there. For example, they can be prepared as outlined in scheme 5 below.
Scheme 5:
Figure imgf000035_0001
In scheme 5, n, m, R1 and R2 have one of the meanings given above.
According to the method outlined in scheme 5, a 1 ,2-diphenylaminoethane III is converted into the corresponding isothiocyanate V by conventional means, e.g. by reacting III with thiophosgene (see e.g. Houben-Weyl, E4, "Methoden der Organischen Che- mie", chapter INc, pp. 837-842. The isothiocyanate V is then reacted with 2- aminoethanol of the formula VIII, thereby obtaining the thiourea compound of the formula II. The reaction of aminoethanol VIII with isothiocyanate V can be performed in accordance with standard methods of organic chemistry, see e.g. Biosci. Biotech. Bio- chem. 1992, 56 (7), 1062-1065 (cf. eg WO 2005/063724).
Diphenylethylamines of the formula III are known in the art (e.g. 1 ,2- diphenylethylamine, CAS-Nr.[ 3082-58-4] ) or they can be prepared by methods familiar to an Organic chemist and well known in the art. Suitable methods for preparing diphenylethylamines III comprise inter alia the reductive amination of the corresponding phenylbenzylketones or the reduction of the corresponding phenylbenzyloximes (see e.g. J. Med. Chem. 1995, 38, 1600-1607; J. Med. Chem 1994, 37 (7), 913-923). 2-Aminoethanol VIII is commercially available.
lsothiocyanates of the general formula IV can for instance be prepared according to the procedures described in Coll. Czech. Chem. Comm. 1986, 51 , 112 - 1 17. Carboxylic acid 2-aminoethyl ester of formula (Vl) and amine compounds of formula (VII) are commercially available or they can be prepared according to routine methods, which are familiar to an organic chemist.
As a rule, the compounds of formula I can be prepared by the methods described above. If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds of formula I or by customary modifications of the synthesis routes described. For example, in individual cases, certain compounds of formula I can advantageously be prepared from other compounds of formula I by ester hydrolysis, amidation, esterification, ether cleavage, olefi- nation, reduction, metal catalyzed coupling reactions, oxidation and the like.
If individual compounds cannot be prepared via the above-described routes, they can be prepared by derivatization of other compounds I or by customary modifications of the synthesis routes described.
The reaction mixtures are worked up in the customary manner, for example by mixing with water, separating the phases, and, if appropriate, purifying the crude products by chromatography, for example on alumina or 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 digestion.
Due to their excellent activity, the compounds of formula I may be used for controlling invertebrate pests.
Accordingly, the present invention also provides a method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a cultivated plant, plant propagation materials (such as seed), soil, area, material or environment in which the pests are growing or may grow, or the materials, cultivated plants, plant propagation materials (such as seed), soils, surfaces or spaces to be protected from pest attack or infestation with a pesticidally effective amount of a compound of formula I or a salt thereof or a composition as defined above.
Preferably, the method of the invention serves for protecting plant propagation material (such as seed) and the plant which grows therefrom from animal pest attack or infestation and comprises treating the plant propagation material (such as seed) with a pesti- cidally effective amount of a compound of the formula I or an agriculturally acceptable salt thereof as defined above or with a pesticidally effective amount of an agricultural composition as defined above and below. The method of the invention is not limited to the protection of the "substrate" (plant, plant propagation materials, soil material etc.) which has been treated according to the invention, but also has a preventive effect, thus, for example, according protection to a plant which grows from a treated plant propagation materials (such as seed), the plant itself not having been treated.
In the sense of the present invention, "invertebrate pests" are preferably selected from arthropods and nematodes, more preferably from harmful insects, arachnids and nematodes, and even more preferably from insects, acarids and nematodes.
The invention further provides an agricultural composition for combating such invertebrate pests, which comprises such an amount of at least one compound of formula I or at least one agriculturally useful salt thereof and at least one inert liquid and/or solid agronomically acceptable carrier that has a pesticidal action and, if desired, at least one surfactant.
Such a composition may contain a single active compound of formula I or a salt thereof or a mixture of several active compounds of formula I or their salts according to the present invention. The composition according to the present invention may comprise an individual isomer or mixtures of isomers as well as individual tautomers or mixtures of tautomers.
The compounds of the formula I and the pestidicidal compositions comprising them are effective agents for controlling arthropod pests and nematodes. Invertebrate pests controlled by the compounds of formula I include for example:
insects from the order of the lepidopterans (Lepidoptera), for example Agrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsia gemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius, Cacoecia murinana, Capua reticulana, Cheima- tobia brumata, Choristoneura fumiferana, Choristoneura occidentalis, Cirphis unipunc- ta, Cydia pomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella, Ea- rias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella, Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholitha funebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens, Heliothis zea, HeIIuIa undalis, Hibernia defoliaria, Hy- phantria cunea, Hyponomeuta malinellus, Keiferia lycopersicella, Lamb-dina fiscellaria, Laphygma exigua, Leucoptera coffeella, Leucoptera scitella, Lithocol-letis blancardella, Lobesia botrana, Loxostege sticticalis, Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosoma neustria, Mamestra brassicae, Orgyia pseu-dotsugata, Ostrinia nubilalis, Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalera bucephala, Phthorimaea operculella, Phyllocnistis citrella, Pieris bras-sicae, Plathypena scabra, Plutella xylostella, Pseudoplusia includens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotroga cerealella, Sparganothis pilleriana, Spodoptera frugi- perda, Spodoptera littoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrix viri- dana, Trichoplusia ni and Zeiraphera canadensis;
beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus, Agriotes obscu- rus, Amphimallus solstitialis, Anisandrus dispar, Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophagus piniperda, Blitophaga undata, Bruchus rufi- manus, Bruchus pisorum, Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cero- toma trifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnema tibialis, Conoderus vespertinus, Crioceris asparagi, Diabrotica Iongicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachna varivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobius abietis, Hypera brunneipennis, Hypera postica, lps typographus, Lema bilineata, Lema melanopus, Leptinotarsa decemlineata, Limonius californicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethes aeneus, Melolontha hip- pocastani, Melolontha melolontha, Oulema oryzae, Ortiorrhynchus sulcatus, Otiorrhyn- chus ovatus, Phaedon cochleariae, Phyllotreta chrysocephala, Phyllophaga sp., Phyl- lopertha horticola, Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitona lineatus and Sitophilus granaria;
dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrepha ludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana, Chrysomya homi- nivorax, Chrysomya macellaria, Contarinia sorghicola, Cordylobia anthropophaga, Cu- lex pipiens, Dacus cucurbitae, Dacus oleae, Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans, Haematobia irritans, Haplodiplosis equestris, Hylemyia platura, Hypoderma lineata, Liriomyza sativae, Liriomyza trifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mayetiola destruc- tor, Musca domestica, Muscina stabulans, Oestrus ovis, Oscinella frit, Pegomya hyso- cyami, Phorbia antiqua, Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rha- goletis pomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa;
thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniella fusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothrips citri, Thrips oryzae, Thrips palmi and Thrips tabaci; hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Atta sexdens, Atta texana, Hoplocampa minuta, Hoplocampa testudinea, Monomorium pharaonis, So- lenopsis geminata and Solenopsis invicta;
heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissus leucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercus intermedius, Eurygaster integriceps, Eu- schistus impictiventris, Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Ne- zara viridula, Piesma quadrata, Solubea insularis and Thyanta perditor;
homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis, Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphis gossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphis sambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii, Brachycaudus cardui, Brachycaudus helichrysi, Brachy- caudus persicae, Brachycaudus prunicola, Brevicoryne brassicae, Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii, Cryptomyzus ribis, Dreyfusia nordman- nianae, Dreyfusia piceae, Dysaphis radicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphis pyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactu- cae, Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megoura viciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae, Myzus as- calonicus, Myzus cerasi, Myzus persicae, Myzus varians, Nasonovia ribis-nigri, NiIa- parvata lugens, Pemphigus bursarius, Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri, Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosi- phum padi, Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphis graminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furcifera Trialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;
termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes, Reticulitermes flavipes, Reticulitermes lucifugus und Termes natalensis;
orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis, Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa, Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum, Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus, Nomadacris septemfasciata, Periplaneta americana, Schistocerca ameri- cana, Schistocerca peregrina, Stauronotus maroccanus and Tachycines asynamorus;
Arachnoidea, such as arachnids (Acarina), e.g. of the families Argasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum, Amblyomma variegatum, Argas persi- cus, Boophilus annulatus, Boophilus decoloratus, Boophilus microplus, Dermacentor silvarum, Hyalomma truncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus mou- bata, Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalus appendi- culatus, Rhipicephalus evertsi, Sarcoptes scabiei, and Eriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivora and Eriophyes sheldoni; 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 ulmi, Panonychus citri, and oligonychus pratensis;
Siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp ;
The compositions and compounds of formula I are useful for the control of 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; Het- erodera 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 longicaudatus and other Belonolaimus species; Pine nematodes, Bursaphelenchus xylophilus and other Bursaphelenchus species; Ring nematodes, Criconema species, Criconemella species, Criconemoides species, Mesocriconema species; Stem and bulb nematodes, Ditylen- chus destructor, Ditylenchus dipsaci and other Ditylenchus species; AwI nema-todes, Dolichodorus species; Spiral nematodes, Heliocotylenchus multicinctus and other HeIi- cotylenchus species; Sheath and sheathoid nematodes, Hemicycliophora species and Hemicriconemoides species; Hirshmanniella species; Lance nematodes, Hoploaimus species; false rootknot nematodes, Nacobbus species; Needle nematodes, Longidorus elongatus and other Longidorus species; Pin nematodes, Paratylen-chus species; Lesion nematodes, Pratylenchus neglectus, Pratylenchus penetrans, Pratylenchus curvi- tatus, Pratylenchus goodeyi and other Pratylenchus species; Burrowing nematodes, Radopholus similis and other Radopholus species; Reniform nematodes, Rotylenchus robustus and other Rotylenchus species; Scutellonema species; Stubby root nematodes, Trichodorus primitivus and other Trichodorus species, Paratrichodorus species; Stunt nematodes, Tylenchorhynchus claytoni, Tylenchorhynchus dubius and other Ty- lenchorhynchus species; Citrus nematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; and other plant parasitic nematode species.
In a preferred embodiment of the invention the compounds of formula I are used for controlling insects or arachnids, in particular insects of the orders Lepidoptera, Coleop- tera, Thysanoptera and Homoptera and arachnids of the order Acarina. The com- pounds of the formula I according to the present invention are particularly useful for controlling insects of the order Thysanoptera and Homoptera.
The compounds of formula I or the pesticidal compositions comprising them may be used to protect growing plants and crops from attack or infestation by invertebrate pests, especially insects, acaridae or arachnids by contacting the plant/crop with a pes- ticidally effective amount of compounds of formula I. The term "crop" refers both to growing and harvested crops.
The compounds of formula I can be converted into the customary formulations, for example solutions, emulsions, suspensions, dusts, powders, pastes and granules. The use form depends on the particular intended purpose; in each case, it should ensure a fine and even distribution of the compound according to the invention.
The formulations are prepared in a known manner (see e.g. for review US 3,060,084, EP-A 707 445 (for liquid concentrates), Browning, "Agglomeration", Chemical Engineering, Dec. 4, 1967, 147-48, Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York, 1963, pages 8-57 and et seq. WO 91/13546, US 4,172,714, US 4,144,050, US 3,920,442, US 5,180,587, US 5,232,701 , US 5,208,030, GB 2,095,558, US 3,299,566, Klingman, Weed Control as a Science, John Wiley and Sons, Inc., New York, 1961 , Hance et al., Weed Control Handbook, 8th Ed., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H., Grubemann, A., Formulation tech-nology, Wiley VCH Verlag GmbH, Weinheim (Germany), 2001 , 2. D. A. Knowles, Chemistry and Technology of Agrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998 (ISBN 0-7514-0443-8), for example by extending the active compound with auxiliaries suitable for the formulation of agrochemicals, such as solvents and/or carriers, if desired emulsifiers, surfactants and dispersants, preservatives, anti-foaming agents, anti-freezing agents, for seed treatment formulation also optionally colorants and/or binders and/or gelling agents.
Examples of suitable solvents are water, aromatic solvents (for example Solvesso products, xylene), paraffins (for example mineral oil fractions), alcohols (for example methanol, butanol, pentanol, benzyl alcohol), ketones (for example cyclohexanone, gam- ma-butyrolactone), pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]), acetates (glycol diacetate), glycols, fatty acid dimethylamides, fatty acids and fatty acid esters. In principle, solvent mixtures may also be used.
Suitable emulsifiers are non-ionic and anionic emulsifiers (for example polyoxyethylene fatty alcohol ethers, alkylsulfonates and arylsulfonates). Examples of dispersants are lignin-sulfite waste liquors and methylcellulose.
Suitable surfactants used are alkali metal, alkaline earth metal and ammonium salts of lignosulfonic acid, naphthalenesulfonic acid, phenolsulfonic acid, dibutylnaphthalene- sulfonic acid, alkylarylsulfonates, alkyl sulfates, alkylsulfonates, fatty alcohol sulfates, fatty acids and sulfated fatty alcohol glycol ethers, furthermore condensates of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensates of naphthalene or of naphthalenesulfonic acid with phenol and formaldehyde, poly- oxyethylene octylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ether, tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcohol and fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropyl- ene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignosulfite waste liquors and methylcellulose.
Substances which are suitable for the preparation of directly sprayable solutions, emulsions, pastes or oil dispersions are mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, furthermore coal tar oils and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons, for example toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or their derivatives, methanol, etha- nol, propanol, butanol, cyclohexanol, cyclohexanone, isophorone, highly polar solvents, for example dimethyl sulfoxide, N-methylpyrrolidone or water.
Also anti-freezing agents such as glycerin, ethylene glycol, propylene glycol and bactericides such as can be added to the formulation.
Suitable antifoaming agents are for example antifoaming agents based on silicon or magnesium stearate.
A suitable preservative is e.g. dichlorophen.
Seed treatment formulations may additionally comprise binders and optionally colorants.
Binders can be added to improve the adhesion of the active materials on the seeds after treatment. Suitable binders are block copolymers EO/PO surfactants but also po- lyvinylalcoholsl, polyvinylpyrrolidones, polyacrylates, polymethacrylates, polybutenes, polyisobutylenes, polystyrene, polyethyleneamines, polyethyleneamides, poly- ethyleneimines (Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, ty- lose and copolymers derived from these polymers.
Optionally, also colorants can be included in the formulation. Suitable colorants or dyes for seed treatment formulations are Rhodamin B, C.I. Pigment Red 112, C.I. Solvent Red 1 , pigment blue 15:4, pigment blue 15:3, pigment blue 15:2, pigment blue 15:1 , pigment blue 80, pigment yellow 1 , pigment yellow 13, pigment red 1 12, pigment red 48:2, pigment red 48:1 , pigment red 57:1 , pigment red 53:1 , pigment orange 43, pigment orange 34, pigment orange 5, pigment green 36, pigment green 7, pigment white 6, pigment brown 25, basic violet 10, basic violet 49, acid red 51 , acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10, basic red 108.
Examples of a gelling agent is carrageen (Satiagel®).
Powders, materials for spreading and dustable products can be prepared by mixing or concomitantly grinding the active substances with a solid carrier.
Granules, for example coated granules, impregnated granules and homogeneous granules, can be prepared by binding the active compounds to solid carriers.
Examples of solid carriers are mineral earths such as silica gels, silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground synthetic materials, fertilizers, such as, for example, ammonium sulfate, ammonium phosphate, ammonium ni- trate, ureas, and products of vegetable origin, such as cereal meal, tree bark meal, wood meal and nutshell meal, cellulose powders and other solid carriers.
In general, the formulations comprise from 0.01 to 95% by weight, preferably from 0.1 to 90% by weight, of the active compound(s). In this case, the active compound(s) are employed in a purity of from 90% to 100% by weight, preferably 95% to 100% by weight (according to NMR spectrum).
For seed treatment purposes, respective formulations can be diluted 2-10 fold leading to concentrations in the ready to use preparations of 0.01 to 60% by weight active compound by weight, preferably 0.1 to 40% by weight.
The compounds of formula I can be used as such, in the form of their formulations or the use forms prepared therefrom, for example in the form of directly sprayable solutions, powders, suspensions or dispersions, emulsions, oil dispersions, pastes, dusta- ble products, materials for spreading, or granules, by means of spraying, atomizing, dusting, spreading or pouring. The use forms depend entirely on the intended purposes; they are intended to ensure in each case the finest possible distribution of the active compound(s) according to the invention.
Aqueous use forms can be prepared from emulsion concentrates, pastes or wettable powders (sprayable powders, oil dispersions) by adding water. To prepare emulsions, pastes or oil dispersions, the substances, as such or dissolved in an oil or solvent, can be homogenized in water by means of a wetter, tackifier, dispersant or emulsifier. Ho- wever, it is also possible to prepare concentrates composed of active substance, wetter, tackifier, dispersant or emulsifier and, if appropriate, solvent or oil, and such concentrates are suitable for dilution with water.
The active compound concentrations in the ready-to-use preparations can be varied within relatively wide ranges. In general, they are from 0.0001 to 10%, preferably from 0.01 to 1 % per weight.
The active compound(s) may also be used successfully in the ultra-low-volume process (ULV), it being possible to apply formulations comprising over 95% by weight of active compound, or even to apply the active compound without additives.
The following are examples of formulations:
1. Products for dilution with water for foliar applications. For seed treatment pur- poses, such products may be applied to the seed diluted or undiluted.
A) Water-soluble concentrates (SL, LS)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of water or a water-soluble solvent. As an alternative, wetters or other auxiliaries are added. The active compound(s) dissolves upon dilution with water, whereby a formulation with 10 % (w/w) of active compound(s) is obtained.
B) Dispersible concentrates (DC)
20 parts by weight of the active compound(s) are dissolved in 70 parts by weight of cyclohexanone with addition of 10 parts by weight of a dispersant, for example polyvinylpyrrolidone. Dilution with water gives a dispersion, whereby a formulation with 20% (w/w) of active compound(s) is obtained. C) Emulsifiable concentrates (EC)
15 parts by weight of the active compound(s) are dissolved in 7 parts by weight of xy- lene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). Dilution with water gives an emulsion, whereby a formulation with 15% (w/w) of active compound(s) is obtained.
D) Emulsions (EW, EO, ES)
25 parts by weight of the active compound(s) are dissolved in 35 parts by weight of xylene with addition of calcium dodecylbenzenesulfonate and castor oil ethoxylate (in each case 5 parts by weight). This mixture is introduced into 30 parts by weight of water by means of an emulsifier machine (e.g. Ultraturrax) and made into a homogeneous emulsion. Dilution with water gives an emulsion, whereby a formulation with 25% (w/w) of active compound(s) is obtained.
E) Suspensions (SC, OD, FS)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
F) Water-dispersible granules and water-soluble granules (WG, SG)
50 parts by weight of the active compound(s) are ground finely with addition of 50 parts by weight of dispersants and wetters and made as water-dispersible or water-soluble granules by means of technical appliances (for example extrusion, spray tower, fluid- ized bed). Dilution with water gives a stable dispersion or solution of the active compound^), whereby a formulation with 50% (w/w) of active compound(s) is obtained.
G) Water-dispersible powders and water-soluble powders (WP, SP, SS, WS)
75 parts by weight of the active compound(s) are ground in a rotor-stator mill with addition of 25 parts by weight of dispersants, wetters and silica gel. Dilution with water gives a stable dispersion or solution of the active compound(s) , whereby a formulation with 75% (w/w) of active compound(s) is obtained. H) Gel-Formulation (GF)
In an agitated ball mill, 20 parts by weight of the active compound(s) are comminuted with addition of 10 parts by weight of dispersants, 1 part by weight of a gelling agent wetters and 70 parts by weight of water or of an organic solvent to give a fine active compound(s) suspension. Dilution with water gives a stable suspension of the active compound(s), whereby a formulation with 20% (w/w) of active compound(s) is obtained.
2. Products to be applied undiluted for foliar applications. For seed treatment purposes, such products may be applied to the seed diluted or undiluted.
I) Dustable powders (DP, DS)
5 parts by weight of the active compound(s) are ground finely and mixed intimately with 95 parts by weight of finely divided kaolin. This gives a dustable product having 5% (w/w) of active compound(s)
J) Granules (GR, FG, GG, MG)
0.5 parts by weight of the active compound(s) is ground finely and associated with 95.5 parts by weightof carriers, whereby a formulation with 0.5% (w/w) of active compound^) is obtained. Current methods are extrusion, spray-drying or the fluidized bed. This gives granules to be applied undiluted for foliar use.
K) ULV solutions (UL)
10 parts by weight of the active compound(s) are dissolved in 90 parts by weight of an organic solvent, for example xylene. This gives a product having 10% (w/w) of active compound(s), which is applied undiluted for foliar use.
The compounds of formula I are also suitable for the treatment of plant propagation materials (such as seed). Conventional seed treatment formulations include for exam- pie flowable concentrates FS, solutions LS, powders for dry treatment DS, water dis- persible powders for slurry treatment WS, water-soluble powders SS and emulsion ES and EC and gel formulation GF. These formulations can be applied to the seed diluted or undiluted. Application to the seeds is carried out before sowing, either directly on the seeds or after having preger-minated the latter In a preferred embodiment a FS formulation is used for seed treatment. Typcially, a FS formulation may comprise 1-800 g/l of active ingredient, 1-200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0 to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of a solvent, preferably water.
Other preferred FS formulations of compounds of formula I for seed treatment comprise from 0.5 to 80 wt% of the active ingredient, from 0,05 to 5 wt% of a wetter, from 0.5 to 15 wt% of a dispersing agent, from 0,1 to 5 wt% of a thickener, from 5 to 20 wt% of an anti-freeze agent, from 0,1 to 2 wt% of an anti-foam agent, from 1 to 20 wt% of a pigment and/or a dye, from 0 to 15 wt% of a sticker /adhesion agent, from 0 to 75 wt% of a filler/vehicle, and from 0,01 to 1 wt% of a preservative.
Various types of oils, wetters, adjuvants, herbicides, fungicides, other pesticides, or bactericides may be added to the active ingredients, if appropriate just immediately prior to use (tank mix). These agents usually are admixed with the agents according to the invention in a weight ratio of 1 :10 to 10:1.
The compounds of formula I are effective through both contact (via soil, glass, wall, bed net, carpet, plant parts or animal parts), and ingestion (bait, or plant part).
For use against ants, termites, wasps, flies, mosquitos, crickets, or cockroaches, compounds of formula I are preferably used in a bait composition.
The bait can be a liquid, a solid or a semisolid preparation (e.g. a gel). Solid baits can be formed into various shapes and forms suitable to the respective application e.g. granules, blocks, sticks, disks. Liquid baits can be filled into various devices to ensure proper application, e.g. open containers, spray devices, droplet sources, or evaporation sources. Gels can be based on aqueous or oily matrices and can be formulated to par- ticular necessities in terms of stickyness, moisture retention or aging characteristics.
The bait employed in the composition is a product, which is sufficiently attractive to incite insects such as ants, termites, wasps, flies, mosquitos, crickets etc. or cockroaches to eat it. The attractiveness can be manipulated by using feeding stimulants or sex pheromones. Food stimulants are chosen, for example, but not exclusively, from animal and/or plant proteins (meat-, fish- or blood meal, insect parts, egg yolk), from fats and oils of animal and/or plant origin, or mono-, oligo- or polyorganosaccharides, especially from sucrose, lactose, fructose, dextrose, glucose, starch, pectin or even molasses or honey. Fresh or decaying parts of fruits, crops, plants, animals, insects or specific parts thereof can also serve as a feeding stimulant. Sex pheromones are known to be more insect specific. Specific pheromones are described in the literature and are known to those skilled in the art.
Formulations of compounds of formula I as aerosols (e.g in spray cans), oil sprays or pump sprays are highly suitable for the non-professional user for controlling pests such as flies, fleas, ticks, mosquitos or cockroaches. Aerosol recipes are preferably composed of the active compound, solvents such as lower alcohols (e.g. methanol, etha- nol, propanol, butanol), ketones (e.g. acetone, methyl ethyl ketone), paraffin hydrocar- bons (e.g. kerosenes) having boiling ranges of approximately 50 to 2500C, dimethyl- fomaamide, N methylpyrrolidone, dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene, water, furthermore auxiliaries such as emulsifiers such as sorbitol mo- nooleate, oleyl ethoxylate having 3-7 mol of ethylene oxide, fatty alcohol ethoxylate, perfume oils such as ethereal oils, esters of medium fatty acids with lower alcohols, aromatic carbonyl compounds, if appropriate stabilizers such as sodium benzoate, amphoteric surfactants, lower epoxides, triethyl orthoformate and, if required, propellants such as propane, butane, nitrogen, compressed air, dimethyl ether, carbon dioxide, nitrous oxide, or mixtures of these gases.
The oil spray formulations differ from the aerosol recipes in that no propellants are used.
The compounds of formula I and their respective compositions can also be used in mosquito and fumigating coils, smoke cartridges, vaporizer plates or long-term vapor- izers and also in moth papers, moth pads or other heat-independent vaporizer systems.
Methods to control infectious diseases transmitted by insects (e.g. malaria, dengue and yellow fever, lymphatic filariasis, and leishmaniasis) with compounds of formula I and their respective compositions also comprise treating surfaces of huts and houses, air spraying and impregnation of curtains, tents, clothing items, bed nets, tsetse-fly trap or the like, lnsecticidal compositions for application to fibers, fabric, knitgoods, nonwov- ens, netting material or foils and tarpaulins preferably comprise a mixture including the insecticide, optionally a repellent and at least one binder. Suitable repellents for exam- pie are N,N-diethyl-meta-toluamide (DEET), N,N-diethylphenylacetamide (DEPA), 1-(3- cyclohexan-1-yl-carbonyl)-2-methylpiperine, (2-hydroxymethylcyclohexyl) acetic acid lactone, 2-ethyl-1 ,3-hexandiol, indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insect control such as {(+/-)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)- trans-chrysantemate (Esbiothrin), a repellent derived from or identical with plant ex- tracts like limonene, eugenol, (+)-Eucamalol (1 ), (-)-i-epi-eucamalol or crude plant extracts from plants like Eucalyptus maculata, Vitex rotundifolia, Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogan nartdus (citronella). Suitable binders are selected for example from polymers and copolymers of vinyl esters of aliphatic ac- ids (such as such as vinyl acetate and vinyl versatate), acrylic and methacrylic esters of alcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methyl acrylate, mono- and diethylenically unsaturated hydrocarbons, such as styrene, and aliphatic diens, such as butadiene.
The impregnation of curtains and bednets is done in general by dipping the textile material into emulsions or dispersions of the active compounds of formula I or spraying them onto the nets.
Methods which can be employed for treating the seed are, in principle, all suitable seed treatment and especially seed dressing techniques known in the art, such as seed coating (e.g. seed pelleting), seed dusting and seed imbibition (e.g. seed soaking). Here, "seed treatment" refers to all methods that bring seeds and the compounds of formula I into contact with each other, and "seed dressing" to methods of seed treatment which provide the seeds with an amount of the compounds of formula I, i.e. which generate a seed comprising the compound of formula I. In principle, the treatment can be applied to the seed at any time from the harvest of the seed to the sowing of the seed. The seed can be treated immediately before, or during, the planting of the seed, for example using the "planter's box" method. However, the treatment may also be carried out several weeks or months, for example up to 12 months, before planting the seed, for example in the form of a seed dressing treatment, without a substantially reduced efficacy being observed.
Expediently, the treatment is applied to unsown seed. As used herein, the term "unsown seed" is meant to include seed at any period from the harvest of the seed to the sowing of the seed in the ground for the purpose of germination and growth of the plant.
Specifically, a procedure is followed in the treatment in which the seed is mixed, in a suitable device, for example a mixing device for solid or solid/liquid mixing partners, with the desired amount of seed treatment formulations, either as such or after previous dilution with water, until the composition is distributed uniformly on the seed. If appropriate, this is followed by a drying step. The compounds of formula I or veterinarily acceptable salts thereof are in particular also suitable for being used for combating parasites in and on animals.
A further object of the present invention is therefore to provide new methods for con- trolling parasites in and on animals. Another object of the invention is to provide safer pesticides for animals. Another object of the invention is further to provide pesticides for animals that may be used in lower doses than existing pesticides. And another object of the invention is to provide pesticides for animals, which provide a long residual control of the parasites.
The invention also relates to compositions containing a parasiticidally effective amount of compounds of formula I or veterinarily acceptable salts thereof and an acceptable carrier, for combating parasites in and on animals.
The present invention also provides a method for treating, controlling, preventing and protecting animals against infestation and infection by parasites, which comprises orally, topically or parenterally administering or applying to the animals a parasiticidally effective amount of a compound of formula I or veterinarily ac-ceptable salts thereof or a composition comprising it.
The invention also provides a process for the preparation of a composition for treating, controlling, preventing or protecting animals against infestation or infection by parasites which comprises a parasiticidally effective amount of a compound of formula I or the veterinarily acceptable salts thereof or a composition comprising it.
Activity of compounds against agricultural pests does not suggest their suitability for control of endo- and ectoparasites in and on animals which requires, for example, low, nonemetic dosages in the case of oral application, metabolic compatibility with the animal, low toxicity, and a safe handling.
Surprisingly, it has been found that compounds of formula I are suitable for combating endo- and ectoparasites in and on animals.
Compounds of formula I or veterinarily acceptable salts thereof and compositions com- prising them are preferably used for controlling and preventing infestations and infections animals including warm-blooded animals (including humans) and fish. They are for example suitable for controlling and preventing infestations and infections in mammals such as cattle, sheep, swine, camels, deer, horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo, donkeys, fallow deer and reindeer, and also in fur-bearing animals such as mink, chinchilla and raccoon, birds such as hens, geese, turkeys and ducks and fish such as fresh- and salt-water fish such as trout, carp and eels.
Compounds of formula I or veterinarily acceptable salts thereof and compositions com- prising them are preferably used for controlling and preventing infestations and infections in domestic animals, such as dogs or cats.
Infestations in warm-blooded animals and fish include, but are not limited to, lice, biting lice, ticks, nasal bots, keds, biting flies, muscoid flies, flies, myiasitic fly larvae, chig- gers, gnats, mosquitoes and fleas.
The compounds of formula I or veterinarily acceptable salts thereof and compositions comprising them are suitable for systemic and/or non-systemic control of ecto- and/or endoparasites. They are active against all or some stages of development.
The compounds of formula I are especially useful for combating ectoparasites.
The compounds of formula I are especially useful for combating parasites of the following orders and species, respectively:
fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis, Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllus fasciatus,
cockroaches (Blattaria - Blattodea), e.g. Blattella germanica, Blattella asahinae, Pe- riplaneta americana, Periplaneta japonica, Periplaneta brunnea, Periplaneta fuliggi- nosa, Periplaneta australasiae, and Blatta orientalis,
flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedes vexans, An- astrepha ludens, Anopheles maculipennis, Anopheles crucians, Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anopheles leucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphora vicina, Chrysomya bezziana, Chrysomya hominivorax, Chrysomya macellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus, Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens, Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culex tarsalis, Culiseta inor- nata, Culiseta melanura, Dermatobia hominis, Fannia canicularis, Gasterophilus intes- tinalis, Glossina morsitans, Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobia irritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata, Lep- toconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans, Oestrus ovis, Phlebotomus ar- gentipes, Psorophora columbiae, Psorophora discolor, Prosimulium mixtum, Sar- cophaga haemorrhoidalis, Sarcophaga sp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanus atratus, Tabanus lineola, and Tabanus similis,
lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanus corporis, Pthi- rus pubis, Haematopinus eurysternus, Haematopinus suis, Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthus stramineus and Solenopotes capillatus.
ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodes scapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalus sanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyomma americanum, Ambryomma maculatum, Orni- thodorus hermsi, Ornithodorus turicata and parasitic mites (Mesostigmata), e.g. Orni- thonyssus bacoti and Dermanyssus gallinae,
actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp., Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp., Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp., Notoedres spp.,Knemidocoptes spp., Cytodites spp., and Laminosioptes spp,
bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduvius senilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Arilus critatus,
Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., and Solenopotes spp,
Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Tricho- dectes spp., and Felicola spp,
Roundworms Nematoda:
Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae (Trichinella spp.), (T ri- churidae) Trichuris spp., Capillaria spp,
Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,
Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus, Bunosto- mum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus., Ostertagia spp., Cooperia spp., Nematodirus spp., Dictyocaulus spp., Cyathostoma spp., Oe- sophagostomum spp., Stephanurus dentatus, Ollulanus spp., Chabertia spp., Stepha- nurus dentatus , Syngamus trachea, Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp., Metastrongylus spp., Muellerius capillaris, Protostrongylus spp., Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylus abstrusus, and Dioc- tophyma renale,
Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascaris suum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis (Threadworm), Toxocara canis, To- xascaris leonine, Skrjabinema spp., and Oxyuris equi,
Camallanida, e.g. Dracunculus medinensis (guinea worm)
Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocerca spp., Dirofilari spp. a, Dipetalonema spp., Setaria spp., Elaeophora spp., Spirocerca lupi, and Hab- ronema spp.,
Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp., Macracantho- rhynchus hirudinaceus and Oncicola spp,
Planarians (Plathelminthes):
Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimus spp., Dicro- coelium spp., Fasciolopsis buski, Clonorchis sinensis, Schistosoma spp., Trichobilhar- zia spp., Alaria alata, Paragonimus spp., and Nanocyetes spp,
Cercomeromorpha, in particular Cestoda (Tapeworms), e.g. Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidium caninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp., Vampirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp., Anoplocephala spp., and Hymenolepis spp.
The compounds of formula I and compositions containing them are particularly useful for the control of pests from the orders Diptera, Siphonaptera and Ixodida.
Moreover, the use of compounds of formula I and compositions containing them for combating mosquitoes is especially preferred.
The use of the compounds of formula I and compositions containing them for combating flies is a further preferred embodiment of the present invention. Furthermore, the use of the compounds of formula I and compositions containing them for combating fleas is especially preferred.
The use of the compounds of formula I and of the compositions containing them for combating ticks is a further preferred embodiment of the present invention.
The compounds of formula I also are especially useful for combating endoparasites (roundworms nematoda, thorny headed worms and planarians).
Administration can be carried out both prophylactically and therapeutically.
Administration of the active compounds is carried out directly or in the form of suitable preparations, orally, topically/dermally or parenterally.
For oral administration to warm-blooded animals, the compounds of formula I may be formulated as animal feeds, animal feed premixes, animal feed concentrates, pills, solutions, pastes, suspensions, drenches, gels, tablets, boluses and capsules. In addition, the compounds of formulae I may be administered to the animals in their drinking water. For oral administration, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula I, preferably with 0.5 mg/kg to 100 mg/kg of animal body weight per day.
Alternatively, the compounds of formula I may be administered to animals parenterally, for example, by intraruminal, intramuscular, intravenous or subcutaneous injection. The compounds of formula I may be dispersed or dissolved in a physiologically acceptable carrier for subcutaneous injection. Alternatively, the compounds of formula I may be formulated into an implant for subcutaneous administration. In addition the compounds of formula I may be transdermally administered to animals. For parenteral administra- tion, the dosage form chosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animal body weight per day of the compounds of formula I.
The compounds of formula I may also be applied topically to the animals in the form of dips, dusts, powders, collars, medallions, sprays, shampoos, spot-on and pour-on for- mulations and in ointments or oil-in-water or water-in-oil emulsions. For topical application, dips and sprays usually contain 0.5 ppm to 5,000 ppm and preferably 1 ppm to 3,000 ppm of the compounds of formula I. In addition, the compounds of formula I may be formulated as ear tags for animals, particularly quadrupeds such as cattle and sheep. Suitable preparations are:
Solutions such as oral solutions, concentrates for oral administration after dilution, solu- tions for use on the skin or in body cavities, pouring-on formulations, gels;
Emulsions and suspensions for oral or dermal administration; semi-solid preparations;
Formulations in which the active compound is processed in an ointment base or in an oil-in-water or water-in-oil emulsion base;
Solid preparations such as powders, premixes or concentrates, granules, pellets, tablets, boluses, capsules; aerosols and inhalants, and active compound-containing shaped articles.
Compositions suitable for injection are prepared by dissolving the active ingredient in a suitable solvent and optionally adding further ingredients such as acids, bases, buffer salts, preservatives, and solubilizers. The solutions are filtered and filled sterile.
Suitable solvents are physiologically tolerable solvents such as water, alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propylene glycol, polyethylene glycols, N- methylpyrrolidone, 2-pyrrolidone, and mixtures thereof.
The active compounds can optionally be dissolved in physiologically tolerable vegeta- ble or synthetic oils which are suitable for injection.
Suitable solubilizers are solvents which promote the dissolution of the active compound in the main solvent or prevent its precipitation. Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylated castor oil, and polyoxyethylated sorbitan ester.
Suitable preservatives are benzyl alcohol, trichlorobutanol, p-hydroxybenzoic acid esters, and n-butanol.
Oral solutions are administered directly. Concentrates are administered orally after prior dilution to the use concentration. Oral solutions and concentrates are prepared according to the state of the art and as described above for injection solutions, sterile procedures not being necessary. Solutions for use on the skin are trickled on, spread on, rubbed in, sprinkled on or sprayed on.
Solutions for use on the skin are prepared according to the state of the art and accord- ing to what is described above for injection solutions, sterile procedures not being necessary.
Further suitable solvents are polypropylene glycol, phenyl ethanol, phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate, ethers such as alkyleneglycol alkylether, e.g. dipropylenglycol monomethylether, ketons such as acetone, me- thylethylketone, aromatic hydrocarbons, vegetable and synthetic oils, dimethylforma- mide, dimethylacetamide, transcutol, solketal, propylencarbonate, and mixtures thereof.
It may be advantageous to add thickeners during preparation. Suitable thickeners are inorganic thickeners such as bentonites, colloidal silicic acid, aluminium monostearate, organic thickeners such as cellulose derivatives, polyvinyl alcohols and their copolymers, acrylates and methacrylates.
Gels are applied to or spread on the skin or introduced into body cavities. Gels are prepared by treating solutions which have been prepared as described in the case of the injection solutions with sufficient thickener that a clear material having an ointment- like consistency results. The thickeners employed are the thickeners given above.
Pour-on formulations are poured or sprayed onto limited areas of the skin, the active compound penetrating the skin and acting systemically.
Pour-on formulations are prepared by dissolving, suspending or emulsifying the active compound in suitable skin-compatible solvents or solvent mixtures. If appropriate, other auxiliaries such as colorants, bioabsorption-promoting substances, antioxidants, light stabilizers, adhesives are added.
Suitable solvents are water, alkanols, glycols, polyethylene glycols, polypropylene glycols, glycerol, aromatic alcohols such as benzyl alcohol, phenylethanol, phenoxyetha- nol, esters such as ethyl acetate, butyl acetate, benzyl benzoate, ethers such as al- kylene glycol alkyl ethers such as dipropylene glycol monomethyl ether, diethylene glycol mono-butyl ether, ketones such as acetone, methyl ethyl ketone, cyclic carbonates such as propylene carbonate, ethylene carbonate, aromatic and/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF, dimethylacetamide, n-alkylpyrrolidones such as methylpyrrolidone, n-butylpyrrolidone or n-octylpyrrolidone, N methylpyrroli- done, 2-pyrrolidone, 2,2-dimethyl-4-oxy-methylene-1 ,3-diox- olane and glycerol formal.
Suitable colorants are all colorants permitted for use on animals and which can be dis- solved or suspended.
Suitable absorption-promoting substances are, for example, DMSO, spreading oils such as isopropyl myristate, dipropylene glycol pelargonate, silicone oils and copolymers thereof with polyethers, fatty acid esters, triglycerides, fatty alcohols.
Suitable antioxidants are sulfites or metabisulfites such as potassium metabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole, tocopherol.
Suitable light stabilizers are, for example, novantisolic acid.
Suitable adhesives are, for example, cellulose derivatives, starch derivatives, polyacry- lates, natural polymers such as alginates, gelatin.
Emulsions can be administered orally, dermally or as injections.
Emulsions are either of the water-in-oil type or of the oil-in-water type.
They are prepared by dissolving the active compound either in the hydrophobic or in the hydrophilic phase and homogenizing this with the solvent of the other phase with the aid of suitable emulsifiers and, if appropriate, other auxiliaries such as colorants, absorption-promoting substances, preservatives, antioxidants, light stabilizers, viscosity-enhancing substances.
Suitable hydrophobic phases (oils) are: liquid paraffins, silicone oils, natural vegetable oils such as sesame oil, almond oil, castor oil, synthetic triglycerides such as caprylic/capric biglyceride, triglyceride mixture with vegetable fatty acids of the chain length Cs-Ci2 or other specially selected natural fatty acids, partial glyceride mixtures of saturated or unsaturated fatty acids possibly also containing hydroxyl groups, mono- and diglycerides of the Cs-do fatty acids, fatty acid esters such as ethyl stearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycol perlargonate, esters of a branched fatty acid of medium chain length with saturated fatty alcohols of chain length C16-C18, isopropyl myristate, isopropyl palmitate, caprylic/capric acid esters of saturated fatty alcohols of chain length C12-C18, isopropyl stearate, oleyl oleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acid esters such as synthetic duck coccygeal gland fat, dibutyl phthalate, diisopropyl adipate, and ester mixtures related to the latter, fatty alcohols such as isotridecyl alcohol, 2-octyl- dodecanol, cetylstearyl alcohol, oleyl alcohol, and fatty acids such as oleic acid and mixtures thereof.
Suitable hydrophilic phases are: water, alcohols such as propylene glycol, glycerol, sorbitol and mixtures thereof.
Suitable emulsifiers are: non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylated sorbitan monoo- leate, sorbitan monostearate, glycerol monostearate, polyoxyethyl stearate, alkylphenol polyglycol ether; ampholytic surfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin; anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ether sulfates, mo- no/dialkyl polyglycol ether orthophosphoric acid ester monoethanolamine salt; cation-active surfactants, such as cetyltrimethylammonium chloride.
Suitable further auxiliaries are: substances which enhance the viscosity and stabilize the emulsion, such as carboxymethylcellulose, methylcellulose and other cellulose and starch derivatives, polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone, polyvinyl alcohol, copolymers of methyl vinyl ether and maleic anhydride, polyethylene glycols, waxes, colloidal silicic acid or mixtures of the substances mentioned.
Suspensions can be administered orally or topically/dermally. They are prepared by suspending the active compound in a suspending agent, if appropriate with addition of other auxiliaries such as wetting agents, colorants, bioabsorption-promoting substances, preservatives, antioxidants, light stabilizers.
Liquid suspending agents are all homogeneous solvents and solvent mixtures.
Suitable wetting agents (dispersants) are the emulsifiers given above.
Other auxiliaries which may be mentioned are those given above.
Semi-solid preparations can be administered orally or topically/dermally. They differ from the suspensions and emulsions described above only by their higher viscosity.
For the production of solid preparations, the active compound is mixed with suitable excipients, if appropriate with addition of auxiliaries, and brought into the desired form. Suitable excipients are all physiologically tolerable solid inert substances. Those used are inorganic and organic substances. Inorganic substances are, for example, sodium chloride, carbonates such as calcium carbonate, hydrogencarbonates, aluminium ox- ides, titanium oxide, silicic acids, argillaceous earths, precipitated or colloidal silica, or phosphates. Organic substances are, for example, sugar, cellulose, foodstuffs and feeds such as milk powder, animal meal, grain meals and shreds, starches.
Suitable auxiliaries are preservatives, antioxidants, and/or colorants which have been mentioned above.
Other suitable auxiliaries are lubricants and glidants such as magnesium stearate, stearic acid, talc, bentonites, disintegration-promoting substances such as starch or crosslinked polyvinylpyrrolidone, binders such as starch, gelatin or linear polyvinylpyr- rolidone, and dry binders such as microcrystalline cellulose.
In general, "parasiticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The parasiticidally effective amount can vary for the various compounds/compositions used in the invention. A parasiticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired parasiticidal effect and duration, target species, mode of application, and the like.
The compositions which can be used in the invention can comprise generally from about 0.001 to 95% of the compounds of formula I.
Generally, it is favorable to apply the compounds of formula I in total amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to 50 mg/kg per day.
Ready-to-use preparations contain the compounds acting against parasites, preferably ectoparasites, in concentrations of 10 ppm to 80 percent by weight, preferably from 0.1 to 65 percent by weight, more preferably from 1 to 50 percent by weight, most prefera- bly from 5 to 40 percent by weight.
Preparations which are diluted before use contain the compounds acting against ectoparasites in concentrations of 0.5 to 90 percent by weight, preferably of 1 to 50 percent by weight. Furthermore, the preparations comprise the compounds of formula I against endopara- sites in concentrations of 10 ppm to 2 per cent by weight, preferably of 0.05 to 0.9 percent by weight, very particularly preferably of 0.005 to 0.25 percent by weight.
In a preferred embodiment of the present invention, the compositions comprising the compounds of formula I are applied dermally / topically.
In a further preferred embodiment, the topical application is conducted in the form of compound-containing shaped articles such as collars, medallions, ear tags, bands for fixing at body parts, and adhesive strips and foils.
Generally, it is favorable to apply solid formulations which release compounds of formula I in total amounts of 10 mg/kg to 300 mg/kg, preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kg body weight of the treated animal in the course of three weeks.
For the preparation of the shaped articles, thermoplastic and flexible plastics as well as elastomers and thermoplastic elastomers are used. Suitable plastics and elastomers are polyvinyl resins, polyurethane, polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamides and polyester which are sufficiently compatible with the compounds of formula I. A detailed list of plastics and elastomers as well as preparation procedures for the shaped articles is given e.g. in WO 03/086075.
Compositions to be used according to this invention may also contain other active ingredients, for example other pesticides, insecticides, herbicides, fungicides, other pesticides, or bactericides, fertilizers such as ammonium nitrate, urea, potash, and superphosphate, phytotoxicants and plant growth regulators, safeners and nematicides. These additional ingredients may be used sequentially or in combination with the abo- ve-described compositions, if appropriate also added only immediately prior to use (tank mix). For example, the plant(s) may be sprayed with a composition of this invention either before or after being treated with other active ingredients.
These agents can be admixed with the agents used according to the invention in a weight ratio of 1 :10 to 10:1. Mixing the compounds of formula I or the compositions comprising them in the use form as pesticides with other pesticides frequently results in a broader pesticidal spectrum of action. The following list M of pesticides together with which the compounds according to the invention can be used and with which potential synergistic effects might be produced, is intended to illustrate the possible combinations, but not to impose any limitation:
M.1. Organo(thio)phosphate compounds: acephate, azamethiphos, azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos, chlormephos, chlorpyrifos, chlorpyri- fos-methyl, coumaphos, cyanophos, demeton-S-methyl, diazinon, dichlorvos/ DDVP, dicrotophos, dimethoate, dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, fam- phur, fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate, heptenophos, isoxathion, malathion, mecarbam, methamidophos, methidathion, mevinphos, monocrotophos, naled, omethoate, oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos, propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos, sulfo- tep, tebupirimfos, temephos, terbufos, tetrachlorvinphos, thiometon, triazophos, tri- chlorfon, vamidothion;
M.2. Carbamate compounds: aldicarb, alanycarb, bendiocarb, benfuracarb, butocar- boxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan, ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb, methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur, thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;
M.3. Pyrethroid compounds: acrinathrin, allethrin, d-cis-trans allethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrin S-cylclopentenyl, bioresmethrin, cycloprothrin, cyflu- thrin, beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin, cyperme- thrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin, esfenvalerate, etofenprox, fenpropathrin, fen- valerate, flucythrinate, flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin, permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum), resmethrin, si- lafluofen, tefluthrin, tetramethrin, tralomethrin, transfluthrin;
M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene, fenoxycarb, pyriproxyfen;
M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid, bensultap, car- tap hydrochloride, clothianidin, dinotefuran, imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allosteric agonist), spinetoram (allosteric agonist), thiacloprid, thio- cyclam, thiosultap-sodium and AKD1022.
M.6. GABA gated chloride channel antagonist compounds: chlordane, endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole, pyriprole M.7. Chloride channel activators: abamectin, emamectin benzoate, milbemectin, Ie- pimectin;
M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen, pyridaben, tebufen- pyrad, tolfenpyrad, flufenerim, rotenone;
M.9. METI Il and III compounds: acequinocyl, fluacyprim, hydramethylnon;
M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;
M.1 1. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin, diafenthiuron, fen- butatin oxide, propargite, tetradifon;
M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide, methoxy- fenozide, tebufenozide;
M.13. Synergists: piperonyl butoxide, tribufos;
M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;
M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;
M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;
M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;
M.18. Chitin synthesis inhibitors: buprofezin, bistrifluron, chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron, noviflumuron, te- flubenzuron, triflumuron;
M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen, spirotetramat;
M.20. Octapaminergic agonsits: amitraz;
M.21. Ryanodine receptor modulators: flubendiamide and the phthalamid compound (R)-, (S)- 3- Chloro-N1-{2-methyl-4-[1 ,2,2,2 - tetrafluoro-1- (trifluoromethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid (M21.1 )
M.22. Isoxazoline compounds: 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro- isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide (M22.1 ), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N- (2,2,2-trifluoro-ethyl)-benzamide (M22.2), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl- 4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbamoyl)-methyl]- benzamide (M22.3), 4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3- yl]-naphthalene-1-carboxylic acid [(2,2,2-trifluoro-ethylcarbamoyl)-methyl]-amide (M22.4)4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-N- [(methoxyimino)methyl]-2-methylbenzamide (M22.5), 4-[5-(3-Chloro-5-trifluoromethyl- phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro- ethylcarbamoyl)-methyl]-benzamide (M22.6), 4-[5-(3-Chloro-5-trifluoromethyl-phenyl)- S-trifluoromethyl^δ-dihydro-isoxazol-S-yO-naphthalene-i-carboxylic acid [(2,2,2- trifluoro-ethylcarbamoyl)-methyl]-amide (M22.7) and 5-[5-(3,5-Dichloro-4-fluoro- phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-[1 ,2,4]triazol-1-yl-benzonitrile (M22.8)
M.23. Anthranilamide compounds: chloranthraniliprole,cyantraniliprole,
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-cyano-2-(1 - cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide (M23.1),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-chloro-4-cyano-6-(1 - cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.2), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-cyano-6- (1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.3),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2-bromo-4-chloro-6- (1 -cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.4), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [2,4-dichloro-6-(1 - cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.5),
5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid [4-chloro-2-(1 - cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide (M23.6), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3- methyl-benzoyl)-hydrazinecarboxylic acid methyl ester (M23.7), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3- methyl-benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.8), N'-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3- methyl-benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.9), N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-hydrazinecarboxylic acid methyl ester (M23.10),
N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-N'-methyl-hydrazinecarboxylic acid methyl ester (M23.1 1 ) and N'-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}- benzoyl)-N,N'-dimethyl-hydrazinecarboxylic acid methyl ester (M23.12) M.24. Malononitrile compounds: 2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoro- propyl)malononitrile (CF2H-CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF3) (M24.1 ) and2- (2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile (CF2H- CF2-CF2-CF2-CH2-C(CN)2-CH2-CH2-CF2-CF3) (M24.2);
M.25. Microbial disruptors: Bacillus thuringiensis subsp. Israelensi, Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillus thuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp. Tenebrionis;
M.26. Aminofuranone compounds:
4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.1 ), 4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.2), 4-{[(2-Chloro1 ,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.3), 4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.4), 4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on (M26.5), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.6), 4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on (M26.7), 4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.8), 4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on (M26.9) and 4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on (M26.10);
M.27. Various compounds: aluminium phosphide, amidoflumet, benclothiaz, benzoxi- mate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen, cyflumetofen, chi- nomethionate, dicofol, fluoroacetate, phosphine, pyridalyl, pyrifluquinazon, sulfur, or- ganic sulfur compounds, tartar emetic, sulfoxaflor, N-R'-2,2-dihalo-1-R"cyclo- propanecarboxamide-2-(2,6-dichloro-α ,α ,α -trifluoro-p-tolyl)hydrazone or N-R'-2,2- di(R"')propionamide-2-(2,6-dichloro-α ,α ,α -trifluoro-p-tolyl)-hydrazone, wherein R' is methyl or ethyl, halo is chloro or bromo, R" is hydrogen or methyl and R'" is methyl or ethyl, 4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1-yl)-2-fluoro-pyrimidine (M27.1 ), Cyclopropaneacetic acid, 1 ,1 '-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2- cyclopropylacetyl)oxy]methyl]-1 , 3,4 ,4a, 5,6,6a, 12,12a, 12b-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(M27.2) and 8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3- yl)-3-aza-bicyclo[3.2.1]octane(M27.3).
The commercially available compounds of the group M may be found in The Pesticide Manual, 13th Edition, British Crop Protection Council (2003) among other publications.
Paraoxon and their preparation have been described in Farm Chemicals Handbook, Volume 88, Meister Publishing Company, 2001. Flupyrazofos has been described in Pesticide Science 54, 1988, p.237-243 and in US 4822779. AKD 1022 and its preparation have been described in US 6300348. The anthranilamides M23.1 to M23.6 have been described in WO 2008/72743 and WO 200872783 those M23.7 to M23.12 in WO2007/043677. The phthalamide M 21.1 is known from WO 2007/101540. The al- kynylether compound M27.1 is described e.g. in JP 2006131529. Organic sulfur compounds have been described in WO 2007060839. The isoxazoline compounds M 22.1 to M 22.8 have been described in e.g. WO2005/085216, WO 2007/079162, WO 2007/026965, WO 2009/126668 and WO2009/051956. The aminofuranone compounds M 26.1 to M 26.10 have been described eg. in WO 2007/1 15644. The pyripy- ropene derivative M 27.2 has been described in WO 2008/66153 and WO
2008/108491. The pyridazin compound M 27.3 has been described in JP 2008/1 15155. Malononitrile compounds as those (M24.1 ) and (M24.2) have been described in WO 02/089579, WO 02/090320, WO 02/090321 , WO 04/006677, WO 05/068423, WO 05/068432 and WO 05/063694.
Fungicidal mixing partners are those selected from the group consisting of acylalanines such as benalaxyl, metalaxyl, ofurace, oxadixyl, amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph, fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph, anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl, antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin, polyoxin or streptomycin, azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole, dinicona- zole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole, hexaconazole, imazalil, metconazole, myclobutanil, penconazole, propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon, triadimenol, triflumizol, triticonazole, flutriafol, dicarboximides such as iprodion, myclozolin, procymidon, vinclozolin, dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram, pro- pineb, polycarbamate, thiram, ziram, zineb, heterocyclic compounds such as anilazine, benomyl, boscalid, carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon, famoxadon, fenamidon, fenarimol, fube- ridazole, flutolanil, furametpyr, isoprothiolane, mepronil, nuarimol, probenazole, pro- quinazid, pyrifenox, pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid, thio- phanate-methyl, tiadinil, tricyclazole, triforine, copper fungicides such as Bordeaux mixture, copper acetate, copper oxychloride, basic copper sulfate, nitrophenyl derivatives such as binapacryl, dinocap, dinobuton, nitrophthalisopropyl, phenylpyrroles such as fenpiclonil or fludioxonil, sulfur, other fungicides such as acibenzolar-S-methyl, benthiavalicarb, carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin, diclocymet, diethofencarb, edifen- phos, ethaboxam, fenhexamid, fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl, fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon, pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene, zoxamid, strobilurins such as azoxystrobin, dimoxystrobin, fluoxastrobin, kresoxim-methyl, me- tominostrobin, orysastrobin, picoxystrobin or trifloxystrobin, sulfenic acid derivatives such as captafol, captan, dichlofluanid, folpet, tolylfluanid, cinnemamides and analogs such as dimethomorph, flumetover or flumorph.
The invertebrate pest, i.e. arthropodes and nematodes, the plant, soil or water in which the plant is growing can be contacted with the present compound(s) of formula I or composition(s) containing them by any application method known in the art. As such, "contacting" includes both direct contact (applying the compounds/compositions di- rectly on the animal pest or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the animal pest or plant).
Moreover, invertebrate pests may be controlled by contacting the target pest, its food supply, habitat, breeding ground or its locus with a pesticidally effective amount of compounds of formula I. As such, the application may be carried out before or after the infection of the locus, growing crops, or harvested crops by the pest.
"Locus" means a habitat, breeding ground, cultivated plants, plant propagation material (such as seed), soil, area, material or environ-ment in which a pest or parasite is growing or may grow.
In general "pesticidally effective amount" means the amount of active ingredient needed to achieve an observable effect on growth, including the effects of necrosis, death, retardation, prevention, and removal, destruction, or otherwise diminishing the occurrence and activity of the target organism. The pesticidally effective amount can vary for the various compounds/compositions used in the invention. A pesticidally effective amount of the compositions will also vary according to the prevailing conditions such as desired pesticidal effect and duration, weather, target species, locus, mode of application, and the like.
The compounds of formula I and their compositions can be used for protecting wooden materials such as trees, board fences, sleepers, etc. and buildings such as houses, outhouses, factories, but also construction materials, furniture, leathers, fibers, vinyl articles, electric wires and cables etc. from ants and/or termites, and for controlling ants and termites from doing harm to crops or human being (e.g. when the pests invade into houses and public facilities). The compounds of are applied not only to the surrounding soil surface or into the under-floor soil in order to protect wooden materials but it can also be applied to lumbered articles such as surfaces of the under-floor concrete, alcove posts, beams, plywood, furniture, etc., wooden articles such as particle boards, half boards, etc. and vinyl articles such as coated electric wires, vinyl sheets, heat insulating material such as styrene foams, etc. In case of application against ants doing harm to crops or human beings, the ant controller of the present invention is applied to the crops or the surrounding soil, or is directly applied to the nest of ants or the like.
The compounds of formula I can also be applied preventively to places at which occurrence of the pests is expected.
The compounds of formula I may be also used to protect growing plants from attack or infestation by pests by contacting the plant with a pesticidally effective amount of compounds of formula I. As such, "contacting" includes both direct contact (applying the compounds/compositions directly on the pest and/or plant - typically to the foliage, stem or roots of the plant) and indirect contact (applying the compounds/compositions to the locus of the pest and/or plant).
In the case of soil treatment or of application to the pests dwelling place or nest, the quantity of active ingredient ranges from 0.0001 to 500 g per 100 m2, preferably from 0.001 to 2O g per 100 m2.
Customary application rates in the protection of materials are, for example, from 0.01 g to 1000 g of active compound per m2 treated material, desirably from 0.1 g to 50 g per m2.
lnsecticidal compositions for use in the impregnation of materials typically contain from 0.001 to 95 % by weight, preferably from 0.1 to 45 % by weight, and more preferably from 1 to 25 % by weight of at least one repellent and/or insecticide.
For use in bait compositions, the typical content of active ingredient is from 0.001 % by weight to 15 % by weight, desirably from 0.001 % by weight to 5 % by weight of active compound. For use in spray compositions, the content of active ingredient is from 0.001 to 80 % by weight, preferably from 0.01 to 50 % by weight and most preferably from 0.01 to 15 % by weight.
For use in treating crop plants, the rate of application of the active ingredients of this invention may be in the range of 0.1 g to 4000 g per hectare, desirably from 25 g to 600 g per hectare, more desirably from 50 g to 500 g per hectare.
In the treatment of seed, the application rates of the active ingredients are generally from 0.1 g to 10 kg per 100 kg of seed, preferably from 1 g to 5 kg per 100 kg of seed, in particular from 1 g to 200 g per 100 kg of seed.
The present invention is now illustrated in further detail by the following examples.
I. Preparation Examples
Example 1 (Compound of formula I, wherein (R1)n is 3,5-di-CH3, (R2)m is 2-CH3, 3-CF3, X is (CO) and Y is 2-pyridyl)
A mixture of 2-(3,5-dimethyl-phenyl)-1 -(2-methyl-3-trifluoromethyl-phenyl)- ethylisothiocyanate (400 mg), pyridine-2-carboxylic acid 2-amino-ethyl ester dihydro- chloride salt (prepared according to Chem. Pharm. Bull. 1983, 31 (1 1 ), 41 16-4126, compound no. 1 ) (274 mg) and potassium carbonate (1.5 equiv.) was stirred at room temperature for 2 hours, triethylamine was added (2 equiv.) and stirring continued at reflux for 24 h. The mixture was filtrated and the filtrate concentrated under reduced pressure. The residue was purified by column chromatography to yield the title compound (250 mg).
1H-NMR (CDCI3): δ = 2.20 (me), 2.35 (s), 2.95 (me), 3.4 (me), 4.4 (me), 5.65 (br s), 6.6 (S), 6.8 (S), 6.9 (S), 7.15 (t), 7.4-7.5 (m), 7.8 (t), 8.0 (d), 8.6 (me).
The compounds of the general formula I (examples 2 to 51 ) can be prepared accordingly. The spectroscopical data of the compounds of examples 1 to 51 are listed in table I.
Table I:
Figure imgf000069_0001
Figure imgf000069_0002
Figure imgf000070_0001
Figure imgf000071_0001
Figure imgf000072_0001
Figure imgf000073_0001
*: the sign "-" has the meaning of n being 0 #: the sign "-" has the meaning of m being 0
II. Evaluation of pesticidal activity:
11.1. Cotton Aphid (Aphis gossypii)
The active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica® surfactant.
Cotton plants in the cotyledon stage (variety 'Delta Pine') are infested with approximately 100 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The cotyledons of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
In this test, the compounds of examples 1 , 3, 4, 5, 6, 9,10,18, 19, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 45, 46, 48, 49, 50 and 51 at 300 ppm showed at least 80 % mortality in comparison with untreated controls.
11.2 Green Peach Aphid (Myzus persicae)
The active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica® surfactant.
Pepper plants in the 2nd leaf-pair stage (variety 'California Wonder') are infested with approximately 40 laboratory-reared aphids by placing infested leaf sections on top of the test plants. The leaf sections are removed after 24 hours. The leaves of the intact plants are dipped into gradient solutions of the test compound. Aphid mortality on the treated plants, relative to mortality on check plants, is determined after 5 days.
In this test, the compounds of examples 1 , 2, 3, 4, 5, 6, 7, 9, 10, 13, 18, 19, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 44, 45, 46, 48, 49 and 50 at 300 ppm showed at least 80 % mortality in comparison with untreated controls.
11.3 Bean aphid (Aphis fabae)
The active compounds were formulated in 50:50 (vohvol) acetone:water and 100 ppm Kinetica® surfactant.
Nasturtium plants grown in Metro mix in the 1st leaf-pair stage (variety 'Mixed Jewel') were infested with approximately 2-30 laboratory-reared aphids by placing infested cut plants on top of the test plants. The cut plants were removed after 24 hr. Each plant was dipped into the test solution to provide complete coverage of the foliage, stem, protruding seed surface and surrounding cube surface and allowed to dry in the fume hood. The treated plants were kept at about 25°C with continuous fluorescent light. Aphid mortality is determined after 3 days. In this test, the compounds of examples 25, 26, 27, 31 , 38 and 39 at 300 ppm showed a mortality of at least 80% in comparison with untreated controls.
11.4 Cowpea aphid (Aphis craccivora)
The active compounds were formulated in 50:50 (vohvol) acetone : water and 100 ppm Kinetica® surfactant.
Potted cowpea plants colonized with 100 - 150 aphids of various stages were sprayed after the pest population has been recorded. Population reduction was recorded after 24, 72, and 120 hours.
In this test, the compounds of examples 1 , 3, 4, 5, 6, 18, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 35, 36, 37, 38, 39, 40, 41 , 42, 43, 45, 46, 48, 49, 50 and 51 at 300 ppm showed at least 80% mortality in comparison with untreated controls.
11.5 Silverleaf whitefly
The active compounds were formulated in 50 : 50 (vohvol) acetone : water and 100 ppm Kinetica® surfactant.
Selected cotton plants were grown to the cotyledon state (one plant per pot). The coty- ledons were dipped into the test solution to provide complete coverage of the foliage and placed in a well-vented area to dry. Each pot with treated seedling was placed in a plastic cup and 10 to 12 whitefly adults (approximately 3-5 day old) were introduced. The insects were colleted using an aspirator and a 0.6 cm, non-toxic Tygon® tubing (R- 3603) connected to a barrier pipette tip. The tip, containing the collected insects, was then gently inserted into the soil containing the treated plant, allowing insects to crawl out of the tip to reach the foliage for feeding. The cups were covered with a re-usable screened lid (150 micron mesh polyester screen PeCap from Tetko Inc). Test plants were maintained in the holding room at about 25 oC and 20-40% relative humid-ity for 3 days avoiding direct exposure to the fluorescent light (24 hour photoperiod) to pre- vent trapping of heat inside the cup. Mortality was assessed 3 days after treatment of the plants.
In this test, the compounds of examples 1 , 3, 38, 45, 47, 48, 49 and 50 at 300 ppm showed at least 80% mortality in comparison with untreated controls.

Claims

Claims
1. The use of a thiourea compound of the formula I and the salts thereof
Figure imgf000076_0001
wherein m is 0, 1 , 2, 3, 4 or 5;
n is 0, 1 , 2, 3, 4 or 5;
X is a single bond, -C(O)- or -C(S)-;
Y is Ci-Cio-alkyl, C2-Cio-alkenyl, C4-Cio-alkadienyl, C2-Cio-alkynyl, where the four last-mentioned groups may be unsubstituted, partially or fully halo- genated or may carry 1 , 2 or 3 radicals Ry, where Ry is CN, ORy1, -SRy2, -S(O)2Ry2, -NRy3Ry4, -C(O)Ry5, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-
Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10-membered hetaryl, where 5- to 10-membered heterocyclyl and 5- to 10- membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10- membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2- cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy,
and
Y may be further C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2- cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or 5- to 10- membered hetaryl where 5- to 10-membered heterocyclyl and 5- to 10- membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10- membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-C12- cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rw,
and in the case that X is a single bond,
Y may be further NRy5Ry7, P(O)Ry8Ry9, P(S)Ry10Ry11, SO2Ry12 or SiRy13Ry14Ry15;
wherein
Ry is hydrogen, Ci-C8-alkyl, Ci-C8-haloalkyl, C2-C8-alkenyl, C2-C8- haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, Ci-C8-alkylcarbonyl, Ci-C8-haloalkylcarbonyl, C2-C8-alkenylcarbonyl, C2-C8- haloalkenylcarbonyl, C2-C8-alkynylcarbonyl, C2-C8- haloalkynylcarbonyl,
C3-Ci2-cycloalkyl, C3-Ci2-cycloalkylcarbonyl, C3-Ci2-cycloalkenyl, C3- Ci2-cycloalkenylcarbonyl, phenyl, phenylcarbonyl, naphthyl, naphthyl- carbonyl, 5- to 10-membered heterocyclyl, 5- to 10-membered het- erocyclylcarbonyl, 5- to 10-membered hetaryl or 5- to 10-membered hetarylcarbonyl, wherein the twelve last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy, and where 5- to 10-membered heterocyclyl, the heterocyclyl moiety in 5- to 10-membered heterocyclylcarbonyl, the heataryl moiety in 5- to 10-membered hetarylcarbonyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members;
Ry2 hydrogen, Ci-C8-alkyl, Ci-C8-haloalkyl, C2-C8-alkenyl, C2-C8- haloalkenyl, C2-C8-alkynyl, C2-C8-haloalkynyl, C3-Ci2-cycloalkyl, C3- Ci2-cycloalkenyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl, or 5- to 10-membered hetaryl, wherein the six last-mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Ryy and where 5- to 10-membered heterocyclyl and 5- to 10- membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members;
Ry3 has one of the meanings given for Ry1 and may also be d-Cs-alkoxy or C2-C8-alkenyloxy;
Ry4 has one of the meanings given for Ry1, or
Ry3 and Ry4 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 , 2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-Cβ-alkyl,
Figure imgf000078_0001
C-i-Cβ-haloalkoxy;
Ry5 has one of the meanings given for Ry2, and may also be hydroxy, Ci- Cs-alkoxy, Ci-Cs-haloalkoxy, C2-C8-alkenyloxy, C2-C8-haloalkenyloxy, C2-C8-alkynyloxy, C2-C8-haloalkynyloxy, Cs-C^-cycloalkyloxy, C3-C12- cycloalkenyloxy, phenyloxy, naphthyloxy, 5- to 10-membered hetero- cyclyloxy or 5- to 10-membered hetaryloxy, wherein the six last- mentioned radicals may be unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rw and where 5- to 10-membered het- erocyclyloxy and 5- to 10-membered hetaryloxy contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyloxy may furthermore contain one or two CO groups as ring members;
Ry6 has one of the meanings given for Ry3;
Ry7 has one of the meanings given for Ry1 or
Ry6 and Ry7 together with the nitrogen atom to which they are attached may also form a saturated 3- to 7-membered heterocycle which is attached via N and may contain one further heteroatom from the group consisting of O, N, S and S(O)2 as ring members and/or may carry 1 ,
2, 3, 4, 5 or 6 substituents selected from the group consisting of halogen, Ci-Cβ-alkyl, Ci-C6-alkoxy,Ci-C6-haloalkyl and Ci-Cβ-haloalkoxy; Ry8 and Ry9 are in each case independently of one another selected from hydrogen, hydroxy, Ci-Cio-alkylamino, di(Ci-Cio-alkyl)amino, CrCβ- alkyl, d-Cβ-alkoxy, Ci-C6-alkylthio, C3-Ci2-cycloalkyl, phenyl, phenyl- Ci-C4-alkyl, phenoxy-Ci-C4-alkyl and phenoxy, wherein C3-C12- cycloalkyl, phenyl and the phenyl moiety of phenyl-Ci-C4-alkyl, phenoxy-Ci-C4-alkyl and phenoxy may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from halogen, Ci-C4-alkyl and Ci-C4-alkoxy;
Ry1° and Ry11 have in each case independently of one another one of the meanings given for Ry8 and Ry9;
Ry12 is hydroxy, Ci-C6-alkyl, d-Ce-alkoxy, Ci-C6-haloalkyl, phenyl, phenoxy and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moi- ety of phenoxy and phenyl-Ci-C4-alkyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl, Cr C4-haloalkyl and Ci-C4-alkoxy;
Ry13, Ry14 and Ry15, are in each case independently of one another selected from CrCβ-alkyl, d-Cβ-alkoxy, phenyl and phenyl-Ci-C4-alkyl, wherein phenyl and the phenyl moiety of phenyl-Ci-C4-alkyl may be unsubstituted or substituted by 1 , 2, 3, 4 or 5 substituents selected from Ci-C4-alkyl and Ci-C4-alkoxy;
Ryy is selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, Ci-C4-alkylamino, di(Ci-C4-alkyl)amino, d- Ce-alkyl, d-Ce-alkoxy, Ci-C6-haloalkoxy, Ci-C6-haloalkyl, CrC6- alkylthio, d-Ce-haloalkylthio, Ci-Ce-alkylsulfonyl, CrC6- haloalkylsulfonyl, C2-C6-alkenyloxy, C2-C6-alkynyloxy, carboxyl, d- Cβ-alkoxycarbonyl and Cs-Cs-cycloalkyl;
Ryyy is selected from the group consisting of halogen, cyano, nitro, ORy1, -SRy2, -S(O)2Ry2, -NRy3Ry4, -C(O)Ry5, d-Ce-alkyl, d-Ce-haloalkyl, C2- Cβ-alkenyl, C2-C6-alkynyl, C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3- Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10-membered heterocyclyl or
5- to 10-membered hetaryl, where 5- to 10-membered heterocyclyl and 5- to 10-membered hetaryl contain 1 , 2, 3 or 4 heteroatoms selected independently from one another from O, S and N as ring members and 5- to 10-membered heterocyclyl may furthermore contain one or two CO groups as ring members and where C3-Ci2-cycloalkyl, C3-Ci2-cycloalkenyl, C3-Ci2-cycloalkynyl, phenyl, naphthyl, 5- to 10- membered heterocyclyl and 5- to 10-membered hetaryl for their part are each unsubstituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals Rw, it being possible for two radicals Rm that are bound to adjacent carbon atoms of the phenyl ring to form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7- membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms se- lected from O, S and N as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 , 2, 3, or 4 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, d-Cβ-alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ-haloalkoxy, d-Cβ-alkylthio, Ci- Ce-haloalkyl and (=0) (oxo);
R1 and R2 are each independently halogen, OH, SH, NH2, SO3H, COOH, cyano, nitro, Ci-Cβ-alkyl, C-i-Cβ-alkoxy, Ci-Cβ-alkylamino, di(Ci-C6-alkyl)amino, Ci- Cs-alkylthio, C2-C6-alkenyl, C2-C6-alkenyloxy, C2-C6-alkenylamino, C2-C6- alkenylthio, C2-C6-alkynyl, C2-C6-alkynyloxy, C2-C6-alkynylamino, C2-C6- alkynylthio, d-Cβ-alkylsulfonyl, d-Cβ-alkylsulfoxyl, C2-C6-alkenylsulfonyl, C2-C6-alkynylsulfonyl, formyl, d-Cβ-alkylcarbonyl, C2-C6-alkenylcarbonyl, C2-C6-alkynylcarbonyl, d-Cβ-alkoxycarbonyl, C2-C6-alkenyloxycarbonyl, C2- Cβ-alkynyloxycarbonyl, d-Cβ-alkylcarbonyloxy, d-Cβ-alkylcarbonyloxy, C2- Cβ-alkenylcarbonyloxy, C2-C6-alkynylcarbonyloxy, wherein the carbon atoms in the aliphatic radicals of the aforementioned groups may carry any combination of 1 , 2 or 3 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C-i-Cβ- alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-C6-haloalkoxy and Ci-Cβ- alkylthio,
C(O)NRa1Ra2, (SO2)NR31R32, wherein Ra1 and Ra2 are each independently hydrogen, Ci-Cβ-alkyl, C2-C6-alkenyl, or C2-C6-alkynyl, wherein the carbon atoms in these groups may carry any combination of 1 , 2 or 3 radicals se- lected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy and d-Cβ-alkylthio,
a radical Z-Ar or a radical Z-Cy, wherein Z is a single bond, oxygen, sulfur, Ci-Cβ-alkanediyl or d-Cβ-alkane- diyloxy,
Ar is phenyl, naphthyl or a mono- or bicyclic 5- to 10-membered het- eroaromatic ring, which contains 1 ,2, 3 or 4 heteroatoms selected from oxygen, sulfur and nitrogen as ring members, wherein Ar is un- substituted or may carry any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, Ci-Cβ-alkoxy, C2-C6-alkenyl- oxy, C2-C6-alkynyloxy, d-Cβ-haloalkyl, C-i-Cβ-haloalkoxy, Ci-Cβ- alkylthio and d-Cβ-haloalkylthio; and
Cy is C3-Ci2-cycloalkyl, which is unsubstituted or substituted with any combination of 1 , 2, 3, 4 or 5 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, Ci-Cβ-alkyl, C-i-Cβ-alkoxy, C2-C6-alkenyloxy, C2-C6-alkynyloxy, Ci-Cβ- haloalkyl, C-i-Cβ-haloalkoxy, d-Cβ-alkylthio and d-Cβ-haloalkylthio;
and wherein two radicals R1 or R2 that are bound to adjacent carbon atoms of the phenyl rings may form together with said carbon atoms a fused benzene ring, a fused saturated or partially unsaturated 5-, 6-, or 7-membered carbocycle or a fused 5-, 6-, or 7-membered heterocycle, which contains 1 , 2, 3 or 4 heteroatoms selected from O, S and N as ring members, and wherein the fused ring is unsubstituted or may carry any combination of 1 ,
2, 3, or 4 radicals selected from the group consisting of halogen, cyano, nitro, hydroxy, mercapto, amino, carboxyl, d-Cβ-alkyl, d-Cβ-alkoxy, C2-C6- alkenyloxy, C2-C6-alkynyloxy, d-Cβ-haloalkoxy, d-Cβ-alkylthio, d-Cβ- haloalkyl and (=0) (oxo);
for combating invertebrate pests.
2. The use according to claim 1 , wherein X is -C(=O)-.
3. The use according to any of claims 1 or 2, wherein Y is d-Cβ-alkyl, d-Cβ-alkoxy- d-Cβ-alkyl, d-d-alkoxycarbonyl-d-Cβ-alkyl, d-d-alkylcarbonyloxy-d-Cβ-alkyl or phenoxy-d-Cβ-alkyl, wherein the phenyl moiety of phenoxy-d-Cβ-alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Cβ- alkyl, d-C6-haloalkyl, d-C6-alkylthio, d-C6-haloalkylthio, d-C6-alkoxy or CrC6- haloalkoxy groups.
4. The use according to any of claims 1 or 2, wherein Y is a 5- or 6-membered het- aryl containing 1 or 2 heteroatoms selected independently from one another from O1 S and N as ring members which is unsubstituted or substituted with any combination of 1 to 3 halogen atoms, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or Ci-C3-haloalkyl groups.
5. The use according to claim 4, wherein Y is pyridyl which is unsubstituted or sub- stituted with any combination of 1 to 3 halogen atoms, Ci-C3-alkyl, Ci-C3-alkoxy,
Ci-C3-haloalkoxy or Ci-C3-haloalkyl groups.
6. The use according to any of the preceding claims, wherein n in formula I is 0, 1 , 2 or 3, in particular 1 , 2 or 3.
7. The use according to any of the preceding claims, wherein m in formula I is 0, 1 , 2 or 3, in particular 1 , 2 or 3.
8. The use as claimed in any of claims 6 or 7, wherein n+m is an integer from 1 , 2, 3, 4 or 5, in particular s, 4 or 5.
9. The use according to any of the preceding claims, wherein R1 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, Ci-C4-haloalkoxy and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 C-i-Ce-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, d-Ce-haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups.
10. The use according to any of the preceding claims, wherein R2 is selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsub- stituted or substituted with any combination of 1 to 5 halogen, 1 to 3 Ci-Cβ-alkyl,
C-i-Ce-haloalkyl, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-C6-alkoxy or Ci-C6- haloalkoxy groups.
1 1. The use according to any of claims 1 to 9, wherein two radicals R2 that are bound to adjacent carbon atoms together form a bivalent radical selected from
-0-CH2-O-, -0-CH2-CH2-O, -0-CH2-CH2-, -0-CH2-CH2-CH2-, -S-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH2-CH2-CH2-CH2-, -CH=CH-CH=CH- and -CH=CH-CH=N-.
12. The use according to any of the preceding claims, wherein the compound of formula I is selected from compounds of formula I'
Figure imgf000083_0001
wherein in formula I' X and Y have one of the meanings given in any of the preceding claims;
R1a and R1b, are, independently of one another, hydrogen or have one of the meanings given in any of the preceding claims for R1; and R2a, R2b and R2c, are, independently of one another other, hydrogen or have one of the meanings given in any of the preceding claims for R2.
13. The use according to claim 12, wherein R1a and R1b are, independently from one another, selected from halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, C1-C4- haloalkoxy and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 d-Ce-alkyl, d-Ce-haloalkyl, d-Ce-alkylthio, Ci-C6- haloalkylthio, Ci-C6-alkoxy or Ci-Cβ-haloalkoxy groups, provided that one of the radicals R1a or R1b may also be hydrogen.
14. The use according to any of claims 12 and 13, wherein R2a and R2b are, independently from one another, halogen, Ci-C4-alkyl, Ci-C4-alkoxy, Ci-C4-haloalkyl, and phenyl, which is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 Ci-C6-alkyl, Ci-C6-haloalkyl, Ci-C6-alkylthio, Ci-C6-haloalkylthio, Ci-Cβ-alkoxy or Ci-Cβ-haloalkoxy groups or R2a and R2b together form a bivalent radical selected from -0-CH2-O-, -0-CH2-CH2-O, -0-CH2-CH2-, -0-CH2-CH2-CH2-, -S-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH2-CH2-CH2-CH2-, -CH=CH-CH=CH- and -CH=CH-CH=N-.
15. The use according to any of claims 12 to 14, wherein X is -C(=O)-;
Y is Ci-C4-alkyl, Ci-C4-alkoxy-Ci-C4-alkyl, Ci-C4-alkoxycarbonyl-Ci-C4-alkyl, Ci-C4-alkylcarbonyloxy-Ci-C4-alkyl or phenoxy-Ci-C4-alkyl, wherein the phenyl moiety of phenoxy-Ci-Cβ-alkyl is unsubstituted or substituted with any combination of 1 to 5 halogen, 1 to 3 Ci-Cβ-alkyl, C-i-Cβ-haloalkyl, Cr Cβ-alkylthio, d-Cε-haloalkylthio, d-Cβ-alkoxy or Ci-Cβ-haloalkoxy groups, or pyridyl which is unsubstituted or substituted with any combination of 1 to 3 halogen atoms, Ci-C3-alkyl, Ci-C3-alkoxy, Ci-C3-haloalkoxy or C1-C3- haloalkyl groups; R1a and R1b are, independently from one another, halogen, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R1a or R1b may also be hydrogen; R2a and R2b are, independently from one another halogen, Ci-C4-alkyl, C1-C4- alkoxy, Ci-C4-haloalkyl and Ci-C4-haloalkoxy, where one of the radicals R2a or R2b may also be hydrogen, or
R2a together with R2b forms a bivalent radical selected from -O-CH2-O-, -O-CH2-CH2-O, -O-CH2-CH2-, -O-CH2-CH2-CH2-, -0-CH=CH-, -S-CH=CH-, -CH=CH-CH=CH- and -CH=CH-CH=N-; and R2c is hydrogen.
16. The use according to claim 15, wherein R1a and R1b are each methyl and wherein R2a and R2b are, independently from one another halogen or methyl, or R2a together with R2b forms a bivalent radical selected from -O-CH2-O-, -O-CH2-CH2-O, -O-CH2-CH2-, -O-CH2-CH2-CH2-, -0-CH=CH-, where the oxygen atom in the last three mentioned radicals is preferably bound to the R2a position,
-S-CH=CH-, where sulphur is preferably bound to the R2a position, -CH=CH-CH=CH- and -CH=CH-CH=N-, where nitrogen is preferably bound to the R2a position.
17. The use of a thiourea compound as defined in any of the preceding claims or a salt thereof for combating arthropod pests and/or nematodes.
18. The use as claimed in claim 17 for combating insects.
19. The use as claimed in claim 17 for combating acaridae.
20. Thiourea compound of the formula I
Figure imgf000084_0001
wherein m, n, X, Y, R1 and R2 are as defined in any of claims 1 to 16 and their salts, except for the compounds of the formula I in which X is -C(=O)-, if Y is phenyl or methyl.
21. An agricultural composition comprising at least one thiourea compound as defined in any of claims 1 to 16 and/or an agriculturally acceptable salt thereof and at least one liquid or solid carrier.
22. A method for controlling invertebrate pests which method comprises treating the pests, their food supply, their habitat or their breeding ground or a plant, plant propagation material, soil, area, material or environment in which the pests are growing or may grow, or the materials, plants, plant propagation material, soils, surfaces or spaces to be protected from pest attack or infestation with a pesti- cidally effective amount of a thiourea compound or a salt thereof as defined in any of claims 1 to 16.
23. The method as claimed in claim 22 for protecting plants, which method comprises treating the plants with a pesticidally effective amount of a thiourea compound or an agriculturally acceptable salt thereof as defined in any of claims 1 to 16.
24. The method as claimed in claim 22 for protecting plant propagation material and/or the plants which grow therefrom, which method comprises treating the plant propagation material with a pesticidally effective amount of a thiourea compound or an agriculturally acceptable salt thereof as defined in any of claims 1 to 16.
25. Plant propagation material, comprising at least one thiourea compound as defined in any of claims 1 to 16 and/or an agriculturally acceptable salt thereof.
26. The use of a thiourea compound of the formula I as defined in any of claims 1 to 16 and/or a veterinarily acceptable salt thereof for treating or protecting an animal from infestation or infection by invertebrate parasites.
27. A method for treating or protecting an animal from infestation or infection by in- vertebrate parasites which comprises bringing the animal in contact with a para- siticidally effective amount of a thiourea compound or a veterinarily acceptable salt thereof as defined in any of claims 1 to 16.
PCT/EP2009/067382 2008-12-18 2009-12-17 Thiourea compounds for combating invertebrate pests Ceased WO2010070035A1 (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006125745A2 (en) * 2005-05-23 2006-11-30 Basf Aktiengesellschaft 1-(1,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests
WO2007060120A1 (en) * 2005-11-25 2007-05-31 Basf Se Indanyl-and tetrahydronaphtyl-amino-thiourea compounds for combating animal pests
WO2008141980A1 (en) * 2007-05-24 2008-11-27 Basf Se Substituted amino-thiourea compounds for combating animal pests

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2006125745A2 (en) * 2005-05-23 2006-11-30 Basf Aktiengesellschaft 1-(1,2-diphenyl-ethyl)-3-(2-hydroxyethyl)-thiourea compounds for combating animal pests
WO2007060120A1 (en) * 2005-11-25 2007-05-31 Basf Se Indanyl-and tetrahydronaphtyl-amino-thiourea compounds for combating animal pests
WO2008141980A1 (en) * 2007-05-24 2008-11-27 Basf Se Substituted amino-thiourea compounds for combating animal pests

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