WO2010012793A1 - Fungicide aminothiazole derivatives - Google Patents

Fungicide aminothiazole derivatives Download PDF

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Publication number
WO2010012793A1
WO2010012793A1 PCT/EP2009/059839 EP2009059839W WO2010012793A1 WO 2010012793 A1 WO2010012793 A1 WO 2010012793A1 EP 2009059839 W EP2009059839 W EP 2009059839W WO 2010012793 A1 WO2010012793 A1 WO 2010012793A1
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WIPO (PCT)
Prior art keywords
substituted
alkyl
amino
aryl
thiocarbonyl
Prior art date
Application number
PCT/EP2009/059839
Other languages
French (fr)
Inventor
Martin Adamczewski
Christian Arnold
Angela Becker
Lionel Carles
Peter Dahmen
Ralf Dunkel
Eva-Maria Franken
Ulrich Görgens
Marie-Claire Grosjean-Cournoyer
Hendrik Helmke
Stefan Hillebrand
Hadano Hiroyuki
Joachim Kluth
Thomas Knobloch
Peter Lösel
Dirk Nennstiel
Heiko Rieck
Rachel Rama
Rüdiger SUELMANN
Arnd Voerste
Ulrike Wachendorff-Neumann
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Bayer Cropscience Sa
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Publication of WO2010012793A1 publication Critical patent/WO2010012793A1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
    • C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
    • C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members 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
    • C07D277/56—Carbon atoms having three bonds to hetero atoms with at the most one bond to halogen
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
    • A01N43/78—1,3-Thiazoles; Hydrogenated 1,3-thiazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/82—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with three ring hetero atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/72—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms
    • A01N43/84—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms six-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,4

Definitions

  • the present invention relates to aminothiazole derivatives, their process of preparation, preparation intermediate compounds, their use as fungicide, acaricide and/or insecticide active agents, particularly in the form of fungicide, acaricide and/or insecticide compositions and methods for the control of phytopathogenic fungi, or of insects, using these compounds or compositions.
  • R 4 can represent a group CO-C. These compounds do not form part of the present invention.
  • R 1 , R 2 and R 3 independently represent hydrogen, a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tri(C r C 8 -alkyl)silyl-C r C 8 -alkyl, a substituted or non-substituted C 3 - C 8 -cycloalkyl, a substituted or non-substituted tri(C r C 8 -alkyl)silyl-C 3 -C 8 -cycloalkyl, a substituted or non-substituted C r C 8 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 - alkenyl, C 3
  • Z 1 , Z 2 , Z 3 , Z 4 , Z 5 and Z 6 independently represent a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tr ⁇ CrCValkylJsilyl-CrCs-alkyl, a substituted or non-substituted C 3 -C 8 -cycloalkyl, a substituted or non-substituted tri(C r C 8 -alkyl)silyl-C 3 -C 8 - cycloalkyl, a substituted or non-substituted C r C 8 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non -substituted C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkyl,
  • C 6 -alkyl a substituted or non-substituted (benzyloxyimino)-C r C 6 -alkyl, a substituted or non- substituted aryl-[ C r C 8 ]-alkyl, a substituted or non-substituted C r C 8 -alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted C r C 8 -alkyl-(n-alkoxy)-imidoyl, a substituted or non- substituted aryl-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non- substituted aryl-amino-(n-
  • C r C 8 -alkyl-hydrazino hydroxy-amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted C r C 8 -alkoxy-amino, a substituted or non-substituted alkyl- sulphenyl-amino, a substituted or non-substituted aryl-sulphenyl-amino, a substituted or non-substituted CrCs-alkyl-amino-silyl, a substituted or non-substituted di-CrC 8 -alkyl- amino-silyl, amino-sulphinyl-amino, a substituted or non-substituted alkyl-sulphinyl-amino, a substituted or non-substituted aryl-sulphinyl-amino, amino-sulfonyl-
  • CrCs-alkoxy-carbonyl a substituted or non-substituted CrCs-thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted CrCs-alkyl-thiocarbonyl, a substituted or non-substituted CrCs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino- thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non- substituted
  • halogen means fluorine, chlorine, bromine or iodine ;
  • heteroatom can represent nitrogen, oxygen or sulphur ;
  • a group or a substituent that is substituted according to the invention can be substituted by one or more of the following groups or atoms: a halogen atom, a nitro group, a hydroxy group, a cyano group, an amino group, a sulphenyl group, a pentafluoro- ⁇ 6 - sulphenyl group, a formyl group, a substituted or non-substituted carbaldehyde 0-(C 1 -C 8 - alkyl)oxime, a formyloxy group, a formylamino group, a carbamoyl group, a N-hydroxycarbamoyl group, a formylamino group, a (hydroxyiminoJ-CrCValkyl group, a C r C 8 -alkyl, a In(C 1 -C 8 - alkyl)silyl-C r C 8 -alkyl, C 3
  • any of the compounds according to the invention can exist as one or more stereoisomers depending on the number of stereogenic units (as defined by the IUPAC rules) in the compound.
  • the invention thus relates equally to all the stereoisomers and to the mixtures of all the possible stereoisomers, in all proportions.
  • the stereoisomers can be separated according to the methods which are known per se by the man ordinary skilled in the art.
  • Preferred compounds of formula (I) according to the invention are those wherein R 1 and R 2 independently represent hydrogen, a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tri(C r Cs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C 3 -C 8 -cycloalkyl, a substituted or non-substituted tr ⁇ CrCs-alkylJsilyl-Cs-Cs-cycloalkyl, a substituted or non-substituted C r C 8 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkenyl,
  • R 1 and R 2 independently represent a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tr ⁇ CrCs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C 3 -C 8 -cycloalkyl, a substituted or non- substituted tri(CrC 8 -alkyl)silyl-C 3 -C 8 -cycloalkyl, a substituted or non-substituted C r C 8 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkenyl, a substituted
  • R 1 and R 2 independently represent a substituted or non-substituted alpha substituted benzyl, a substituted or non- substituted alkoxy-aryl, a substituted or non-substituted aryloxy-aryl, hydrogen, substituted or non- substituted cycloalkyl, halogenoalkyl, substituted or non-substituted 2-phenylethyl, substituted or non- substituted alpha substituted alkyl.
  • R 1 and R 2 independently represent 1-cyclopropylpropan-2-yl; 1-phenylethyl; 2-phenylethyl; 1 -cyclohexylethyl; 1- ethylpropyl; 4-[4-(trifluoromethyl)phenoxy]phenyl; 1-cyclopropylpropan-2-yl; dicyclopropylmethyl; 1- cyclopropylethyl; 1-(4-ethoxyphenyl)ethyl; 1-(4-ethylphenyl)ethyl; 1-(4-methoxyphenyl)ethyl; 1 -[4-(propan- 2-yl)phenyl]ethyl; cyclopentyl; cyclohexyl; 4-methyl-cyclohexyl; 1-(3-methoxyphenyl)ethyl; 2-(4- chlorophenyl)ethyl;
  • R 3 represents a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tr ⁇ CrCs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C 3 -C 8 -cycloalkyl, a substituted or non-substituted tri(CrC 8 -alkyl)silyl-C 3 - C 8 -cycloalkyl, a substituted or non-substituted CrC 8 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkenyl, a substituted or non-
  • R 3 represents a substituted or non-substituted C r C 4 -alkyl, a substituted or non-substituted tri(C r C 4 - alkyl)silyl-C r C 4 -alkyl, a substituted or non-substituted C 3 -C 4 -cycloalkyl, a substituted or non-substituted tnXCrQ-alkylJsilyl-Cs-C ⁇ cycloalkyl, a substituted or non-substituted C r C 4 -halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C 3 -C 4 -halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkenyl, a substituted or non-substituted
  • R 3 represents F, Cl, Br, I, in particular Br; a substituted or non-substituted C r C 4 -alkyl in particular methyl, C 2 - C 8 -alkynyl in particular ethynyl, CF 3 , cyclopropyl, benzyl.
  • R 4 and R 5 independently represent a substituted or non-substituted C r C 8 -alkyl-(N-alkyl)-imidoyl, a substituted or non-substituted CrC 8 -alkyl-(N-alkoxy)-imidoyl, a substituted or non-substituted aryl-(N-alkyl)-imidoyl, a substituted or non-substituted aryl-(N-alkoxy)-imidoyl, formamidino, amino-(N-alkyl)-imidoyl, amino-(N- alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(N-alkyl)-imidoyl, a substituted or non- substituted aryl-amino-(N-alkoxy)-imidoyl, a substituted or non- substituted aryl-
  • R 4 and R 5 independently represent formyl, hydrogen, a group selected in the list consisting of A 1 to A 8 , in particular a non substituted phenyl or a phenyl, substituted with 1 to 3 fluorine atoms, methyloxy, ethyloxy or trifluoromehtyl.
  • the present invention also relates to a process for the preparation of compounds of formula (I).
  • the process according to the invention can be carried according to the following schemes and reaction conditions. Specific steps and particular conditions can be adapted by the skilled person in order to prepare the compounds of formula (I) according to the invention.
  • Step A.1 Preparation of the 3-bromo-2-oxobutanoic acid :
  • Step A.2 Preparation of the 5-methyl-2-[(4-phenoxyphenyl)aminol-1 ,3-thiazole-4-carboxylic acid:
  • Step A.3 Preparation of the N-(4-fluorophenyl)-5-methyl-2-[(4-phenoxyphenyl)aminol-1 ,3-thiazole-4- carboxamide:
  • Step B.1 Preparation of the 2-[(tert-butoxycarbonyl)aminol-5-methyl-1 ,3-thiazole-4-carboxylic acid:
  • 3-bromo-2-oxobutanoic acid (20,5 g) is dissolved in DMF (80 ml). Triethylamine (11 ,5 g) is then added dropwise. A solution of N-Boc-thiourea (20 g) in DMF (40 ml) is finally added dropwise. The reaction mixture is stirred at 80 0 C for 3 hours. 4g of 3-bromo-2-oxobutanoic acid and 3 ml of triethylamine are added to complete the reaction. After 2 hours at 80 0 C, the reaction mixture is poured onto ice water and filtered, washed with water, dried with MgSO4.
  • Step B.2 Preparation of the tert-butyl (4-[(4-fluorophenyl)carbamoyll-5-methyl-1 ,3-thiazol-2-yl)carbamate:
  • Step B.3 Preparation of the 2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide:
  • Step B.4 Preparation of the 2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide:
  • Step C.1 Preparation of the 2-[(3-chlorophenyl)aminol-1 ,3-thiazole-4-carboxylic acid:
  • Step C.3 Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-5-iodo-1 ,3-thiazole-4-carboxamide:
  • N-tert-butyl-2-[(3-chlorophenyl)amino]-1 ,3-thiazole-4-carboxamide (595 mg) is dissolved in DMF (6,2 ml) and cooled down at 0 0 C. NIS (616 mg) is then added (orange coloration). After 15 minutes at 0°C, AcOEt is added and several washes are performed: LiCI sat., water, NaHCO3 sat.. After concentration and drying with MgSO4, N-tert-butyl ⁇ -p-chlorophenylJaminoJ- ⁇ -iodo-I .S-thiazole ⁇ -carboxamide is obtained
  • Step C.4 Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-5-(trifluoromethyl)-1 ,3-thiazole-4- carboxamide:
  • N-tert-butyl ⁇ -KS-chlorophenylJaminol- ⁇ -iodo-I .S-thiazole ⁇ -carboxamide (191 mg) is dissolved in DMF/NMP 1/1 (0.4 ml). Copper (I) iodide (114 mg) is added at room temperature.
  • a solution of triethyl(trifluoromethyl)silane (2,226 g) and Potassium fluoride (695 mg) in DMF/NMP 1/1 (0,4 ml) is then added to the reaction mixture. After stirring for 20 minutes at 80 0 C and 1 hour at room temperature, AcOEt is added and several washes with NaCI sat. are performed. The organic phase is concentrated and dried with MgSO4.
  • Step D.1 Preparation of the 2-amino-5-bromo-1 ,3-thiazole-4-carboxylic acid:
  • 2-amino-5-bromo-1 ,3-thiazole-4-carboxylic acid (1 ,129 g) is dissolved in DMF (20 ml).
  • TBTU (1 ,463 g), DIPEA (1 ,178 g) and 3-iodo-aniline (1 ,018 g) are added at room temperature.
  • DMF is evaporated.
  • the crude solid is dissolved in AcOEt and washed with NaHCO3 sat., water, LiCI sat..
  • Step D.3 Preparation of the 5-bromo-2-(formylamino)-N-(3-iodophenyl)-1 ,3-thiazole-4 ⁇ :arboxamide:
  • Step E.1 Preparation of 2-anilino-5-iodo-N-(1 -phenylethyl)-1 ,3-thiazole-4-carboxamide (compound example 722):
  • Step E.2 Preparation of 2-anilino-N-(1-phenylethv ⁇ -5-[(trimethylsilv ⁇ ethvnyll-1 ,3-thiazole-4-carboxamide (compound example 2735):
  • Step F.1 Preparation of methyl 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylate:
  • Step F.3 Preparation of the 2-anilino-5-(methylsulfanv ⁇ -N-(1-phenylethv ⁇ -1 ,3-thiazole-4-carboxamide:
  • Suitable solvents for carrying out processes according to the invention are customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nitriles, such as acetonitrile
  • Suitable bases for carrying out processes according to the invention are inorganic and organic bases which are customary for such reactions.
  • alkaline earth metal alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide
  • alkali metal carbonates such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate
  • alkali metal or alkaline earth metal acetates such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethyl- aminopyridine, 1 ,4-diazabicyclo[2.2.2
  • reaction temperature can independently be varied within a relatively wide range.
  • the process according to the invention is carried out at temperatures between -20 0 C and 160 0 C.
  • Process according to the invention is generally independently carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
  • reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
  • the present invention relates to compounds of formula (II) useful as intermediate compounds or materials for the process of preparation according to the invention.
  • the present invention thus provides compounds of formula (II)
  • R 3 represents a substituted or non-substituted C r C 8 -alkyl, a substituted or non-substituted tri(C r Cs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C 3 -C 8 -cycloalkyl, a substituted or non- substituted tri(C 1 -C 8 -alkyl)silyl-C 3 -C 8 -cycloalkyl, a substituted or non-substituted C 1 -C 8 - halogenoalkyl having 1 to 5 halogen atoms, a substituted or non -substituted C 3 -C 8 - halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C 2 -C 8 -alkenyl,
  • R 4 and R 5 independently represent a substituted or non-substituted C 1 -C 8 -alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted C 1 -C 8 -alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- (n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, hydrazino- imidoyl, a substituted or non-substituted aryl-hydrazino-imidoyl, a substituted or non-substituted CrCs-alkyl-hydrazino-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- amino-(n
  • Preferred intermediate compounds of formula (II) according to the invention are defined by the combinations of preferred features of R 3 , R 4 and R 5 as herein-defined for the compounds of formula (I).
  • the present invention also relates to a fungicide, acaricide and/or insecticide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).
  • an effective and non-phytotoxic amount means an amount of composition according to the invention which is sufficient to control or destroy the fungi, acarids or insects present or liable to appear on the crops and which does not entail any appreciable symptom of phytotoxicity for the said crops.
  • Such an amount can vary within a wide range depending on the fungus, acarids or insect to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide, acaricide and/or insecticide composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.
  • a fungicide, acaricide and/or insecticide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.
  • the term "support” denotes a natural or synthetic organic or inorganic compound with which the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant.
  • This support is thus generally inert and should be agriculturally acceptable.
  • the support can be a solid or a liquid.
  • suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.
  • composition according to the invention can also comprise additional components.
  • the composition can further comprise a surfactant.
  • the surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants.
  • polyacrylic acid salts lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts
  • polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines substituted phenols (in particular alkylphenols or ary
  • surfactant content can be comprised from 5% to 40% by weight of the composition.
  • additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents.
  • the active compounds can be combined with any solid or liquid additive, which complies with the usual formulation techniques.
  • compositions according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight.
  • Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure),gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder
  • the compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity.
  • the mixtures thus obtained have a broadened spectrum of activity.
  • the mixtures with other fungicide compounds are particularly advantageous.
  • the composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous.
  • a method for controlling the phytopathogenic fungi, acarids, and/or insects of plants, crops or seeds characterized in that an agronomically effective and substantially non-phytotoxic quantity of a pesticide composition according to the invention is applied as seed treatment, foliar application, stem application, drench or drip application (chemigation) to the seed, the plant or to the fruit of the plant or to soil or to inert substrate (e.g. inorganic substrates like sand, rockwool, glasswool; expanded minerals like perlite, vermiculite, zeolite or expanded clay), Pumbe, Pyroclastic materials or stuff, synthetic organic substrates (e.g.
  • polyurethane organic substrates (e.g. peat, composts, tree waste products like coir, wood fibre or chips, tree bark) or to a liquid substrate (e.g. floating hydroponic systems, Nutrient Film Technique, Aeroponics) wherein the plant is growing or wherein it is desired to grow.
  • organic substrates e.g. peat, composts, tree waste products like coir, wood fibre or chips, tree bark
  • liquid substrate e.g. floating hydroponic systems, Nutrient Film Technique, Aeroponics
  • the method according to the invention can either be a curing, preventing or eradicating method.
  • a composition used can be prepared beforehand by mixing the two or more active compounds according to the invention.
  • Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.
  • the dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously • for foliar treatments: from 0.1 to 10,000 g/ha, preferably from 10 to 1 ,000 g/ha, more preferably from 50 to 300g/ha; in case of drench or drip application, the dose can even be reduced, especially while using inert substrates like rockwool or perlite;
  • • for seed treatment from 2 to 200 g per 100 kilogram of seed, preferably from 3 to 150 g per 100 kilogram of seed; • for soil treatment: from 0.1 to 10,000 g/ha, preferably from 1 to 5,000 g/ha.
  • the doses herein indicated are given as illustrative Examples of method according to the invention.
  • a person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated. Under specific conditions, for example according to the nature of the phytopathogenic fungus to be treated or controlled, a lower dose can offer adequate protection. Certain climatic conditions, resistance or other factors like the nature of the phytopathogenic fungi or the degree of infestation, for example, of the plants with these fungi, can require higher doses of combined active ingredients. The optimum dose usually depends on several factors, for example on the type of phytopathogenic fungus to be treated, on the type or level of development of the infested plant, on the density of vegetation or alternatively on the method of application.
  • the crop treated with the pesticide composition or combination according to the invention is, for example, grapevine, but this could be cereals, vegetables, lucerne, soybean, market garden crops, turf, wood, tree or horticultural plants.
  • the method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots.
  • the method of treatment according to the invention can also be useful to treat the over-ground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
  • cotton Among the plants that can be protected by the method according to the invention, mention can be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp.
  • Rosaceae sp. for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches
  • Rosaceae sp. for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches
  • Rubiaceae sp. for instance banana trees and plantins
  • Rubiaceae sp. Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons oranges and grapefruit); Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); major crops such as Graminae sp.
  • Asteraceae sp. for instance sunflower
  • Cruciferae sp. for instance colza
  • Fabacae sp. for instance peanuts
  • Papilionaceae sp. for instance soybean
  • Solanaceae sp. for instance potatoes
  • Chenopodiaceae sp. for instance beetroots
  • horticultural and forest crops as well as genetically modified homologues of these crops.
  • plants and plant parts can be treated.
  • plants are meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights).
  • Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods.
  • plant parts are meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed.
  • Crops and vegetative and generative propagating material for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
  • plants that can be protected by the method according to the invention mention may be made of major field crops like corn, soybean, cotton, Brassica oilseeds such as Brassta napus (e.g. canola), Brassica rapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat, sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vine and various fruits and vegetables of various botanical taxa such as Rosaceae sp.
  • Brassta napus e.g. canola
  • Brassica rapa e.g. mustard
  • Brassica carinata e.g. mustard
  • Ribesioidae sp. for instance pip fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, berry fruits such as strawberries
  • Ribesioidae sp. Juglandaceae sp.
  • Betulaceae sp. Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantings), Rubiaceae sp.
  • Theaceae sp. for instance coffee
  • Theaceae sp. Sterculiceae sp.
  • Rutaceae sp. for instance lemons, oranges and grapefruit
  • Solanaceae sp. for instance tomatoes, potatoes, peppers, eggplant
  • Liliaceae sp. Compositiae sp.
  • lettuce, artichoke and chicory - including root chicory, endive or common chicory for instance Umbelliferae sp. (for instance carrot, parsley, celery and celeriac)
  • Cucurbitaceae sp. for instance cucumber - including pickling cucumber, squash, watermelon, gourds and melons
  • Cruciferae sp. for instance white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi, radish, horseradish, cress, Chinese cabbage
  • Leguminosae sp. for instance peanuts, peas and beans beans - such as climbing beans and broad beans
  • Chenopodiaceae sp. for instance mangold, spinach beet, spinach, beetroots
  • Malvaceae for instance okra
  • Asparagaceae for instance asparagus
  • horticultural and forest crops ornamental plants; as well as genetically modified homologues of these crops.
  • the method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds.
  • GMOs genetically modified organisms
  • Genetically modified plants are plants of which a heterologous gene has been stably integrated into genome.
  • the expressbn "heterologous gene” essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology or RNA interference - RNAi - technology).
  • a heterologous gene that is located in the genome is also called a transgene.
  • a transgene that is defined by its particular location in the plant genome is called a transformatbn or transgenic event.
  • the treatment according to the invention may also result in superadditive (“synergistic") effects.
  • superadditive for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
  • the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the inventbn, for example against fungi.
  • Plant- strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms.
  • unwanted microorganisms are to be understood as meaning phytopathogenb fungi, bacteria and viruses.
  • the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment.
  • the period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
  • Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means). Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids. Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses.
  • Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
  • Plants and plant cultivars which may also be treated according to the invention are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation.
  • Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance.
  • Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability. Examples of plants with the above-mentioned traits are non-exhaustively listed in Table A.
  • Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome.
  • cytoplasmic male sterility CMS
  • WO 92/05251 WO 95/09910
  • WO 98/27806 WO 05/002324, WO 06/021972 and US 6,229,072
  • genetic determinants for male sterility can also be located in the nuclear genome.
  • Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering.
  • a particularly useful means of obtaining male-sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
  • Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means.
  • glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS).
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • EPSPS 5-enolpyruvylshikimate-3-phosphate synthase
  • Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in U.S. Patent Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example WO 02/36782, WO 03/092360, WO 05/012515 and WO 07/024782. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 01/024615 or WO 03/013226.
  • herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate.
  • Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition.
  • One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in U.S. Patent Nos.
  • herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD).
  • HPPD hydroxyphenylpyruvatedioxygenase
  • Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate.
  • Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated HPPD enzyme as described in WO 96/38567, WO 99/24585 and WO 99/24586.
  • Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD-inhibitor. Such plants and genes are described in WO 99/34008 and WO 02/36787.
  • Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate deshydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928.
  • Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors.
  • ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides.
  • ALS enzyme also known as acetohydroxyacid synthase, AHAS
  • AHAS acetohydroxyacid synthase
  • plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in U.S. Patent 5,084,082, for rice in WO 97/41218, for sugar beet in U.S. Patent 5,773,702 and WO 99/057965, for lettuce in U.S. Patent 5,198,599, or for sunflower in WO 01/065922.
  • Plants or plant cultivars which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance.
  • An "insect-resistant transgenic plant”, as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:
  • insecticidal portions thereof e.g., proteins of the Cry protein classes CrylAb, CryiAc, Cry1 B, Cry1C, Cry1 D, Cry1 F, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP 1999141 and WO 2007/107302); or
  • a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second other crystal protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cry34 and Cry35 crystal proteins (Moellenbeck et al. 2001 , Nat. Biotechnol. 19: 668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71 , 1765-1774) or the binary toxin made up of the Cry1A or Cry1 F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Appl. No. 12/214,022 and EP 08010791.5); or
  • a hybrid insecticidal protein comprising parts of different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1 ) above or a hybrid of the proteins of 2) above, e.g., the Cry1A.1O5 protein produced by corn event MON89034 (WO 2007/027777); or 4) a protein of any one of 1 ) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation, such as the Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A protein in corn event MIR604; or 5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insect
  • a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VIPIA and VIP2A proteins (WO 94/21795); or
  • a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1 ) above or a hybrid of the proteins in 2) above; or 8) a protein of any one of 5) to 7) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT102; or 9) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a crystal protein from Bacillus thuringiensis, such as the binary toxin made up of VIP3 and Cry1A or Cry1 F (US Patent Appl.
  • an insect-resistant transgenic plant also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 10.
  • an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 10, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.
  • An "insect-resistant transgenic plant”, as used herein, further includes any plant containing at least one transgene comprising a sequence producing upon expression a double-stranded RNA which upon ingestion by a plant insect pest inhibits the growth of this insect pest, as described e.g. in WO 2007/080126.
  • Plants or plant cultivars which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include: 1 ) plants which contain a transgene capable of reducing the expression and/or the activity of poly(ADP-ribose) polymerase (PARP) gene in the plant cells or plants as described in WO
  • PARP poly(ADP-ribose) polymerase
  • plants which contain a stress tolerance enhancing transgene coding for a plant-functional enzyme of the nicotineamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphorybosyltransferase as described e.g. in EP 04077624.7, WO 2006/133827,
  • Plants or plant cultivars obtained by plant biotechnology methods such as genetic engineering which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as :
  • transgenic plants which synthesize a modified starch, which in its physical-chembal characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications.
  • a modified starch which in its physical-chembal characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications.
  • transgenic plants synthesizing a modified starch are disclosed, for example, in EP 0571427, WO 95/04826, EP 0719338, WO 96/15248, WO 96/19581 , WO 96/27674, WO 97/11188, WO 97/26362, WO 97/32985, WO 97/42328, WO
  • transgenic plants which synthesize non starch carbohydrate polymers or which synthesize non starch carbohydrate polymers with altered properties in comparison to wild type plants without genetic modification.
  • Examples are plants producing polyfructose, especially of the inulin and levan-type, as disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460, and WO
  • transgenic plants which produce hyaluronan, as for example disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP 2006304779, and WO 2005/012529.
  • transgenic plants or hybrid plants such as onions with characteristics such as 'high soluble solids content', 'low pungency' (LP) and/or 'long storage' (LS), as described in US Patent Appl. No. 12/020,360 and 61/054,026.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include: a) Plants, such as cotton plants, containing an altered form of cellulose synthase genes as described in WO 98/00549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO 2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO 01/17333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO 02/45485 e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.g.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include: a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g.
  • Plants or plant cultivars which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics.
  • Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering as described in US Patent Appl. No. 61/135,230 and EP 08075648.9.
  • transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non- regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending.
  • APHIS Animal and Plant Health Inspection Service
  • USA United States Department of Agriculture
  • Petition the identification number of the petition.
  • Technical descriptions of the transformation events can be found in the individual petition documents which are obtainable from APHIS, for example on the APHIS website, by reference to this petition number. These descriptions are herein incorporated by reference.
  • Extension of Petition reference to a previous petition for which an extension is requested.
  • Transgenic phenotype the trait conferred to the plants by the transformation event.
  • - Transformation event or line the name of the event or events (sometimes also designated as lines or lines) for which nonregulated status is requested.
  • APHIS documents various documents published by APHIS in relation to the Petition and which can be requested with APHIS.
  • the composition according to the invention can also be used against fungal diseases liable to grow on or inside timber.
  • the term "timber" means all types of species of wood and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood and plywood.
  • the method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
  • Powdery mildew diseases such as : Blumeria diseases, caused for example by Blumeria graminis ;
  • Podosphaera diseases caused for example by Podosphaera leucothcha ;
  • Sphaerotheca diseases caused for example by Sphaerotheca fuliginea ;
  • Uncinula diseases caused for example by Uncinula necator ; • Rust diseases such as :
  • Gymnosporangium diseases caused for example by Gymnosporangium sabinae ;
  • Hemileia diseases caused for example by Hemileia vastat ⁇ x ;
  • Phakopsora diseases caused for example by Phakopsora pachyrhizi or Phakopsora meibomiae ;
  • Puccinia diseases caused for example by Puccinia recondita
  • Uromyces diseases caused for example by Uromyces appendiculatus
  • Albugo diseases caused for example by Albugo Candida
  • Bremia diseases caused for example by Bremia lactucae ;
  • Peronospora diseases caused for example by Peronospora pisi or P. brassicae ;
  • Phytophthora diseases caused for example by Phytophthora infestans ;
  • Plasmopara diseases caused for example by Plasmopara viticola ;
  • Pseudoperonospora diseases caused for example by Pseudoperonospora humuli or
  • Pythium diseases caused for example by Pythium ultimum ; • Leafspot, leaf blotch and leaf blight diseases such as :
  • Alternaria diseases caused for example by Alternaria solani ;
  • Cercospora diseases caused for example by Cercospora beticola ;
  • Cladiosporum diseases caused for example by Cladiosporium cucumerinum ;
  • Cochliobolus diseases caused for example by Cochliobolus sativus
  • Colletotrichum diseases caused for example by Colletotrichum lindemuthanium ;
  • Cycloconium diseases caused for example by Cycloconium oleaginum ;
  • Diaporthe diseases caused for example by Diaporthe citri ;
  • Drechslera Syn: Helminthosporium) or Cochliobolus miyabeanus
  • Elsinoe diseases caused for example by Elsinoe fawcettii ;
  • Gloeosporium diseases caused for example by Gloeospo ⁇ um laeticolor ;
  • Glomerella diseases caused for example by Glomerella cingulata ;
  • Guignardia diseases caused for example by Guignardia bidwelli ;
  • Leptosphaeria diseases caused for example by Leptosphaeria maculans ; Leptosphaeria nodorum ;
  • Magnaporthe diseases caused for example by Magnaporthe grisea ;
  • Mycosphaerella diseases caused for example by Mycosphaerella graminicola ;
  • Mycosphaerella fi ⁇ ensis ;
  • Phaeosphaeria diseases caused for example by Phaeosphae ⁇ a nodorum ;
  • Pyrenophora diseases caused for example by Pyrenophora teres ; Ramularia diseases, caused for example by Ramularia collo-cygni ; Rhynchosporium diseases, caused for example by Rhynchosporium secalis ; Septoria diseases, caused for example by Septoria apii or Septoria lycopercisi ; Typhula diseases, caused for example by Typhula incarnata ; Venturia diseases, caused for example by Venturia inaequalis ;
  • Root and stem diseases such as :
  • Corticium diseases caused for example by Corticium graminearum ;
  • Fusarium diseases caused for example by Fusa ⁇ um oxysporum ;
  • Gaeumannomyces diseases caused for example by Gaeumannomyces graminis ;
  • Rhizoctonia diseases caused for example by Rhizoctonia solani ;
  • Sarocladium diseases caused for example by Sarocladium oryzae;
  • Sclerotium diseases caused for example by Sclerotium oryzae
  • Tapesia diseases caused for example by Tapesia acuformis ;
  • Thielavbpsis diseases caused for example by Thielaviopsis basicola ; • Ear and panicle diseases including maize cob, such as :
  • Alternaria diseases caused for example by Alternaria spp. ;
  • Aspergillus diseases caused for example by Aspergillus flavus ;
  • Cladosporium diseases caused for example by Cladosporium spp. ;
  • Claviceps diseases caused for example by Claviceps purpurea ; Fusarium diseases, caused for example by Fusarium culmorum ;
  • Gibberella diseases caused for example by Gibberella zeae ;
  • Monographella diseases caused for example by Monographella nivalis ;
  • Sphacelotheca diseases caused for example by Sphacelotheca reiliana ;
  • Tilletia diseases caused for example by Tilletia caries ;
  • Urocystis diseases caused for example by Urocystis occulta
  • Ustilago diseases caused for example by Ustilago nuda ;
  • Fruit rot and mould diseases such as : Aspergillus diseases, caused for example by Aspergillus flavus ; Botrytis d iseases, caused for example by Botrytis cinerea ;
  • Penicillium diseases caused for example by Penicillium expansum ;
  • Rhizopus diseases caused by example by Rhizopus stolonifer
  • Sclerotinia diseases caused for example by Sclerotinia sclerotiorum ;
  • Verticilium diseases caused for example by Verticilium alboatrum ; • Seed and soil borne decay, mould, wilt, rot and dampingoff diseases such as :
  • Aphanomyces diseases caused for example by Aphanomyces euteiches
  • Ascochyta diseases caused for example by Ascochyta lentis Aspergillus diseases, caused for example by Aspergillus flavus
  • Cladosporium diseases caused for example by Cladosporium herbarum
  • Cochliobolus diseases caused for example by Cochliobolus sativus
  • Fusarium diseases caused for example by Fusa ⁇ um culmorum
  • Gibberella diseases caused for example by Gibberella zeae
  • Macrophomina diseases caused for example by Macrophomina phaseolina
  • Monographella diseases caused for example by Monographella nivalis
  • Penicillium diseases caused for example by Penicillium expansum
  • Phoma diseases caused for example by Phoma lingam
  • Phomopsis diseases caused for example by Phomopsis sojae
  • Phytophthora diseases caused for example by Phytophthora cactorum
  • Pyrenophora diseases caused for example by Pyrenophora graminea Pyricularia diseases, caused for example by Pyricularia oryzae;
  • Pythium diseases caused for example by Pythium ultimum
  • Rhizoctonia diseases caused for example by Rhizoctonia solani;
  • Rhizopus diseases caused for example by Rhizopus oryzae
  • Sclerotium diseases caused for example by Sclerotium rolfsii
  • Septoria diseases caused for example by Septoria nodorum
  • Typhula diseases caused for example by Typhula incarnata
  • Verticillium diseases caused for example by Verticillium dahliae ;
  • Nectria diseases caused for example by Nectria galligena
  • Blightdiseases such as :
  • Monilinia diseases caused for example by Monilinia laxa ;
  • Leaf blister or leaf curl diseases such as :
  • Taphrina diseases caused for example by Taphrina deformans ; • Decline diseases of wooden plants such as :
  • Esca diseases caused for example by Phaemoniella clamydospora, Phaeomoniella clamydospora,
  • Eutypa dyeback caused for example by Eutypa lata ;
  • Botrytis diseases caused for example by Botrytis cinerea ;
  • Rhizoctonia diseases caused for example by Rhizoctonia solani
  • Helminthosporium diseases caused for example by Helminthospohum solani.
  • Rhizoctonia diseases caused for example by Rhizoctonia solani ;
  • Helminthosporium diseases caused for example by Helminthospohum solani ;
  • Plasmodiophora diseases caused for example by Plamodiophora brassicae ;
  • Bacterial Organisms such as Xanthomanas species for example Xanthomonas campest ⁇ s pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans;
  • Erwinia species for example Erwinia amylovora.
  • the active compounds of the invention in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and/or for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development.
  • the abovementioned pests include:
  • Anoplura for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
  • Acarus siro Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus lat
  • Gastropoda From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
  • helminths from the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Lo
  • Hymenoptera From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Mono- morium pharaonis, Vespa spp.
  • Isopoda for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
  • Orthoptera for example, Acheta domesticus, Blatta orientalis, Blattella germanba, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
  • Siphonaptera for example, Ceratophyllus spp., Xenopsylla cheopis.
  • Symphyla for example, Scutigerella immaculata.
  • Thysanoptera From the order of the Thysanoptera, for example, Basothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
  • Thysanura for example, Lepisma saccharina.
  • the phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.
  • the compounds according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
  • fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
  • the active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ecto- and endoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas.
  • animal parasites ecto- and endoparasites
  • ecto- and endoparasites such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas.
  • parasites include:
  • Anoplurida for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
  • Nematocerina and Brachycerina for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Glossina spp., Chrysomyia s
  • Siphonaptrida From the order of the Siphonaptrida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
  • Actinedida Prostigmata
  • Acaridida Acaridida
  • 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., Laminosioptes spp.
  • the active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice.
  • arthropods By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.
  • the active compounds according to the invention are used in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
  • enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories
  • parenteral administration such as
  • the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10 000-fold dilution, or they can be used as a chemical bath.
  • the compounds according to the invention also have a strong insecticidal action against insects which destroy industrial materials.
  • insects may be mentioned as examples and as preferred - but without any limitation: Beetles, such as Hylotrupes b Camillus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
  • Hymenopterons such as Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
  • Termites such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Bristletails, such as Lepisma saccharina.
  • Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plasties, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions.
  • M+1 means the molecular ion peak, plus 1 am.u. (atomic mass unit), as observed in mass spectroscopy.
  • R-Groups For all other chiral R-Groups we define: The stereochemistry of the R-group ist the stereochemistry of a virtual compound, which we generate by 5 combination of the RGroup with 1.S. ⁇ -triazine ⁇ -carboxylic acid at position 2 of the triazinecarboxylic acid.
  • M+H means the molecular ion peak, plus or minus 1 a.m.u. (atomb mass unit) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy Molecular Weight measurement, Method:
  • Example A In vivo protective test on Venturia inaepualis in apples Solvent 24,5 parts by weight of acetone
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are then placed in a greenhouse at approximately 21 0 C and a relative atmospheric humidity of approximately 90 %.
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of IOOppm of active ingredient: Examples Nr.
  • Example C In vivo protective test on Sphaerotheca fuliginea. in cucumber Solvent 49 parts by weight of N, N - Dimethylformamide
  • Emulsifier 1 part by weight of Alkylarylpolyglycolether
  • a suitable preparation of active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • young plants are sprayed with the preparation of active compound at the stated rate of application.
  • the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. Then the plants are placed in a greenhouse at approximately 23 0 C and a relative atmospheric humidity of approximately 70 %.
  • the test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • Example D In vivo protective test on Leptosphaeria nodorum. in wheat
  • Solvent 50 parts by weight of n,n-dinnethylacetannid Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • the plants are placed in a greenhouse at a temperature of approximately 15 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • Example E In vivo protective test on Pyrenophora teres, in barley
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound or the compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the plants are placed in a greenhouse at a temperature of approximately 2O 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of IOOOppm of active ingredient: Examples Nr.
  • Example F In vivo protective test on Pyricularia oryzae. in rice
  • Emulsifier 1 5 parts by weight of polyoxyethylene alkyl phenyl ether
  • 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • the test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • the following compounds according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient: Examples Nr.
  • Example G In vivo protective test on Rhizoctonia solani. in rice
  • Emulsifier 1 5 parts by weight of polyoxyethylene alkyl phenyl ether
  • 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • Example H In vivo protective test on Cochliobolus miyabeanus. in rice Solvent 28,5 parts by weight of acetone
  • Emulsifier 1 5 parts by weight of polyoxyethylene alkyl phenyl ether
  • Example I In vivo protective test on Phakopsora pachyrhizi. in rice Solvent 28,5 parts by weight of acetone
  • Emulsifier 1 5 parts by weight of polyoxyethylene alkyl phenyl ether
  • active compound 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • solvent and emulsifier 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • young plants are sprayed with the preparation of active compound at the stated rate of application.
  • the plants are inoculated with an aqueous spore suspension of the causal agent of soybean rust Phakopsora pachyrhizi.
  • the plants are then placed in a greenhouse at approximately 2O 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
  • the following compounds according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient: Examples Nr. 1 , 267, 1771 , 1959, 1987, 2009, and 2026.
  • test compound Approximately 20 -30 (Lucilia cuprina larvae) are transferred into a test tube containing 1cm 3 of minced horse meat and 0.5 ml aqueous dilution of test compound.
  • Example K Boophilus microplus - test (BOOPMI Injection) Solvent: dimethyl sulfoxide
  • active compound 10 mg are dissolved in 0.5 ml solvent, and the concentrate is diluted with solvent to the desired concentration.
  • Five adult engorged female ticks (Boophilus microplus) are injected with compound solution into the abdomen. Ticks are transferred into replica plates and incubated in a climate chamber for a period of time. Egg deposition of fertile eggs is monitored.
  • Example L Mvzus persicae - test; (MYZUPE spray application)
  • Emulsifier 0.5 parts by weight alkylarylpolyglycolether
  • active compound 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Example M Phaedon cochleariae - test; (PHAECO spray application) Solvent: 78.0 parts by weight of acetone
  • Emulsifier 0.5 parts by weight alkylarylpolyglycolether
  • a suitable preparation of the active compound 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is dilutes with emulsifier-containing water to the desired concentration.
  • Maize (Zeaaria) leaf sections are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf sections are infested with fall armyworm larvae (Spodoptera frugiperda).
  • Example O Tetranvchus urticae - test: OP-resistant (TETRUR spray application) Solvent: 78.0 parts by weight acetone 1.5 parts by weight dimethylformamide
  • Emulsifier 0.5 parts by weight alkylarylpolyglycolether
  • a suitable preparation of active compound 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with emulsifier- containing water to the desired concentration .Vessels are filled with sand, a solution of the active ingredient, a suspension containing eggs and larvae of Meloidogyne incognita and salad seeds. The salad seeds germinate and the seedlings grow. Galls develop in the roots. After 14 days the nematicidal activity is determined on the basis of the percentage of gall formation. 100% means that no galls were found; 0% means that the number of galls found on the roots of the treated plants was equal to that in untreated control plants. In this test for example, the following compounds from the preparation examples showed 90 % activity at application rate of 20 ppm: Ex no : 1764
  • Example Q Mvzus-Test; oral (MYZUPE O) Solvent: 80.0 parts by weight of acetone
  • active compound 1 part by weight of active compound ist mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration.
  • Containers are infested with a mixed population of the green peach aphid (Myzus persicae), the aphids suck on a preparation of the active compound at the desired concentration.

Abstract

The present invention relates to aminothiazole derivatives of formula (I), their process of preparation, preparation intermediate compounds, their use as fungicide, acaricide or insecticide active agents, particularly in the form of fungicide, acaricide or insecticide compositions and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions. Formula (I) wherein R1 to R5 represent various substituents as described in the description.

Description

FUNGICIDE AMINOTHIAZOLE DERIVATIVES
DESCRIPTION
The present invention relates to aminothiazole derivatives, their process of preparation, preparation intermediate compounds, their use as fungicide, acaricide and/or insecticide active agents, particularly in the form of fungicide, acaricide and/or insecticide compositions and methods for the control of phytopathogenic fungi, or of insects, using these compounds or compositions.
In international patent application WO-2003/059881 there are disclosed certain pharmaceutically active oligopeptide derivatives that can include the following chemical moiety:
Figure imgf000003_0001
These derivatives are reported as being to interact with DNA minor groove. These compounds do not form part of the present invention.
In international patent application WO-2007/051560 there are disclosed certain insecticide 2- acylaminothiazole-4-carboxamide derivatives of the following structure :
Figure imgf000003_0002
wherein R4 can represent a group CO-C. These compounds do not form part of the present invention.
Boularand et al, in Chimica therapeutica (1973), 8(6), 638-46, disclose a compound 10 useful as growth inhibiting agent in Lepidinium sativum development. This compound does not fall within the scope of the present invention.
It is always of high-interest in agriculture to use novel pesticide compounds in order to avoid or to control the development of resistant strains to the active ingredients. It is also of high-interest to use novel compounds being more active than those already known, with the aim of decreasing the amounts of active compound to be used, whilst at the same time maintaining effectiveness at least equivalent to the already known compounds. We have now found a new family of compounds which possess the above mentioned effects or advantages.
Accordingly, the present invention provides aminothiazole derivatives of formula (I)
Figure imgf000004_0001
(I) wherein • R1, R2 and R3 independently represent hydrogen, a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-CrC8-alkyl, a substituted or non-substituted C3- C8-cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8- alkenyl, C3-C8-cycloalkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non- substituted (hydroxyiminoJ-CrCβ-alkyl group, a substituted or non-substituted (C1-C6- alkoxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-C1-C6-alkyl, a substituted or non-substituted (CrCe-alkynyloxyiminoJ-CrCβ-alkyl, a substituted or non- substituted (benzyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted aryl-[ CrC8]-alkyl, a substituted or non-substituted CrC8-alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted C1-C8- alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)- imidoyl, a substituted or non-substituted aryl-amino-(n-alkyl)-imidoyl, a substituted or non- substituted aryl-amino-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(n- alkyl)-imidoyl, a substituted or non-substituted CrCs-alkyl-amino^n-alkoxyJ-imidoyl, a substituted or non-substituted CrCs-alkoxy^n-alkylJ-imidoyl, a substituted or non-substituted CrC8-alkoxy-(n- alkoxy)-imidoyl, a substituted or non-substituted CrC8-aryloxy-(n-alkyl)-imidoyl, a substituted or non-substituted C1-C8-aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-thioalkyl- imidoyl, a substituted or non-substituted thioaryl-imidoyl, a substituted or non-substituted C1-C8- alkyl-carbonyl, a substituted or non-substituted CrCs-halogenoalkyl-carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, amino-carbonyl, hydrazino- carbonyl, a substituted or non-substituted aryl-amino-carbonyl, a substituted or non-substituted CrCs-alkyl-carbamoyl, a substituted or non-substituted CrCs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-carbonyl, a substituted or non- substituted CrC8-alkoxy-carbonyl, a substituted or non-substituted CrCs-thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted CrC8-alkyl- thiocarbonyl, a substituted or non-substituted CrCVhalogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino- thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non-substituted CrC8-alkoxy-carbamothioyl, a substituted or non-substituted CrC8-alkyl- hydrazino-thiocarbonyl, a substituted or non-substituted CrCs-alkyl-carbamothioyl, a substituted or non-substituted CrCVhalogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, hydroxy- thiocarbonyl, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non- substituted CrCs-alkoxy-thiocarbonyl, a substituted or non-substituted CrC8-thioalkyl- thiocarbonyl, a substituted or non-substituted thioaryl-thiocarbonyl, cyano, a substituted or non- substituted CrC8-alkyl-amino, a substituted or non-substituted di-CrC8-alkyl-amino, a substituted or non-substituted CrCs-halogenoalkyl-amino, a substituted or non-substituted di-CrC8- halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl -amino, amino-carbonyl-amino, formyl-amino, a substituted or non-substituted aryl-amino- carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non- substituted Ci-C8-alkyl-carbamoyl-amino, a substituted or non-substituted CrC8-alkyl-carbonyl- amino, amino-thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted C1-C8- alkoxy-thiocarbonyl-amino, a substituted or non-substituted CrCs-alkylamino-thiocarbonyl-amino, a substituted or non-substituted CrC8-alkyl-thiocarbonyl-amino, amino, a substituted or non- substituted aryl-hydrazino, a substituted or non-substituted CrC8-alkyl-hydrazino, hydroxy-amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted CrC8-alkoxy- amino, a substituted or non-substituted alkyl-sulphenyl-amino, a substituted or non-substituted aryl-sulphenyl-amino, a substituted or non-substituted CrC8-alkyl-amino-silyl, a substituted or non-substituted di-CrC8-alkyl-amino-silyl, a substituted or non-substituted alkyl-sulphinyl-amino, a substituted or non-substituted aryl-sulphinyl-amino, amino-sulphinyl-amino, a substituted or non- substituted Ci-C8-alkoxy-sulfonyl-amino, hydroxy-sulfonyl-amino, a substituted or non-substituted aryloxy-sulfonyl-amino, amino-sulfonyl-amino, a substituted or non-substituted arylamino-sulfonyl- amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non-substituted C1- C8-alkylamino-sulfonyl-amino, a substituted or non-substituted CrC8-alkyl-sulfonyl-amino, nitro, nitroso, a substituted or non-substituted CrC8-alkyl-oxy, a substituted or non-substituted C1-C8- alkyl-oxyalkyl-oxy, a substituted or non-substituted CrC8-halogenoalkyl-oxy, a substituted or non- substituted aryl-oxy, formamidino-oxy, amino-carbonyl-oxy, formyl-oxy, a substituted or non- substituted aryl-carbonyl-oxy, a substituted or non-substituted CrCs-alkyl-carbonyl-oxy, hydroxy- thiocarbonyl-oxy, a substituted or non-substituted aryl-thiocarbonyl-oxy, a substituted or non- substituted CrCValkyl-thiocarbonyl-oxy, hydroxy, amino-oxy, a substituted or non-substituted aryl-amino-oxy, a substituted or non-substituted CrCs-alkyl-amino-oxy, a substituted or non- substituted aryl-silyloxy, a substituted or non-substituted CrCValkyl-silyloxy, , a substituted or non-substituted CrCValkyl-sulfonyl-oxy, a substituted or non-substituted CrC8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, thiol, a substituted or non-substituted CrC8-alkyl- silyl, a substituted or non-substituted CrC8-alkyl-sulphinyl, a substituted or non-substituted aryl- sulphinyl, a substituted or non-substituted CrC8-alkyl-sulphonyl, a substituted or non-substituted CrCs-halogenoalkyl-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl- sulphonyl, amino-sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-amino- sulphonyl, a substituted or non-substituted CrCValkyl-hydrazino-sulfonyl, a substituted or non- substituted CrCs-alkyl-amino-sulphonyl, a substituted or non-substituted CrC8-halogenoalkyl- amino-sulphonyl having 1 to 5 halogen atoms, hydroxy-sulphonyl, a substituted or non-substituted aryloxy-sulphonyl, a substituted or non-substituted CrC8-alkoxy-sulphonyl, halogen, a group selected in the list consisting of A1 to A68
Figure imgf000006_0001
Figure imgf000007_0001
Figure imgf000008_0001
o wherein Z1, Z2, Z3, Z4, Z5 and Z6 independently represent a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tr^CrCValkylJsilyl-CrCs-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3-C8- cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non -substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2- C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (CrCe-alkoxyiminoJ-CrCβ-alkyl, a substituted or non-substituted (C2-C6- alkenyloxyimino)-CrC6-alkyl, a substituted or non-substituted
Figure imgf000009_0001
C6-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC6-alkyl, a substituted or non- substituted aryl-[ CrC8]-alkyl, a substituted or non-substituted CrC8-alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8-alkyl-(n-alkoxy)-imidoyl, a substituted or non- substituted aryl-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non- substituted aryl-amino-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-amino-(n- alkoxy)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(n-alkyl)-imidoyl, a substituted or non-substituted CrCs-alkyl-amino^n-alkoxyJ-imidoyl, hydroxy-(n-alkyl)- imidoyl, hydroxy-(n-alkoxy)-imidoyl, a substituted or non-substituted C1-C8-alkoxy-(n-alkyl)- imidoyl, a substituted or non-substituted C1-C8-alkoxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-aryloxy-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8- aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, a substituted or non-substituted CrC8-alkyl- carbonyl, a substituted or non-substituted CrCs-halogenoalkyl-carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, amino-carbonyl, hydrazino-carbonyl, N-hydroxy-carbamoyl, a substituted or non-substituted aryl-amino- carbonyl, a substituted or non-substituted aryl-hydrazino-carbonyl, a substituted or non- substituted CrC8-alkyl-hydrazino-carbonyl, a substituted or non-substituted CrC8-alkyl- carbamoyl, a substituted or non-substituted CrCs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, hydroxy-carbonyl , a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted CrC8-alkoxy-carbonyl, a substituted or non-substituted Cr C8-thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted CrC8-alkyl-thiocarbonyl, a substituted or non-substituted CrC8- halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non-substituted CrC8-alkoxy-carbamothioyl, a substituted or non-substituted CrC8-alkyl-hydrazino-thiocarbonyl, a substituted or non- substituted CrC8-alkyl-carbamothioyl, a substituted or non-substituted CrC8-halogenoalkyl- carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy- thiocarbonyl, a substituted or non-substituted CrC8-alkoxy-thiocarbonyl, a substituted or non-substituted CrC8-thioalkyl-thiocarbonyl, a substituted or non-substituted thioaryl- thiocarbonyl, cyano, hydrogen, a substituted or non-substituted CrC8-alkyl-amino, a substituted or non-substituted di-CrCs-alkyl-amino, a substituted or non-substituted C1-C8- halogenoalkyl-amino, a substituted or non-substituted di-CrCs-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl-amino, a substituted or non-substituted aryl-(n-alkyl)-imidoyl-amino, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl-amino, a substituted or non-substituted C1-C8-alkyl-(n-alkyl)-imidoyl- amino, a substituted or non-substituted CrC8-alkyl-(n-alkoxy)-imidoyl-amino, amino- carbonyl-amino, formyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted aryloxy-carbonyl-amino, a substituted or non-substituted C1- C8-alkoxy-carbonyl-amino, a substituted or non-substituted CrCs-alkyl-carbonyl-amino, amino-thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted CrCs-alkoxy-thiocarbonyl-amino, a substituted or non-substituted CrCs-alkylamino- thiocarbonyl-amino, a substituted or non-substituted CrCs-alkyl-thiocarbonyl-amino, amino, hydrazino, a substituted or non-substituted aryl-hydrazino, a substituted or non-substituted
CrC8-alkyl-hydrazino, hydroxy-amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted CrC8-alkoxy-amino, a substituted or non-substituted alkyl- sulphenyl-amino, a substituted or non-substituted aryl-sulphenyl-amino, a substituted or non-substituted CrCs-alkyl-amino-silyl, a substituted or non-substituted di-CrC8-alkyl- amino-silyl, amino-sulphinyl-amino, a substituted or non-substituted alkyl-sulphinyl-amino, a substituted or non-substituted aryl-sulphinyl-amino, amino-sulfonyl-amino, hydroxy-sulfonyl- amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non- substituted aryloxy-sulfonyl-amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non-substituted CrCs-alkoxy-sulfonyl-amino, a substituted or non-substituted CrCs-alkyl-sulfonyl-amino, nitro, nitroso, a substituted or non-substituted CrC8-alkyl-oxy, a substituted or non-substituted CrC8-alkyl-oxyalkyl-oxy, a substituted or non-substituted C1- C8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, a substituted or non- substituted aryl-(n-alkyl)-imidoyl-oxy, a substituted or non-substituted aryl-(n-alkoxy)- imidoyl-oxy, a substituted or non-substituted CrC8-(n-alkyl)-alkyl-imidoyl-oxy, a substituted or non-substituted CrC8-(n-alkoxy)-alkyl-imidoyl-oxy, formyl-oxy, a substituted or non- substituted aryl-carbonyl-oxy, a substituted or non-substituted CrCs-alkyl-carbonyl-oxy, hydroxy, amino-oxy, a substituted or non-substituted aryl-amino-oxy, a substituted or non- substituted CrC8-alkyl-amino-oxy, a substituted or non-substituted aryl-silyloxy, a substituted or non-substituted CrC8-alkyl-silyloxy, amino-sulphonyl-oxy, a substituted or non-substituted arylamino-sulphonyl-oxy, a substituted or non-substituted aryl-sulphonyl- oxy, a substituted or non-substituted CrCs-alkylamino-sulphonyl-oxy, a substituted or non- substituted CrCs-alkyl-sulfonyl-oxy, a substituted or non-substituted CrC8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, thiol, a substituted or non-substituted C1-C8- alkyl-silyl, a substituted or non-substituted CrCs-alkyl-sulphinyl, a substituted or non- substituted aryl-sulphinyl, a substituted or non-substituted CrCValkyl-sulphonyl, a substituted or non-substituted CrCs-halogenoalkyl-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non-substituted aryl- hydrazino-sulfonyl, a substituted or non-substituted CrC8-alkyl-amino-sulfamoyl, a substituted or non-substituted CrCs-alkyl-hydrazino-sulfonyl, a substituted or non- substituted CrCs-alkyl-amino-sulphonyl, a substituted or non-substituted C1-C8- halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, hydroxy-sulphonyl, a substituted or non-substituted aryloxy-sulphonyl, a substituted or non-substituted C1-C8- alkoxy-sulphonyl, halogen; K1 and K2 independently represent a hydrogen atom, a formyl group, a substituted or non- substituted carbaldehyde O-(CrC8-alkyl)oxime, a carbamoyl group, a N-hydroxycarbamoyl group, a formylamino group, a substituted or non-substituted CτC8-alkyl, a substituted or non-substituted tri(C1-C8-alkyl)silyl-C1-C8-alkyl, a substituted or non-substituted C3-C8- cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a C2- C8-alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted CrCs-alkylamino, a substituted or non-substituted di-CrC8-alkylamino, a substituted or non-substituted CrCs-alkoxy, a substituted or non-substituted CrCs-halogenoalkoxy having 1 to 5 halogen atoms, a substituted or non-substituted C2-C8-alkenyloxy, a substituted or non-substituted C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms, a substituted or non-substituted C2-C8-alkynyloxy, a substituted or non-substituted C2-C8- halogenoalkynyloxy having 1 to 5 halogen atoms, a substituted or non-substituted C1-C8- alkylcarbonyl, a substituted or non-substituted N-(C1-C8-alkoxy)-C1-C8-alkanimidoyl, a substituted or non-substituted N-(C1-C8-alkoxy)-C1-C8-halogenoalkanimidoyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkylcarbamoyl, a substituted or non- substituted di-CrC8-alkylcarbamoyl, a substituted or non-substituted N-C1-C8- alkyloxycarbamoyl, a substituted or non-substituted CrCs-alkoxycarbamoyl, a substituted or non-substituted N-CrCs-alkyl-CrCs-alkoxycarbamoyl, a substituted or non-substituted CrCs-alkoxycarbonyl, a substituted or non-substituted CrCs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkylcarbamothioyl, a substituted or non-substituted di-CrCs-alkylcarbamothioyl, a substituted or non-substituted N-CrCs-alkyloxycarbamothioyll, a substituted or non-substituted C1-C8- alkoxycarbamothioyl, a substituted or non-substituted N-C-i-Cs-alkyl-C-i-Cs- alkoxycarbamothioyl, a substituted or non-substituted CrC8-alkylsulphinyl, a substituted or non-substituted CrCVhalogenoalkylsulphinyl having 1 to 5 halogen atoms, a substituted or non-substituted CrCs-alkylsulphonyl, a substituted or non-substituted CrC8-halogenoalkyl- sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted C1-C8- alkylaminosulfamoyl, a substituted or non-substituted di-CrCs-alkylaminosulfamoyl, a substituted or non-substituted aryl, a substituted or non-substituted aryl-[ CrC8]-alkyl ; provided that R3 does not represent hydrogen and provided that R1 and R2 do not simultaneously represent hydrogen ; R4 and R5 independently represent a substituted or non-substituted CrC8-alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- (n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, hydrazino- imidoyl, a substituted or non-substituted aryl-hydrazino-imidoyl, a substituted or non-substituted CrC8-alkyl-hydrazino-imidoyl, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-amino-(n- alkoxy)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(n-alkyl)-imidoyl, a substituted or non-substituted CrCs-alkyl-amino^n-alkoxyJ-imidoyl, hydroxy-(n-alkyl)-imidoyl, hydroxy-(n- alkoxy)-imidoyl, a substituted or non-substituted C1-C8-alkoxy-(n-alkyl)-imidoyl, a substituted or non-substituted C1-C8-alkoxy-(n-alkoxy)-imidoyl, a substituted or non-substituted C1-C8-aryloxy-(n- alkyl)-imidoyl, a substituted or non-substituted C1-C8-aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, formyl, amino-carbonyl, hydrazino-carbonyl, a substituted or non-substituted aryl-amino-carbonyl, N- hydroxy-carbamoyl, a substituted or non-substituted aryl-hydrazino-carbonyl, a substituted or non- substituted aryloxy-carbamoyl, a substituted or non-substituted CrC8-alkoxy-carbamoyl, a substituted or non-substituted CrCs-alkyl-hydrazino-carbonyl, a substituted or non-substituted C1- C8-alkyl-carbamoyl, a substituted or non-substituted CrCs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted
CrCs-alkoxy-carbonyl, a substituted or non-substituted CrCs-thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted CrCs-alkyl-thiocarbonyl, a substituted or non-substituted CrCs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino- thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non- substituted CrCs-alkoxy-carbamothioyl, a substituted or non-substituted CrC8-alkyl-hydrazino- thiocarbonyl, a substituted or non-substituted CrCs-alkyl-carbamothioyl, a substituted or non- substituted CrCs-halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, a substituted or non- substituted aryloxy-thiocarbonyl, a substituted or non-substituted CrCs-alkoxy-thiocarbonyl, a substituted or non-substituted CrCs-thioalkyl-thiocarbonyl, a substituted or non-substituted thioaryl-thiocarbonyl, cyano, hydrogen, a substituted or non-substituted CrCs-alkyl-amino, a substituted or non-substituted di-CrC8-alkyl-amino, a substituted or non-substituted C1-C8- halogenoalkyl-amino, a substituted or non-substituted di-CrCs-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl -amino, amino-carbonyl- amino, formyl-amino, a substituted or non-substituted aryl-amino-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted CrCs-alkyl-carbamoyl- amino, a substituted or non-substituted CrC8-alkyl-carbonyl-amino, hydroxy-carbonyl-amino, amino-thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted C1-C8- alkoxy-thiocarbonyl-amino, a substituted or non-substituted CrCs-alkylamino-thiocarbonyl-amino, a substituted or non-substituted CrCs-alkyl-thiocarbonyl-amino, amino, a substituted or non- substituted aryloxy-amino, a substituted or non-substituted CrC8-alkoxy-amino, amino-sulfonyl- amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non-substituted CrCs-alkylamino-sulfonyl-amino, a substituted or non-substituted CrCs-alkyl-sulfonyl-amino, a substituted or non-substituted C1-C8- alkyl-oxy, a substituted or non-substituted CrCs-alkyl-oxyalkyl-oxy, a substituted or non- substituted CrC8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, formamidino-oxy, amino-carbonyl-oxy, formyl-oxy, a substituted or non-substituted aryl-carbonyl-oxy, a substituted or non-substituted CrC8-alkyl-carbonyl-oxy, hydrazino-carbonyl-oxy, a substituted or non- substituted aryl-amino-carbonyl-oxy, a substituted or non-substituted aryloxy-carbonyl-oxy, a substituted or non-substituted CrCs-alkoxy-carbonyl-oxy, a substituted or non-substituted C1-C8- alkyl-amino-carbonyl-oxy, a substituted or non-substituted C1-C8-Ih ioalkyl-carbonyl-oxy, a substituted or non-substituted thioaryl-carbonyl-oxy, hydroxy-thiocarbonyl-oxy, a substituted or non-substituted aryl-thiocarbonyl-oxy, a substituted or non-substituted CrCs-alkyl-thiocarbonyl- oxy, amino-thiocarbonyl-oxy, a substituted or non-substituted arylamino-thiocarbonyl-oxy, a substituted or non-substituted aryloxy-thiocarbonyl-oxy, a substituted or non-substituted C1-C8- alkoxy-thiocarbonyl-oxy, a substituted or non-substituted CrC8-alkyl-carbamothioyl-oxy, a substituted or non-substituted CrCs-thioalkyl-thiocarbonyl-oxy, a substituted or non-substituted thioaryl-thiocarbonyl-oxy, hydroxy, a substituted or non-substituted aryl-silyloxy, a substituted or non-substituted CrC8-alkyl-silyloxy, , a substituted or non-substituted CrC8-alkyl-silyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non-substituted CrC8-alkyl-hydrazino-sulfonyl, a substituted or non-substituted aryl- hydrazino-sulfonyl, a substituted or non-substituted CrC8-alkyl-amino-sulfamoyl, a substituted or non-substituted CrCs-alkyl-amino-sulphonyl, a substituted or non-substituted C1-C8- halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, a group independently selected in the list consisting of A1 to A68 as defined for R1, R2 or R3 ; provided that at least one of R4 and R5 does not represent hydrogen ; s salts, N-oxides, metallic complexes and metalloid ic complexes thereof. According to the invention, the following generic terms are generally used with the following meanings:
• halogen means fluorine, chlorine, bromine or iodine ;
• heteroatom can represent nitrogen, oxygen or sulphur ;
• unless indicated otherwise, a group or a substituent that is substituted according to the invention can be substituted by one or more of the following groups or atoms: a halogen atom, a nitro group, a hydroxy group, a cyano group, an amino group, a sulphenyl group, a pentafluoro-λ6- sulphenyl group, a formyl group, a substituted or non-substituted carbaldehyde 0-(C1-C8- alkyl)oxime, a formyloxy group, a formylamino group, a carbamoyl group, a N-hydroxycarbamoyl group, a formylamino group, a (hydroxyiminoJ-CrCValkyl group, a CrC8-alkyl, a In(C1-C8- alkyl)silyl-CrC8-alkyl, C3-C8-cycloalkyl, tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a CrC8-halogenoalkyl having 1 to 5 halogen atoms, a C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a C2-C8- alkenyl, a C2-C8-alkynyl, a C2-C8-alkenyloxy, a C2-C8-alkynyloxy, a CrC8-alkylamino, a di-CrC8- alkylamino, a CrC8-alkoxy, a CrC8-halogenoalkoxy having 1 to 5 halogen atoms, a C1-C8- alkylsulphenyl, a CrC8-halogenoalkylsulphenyl having 1 to 5 halogen atoms, a C2-C8-alkenyloxy, a C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms, a C2-C8-alkynyloxy, a C2-C8- halogenoalkynyloxy having 1 to 5 halogen atoms, a CrC8-alkylcarbonyl, a C1-C8- halogenoalkylcarbonyl having 1 to 5 halogen atoms, a CrC8-alkylcarbamoyl, a di-CrC8- alkylcarbamoyl, a N-CrCs-alkyloxycarbamoyl, a CrCs-alkoxycarbamoyl, a N-CrCs-alkyl-CrCs- alkoxycarbamoyl, a CrCs-alkoxycarbonyl, a CrCs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a CrCs-alkylcarbonyloxy, a CrC8-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms, a CrCs-alkylcarbonylamino, a CrCs-halogenoalkylcarbonylamino having 1 to 5 halogen atoms, a CrCs-alkylaminocarbonyloxy, a di-CrCs-alkylaminocarbonyloxy, a CrCs-alkyloxycarbonyloxy, a CrC8-alkylsulphenyl, a CrCs-halogenoalkylsulphenyl having 1 to 5 halogen atoms, a C1-C8- alkylsulphinyl, a CrC8-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a CrC8-alkyl- sulphonyl, a CrCs-halogenoalkylsulphonyl having 1 to 5 halogen atoms, a C1-C8- alkylaminosulfamoyl, a di-CrCs-alkylaminosulfamoyl, a (CrCe-alkoxyiminoJ-CrCβ-alkyl, a (C2-C6- alkenyloxyiminoJ-CrCβ-alkyl, a (C^Ce-alkynyloxyiminoJ-CrCβ-alkyl, (benzyloxyiminoJ-CrCβ-alkyl, CrCs-alkoxyalkyl, CrCs-halogenoalkoxyalkyl having 1 to 5 halogen atoms, benzyloxy, benzylsulphenyl, benzylamino, phenoxy, phenylsulphenyl, or phenylamino; • the term "aryl" means phenyl or naphthyl.
Any of the compounds according to the invention can exist as one or more stereoisomers depending on the number of stereogenic units (as defined by the IUPAC rules) in the compound. The invention thus relates equally to all the stereoisomers and to the mixtures of all the possible stereoisomers, in all proportions. The stereoisomers can be separated according to the methods which are known per se by the man ordinary skilled in the art. Preferred compounds of formula (I) according to the invention are those wherein R1 and R2 independently represent hydrogen, a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tri(Cr Cs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tr^CrCs-alkylJsilyl-Cs-Cs-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (C1-C6- alkoxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-C1-C6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-C1-C6-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC6-alkyl, a substituted or non-substituted aryl-[CrC8]-alkyl, a substituted or non- substituted CrCs-alkyl-carbonyl, a substituted or non-substituted CrCs-halogenoalkyl-carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, a substituted or non-substituted CrCs-alkyl-carbamoyl, a substituted or non-substituted CrCs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkyl-amino, a substituted or non-substituted di-Cr C8-alkyl-amino, a substituted or non-substituted CrCs-halogenoalkyl-amino, a substituted or non- substituted di-CrCs-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl -amino, formyl-amino, a substituted or non-substituted CrCs-Alkyl-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted aryloxy-carbonyl- amino, a substituted or non-substituted CrCs-alkoxy-carbonyl-amino, a substituted or non-substituted C1- C8-alkyl-oxy, a substituted or non-substituted CrCValkyl-oxyalkyl-oxy, a substituted or non-substituted C1- C8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, a substituted or non-substituted C1-C8- alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, a substituted or non-substituted C1-C8- Alkyl-silyl, a substituted or non-substituted CrCs-alkyl-sulphinyl, a substituted or non-substituted aryl- sulphinyl, a substituted or non-substituted CrC8-alkyl-sulphonyl, a substituted or non-substituted C1-C8- halogenoalkyl-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-sulphonyl, a group A1.
More preferred compounds of formula (I) according to the invention are those wherein R1 and R2 independently represent a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tr^CrCs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non- substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8- alkynyl, a substituted or non-substituted (hydroxyiminoJ-CrCβ-alkyl group, a substituted or non-substituted (CrCe-alkoxyiminoJ-CrCβ-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-CrC6-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC6-alkyl, a substituted or non-substituted aryl-[CrC8]-alkyl, hydrogen, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl-amino, a group A1. Even more preferred compounds of formula (I) according to the invention are those wherein R1 and R2 independently represent a substituted or non-substituted alpha substituted benzyl, a substituted or non- substituted alkoxy-aryl, a substituted or non-substituted aryloxy-aryl, hydrogen, substituted or non- substituted cycloalkyl, halogenoalkyl, substituted or non-substituted 2-phenylethyl, substituted or non- substituted alpha substituted alkyl.
Still even more preferred compounds of formula (I) according to the invention are those wherein R1 and R2 independently represent 1-cyclopropylpropan-2-yl; 1-phenylethyl; 2-phenylethyl; 1 -cyclohexylethyl; 1- ethylpropyl; 4-[4-(trifluoromethyl)phenoxy]phenyl; 1-cyclopropylpropan-2-yl; dicyclopropylmethyl; 1- cyclopropylethyl; 1-(4-ethoxyphenyl)ethyl; 1-(4-ethylphenyl)ethyl; 1-(4-methoxyphenyl)ethyl; 1 -[4-(propan- 2-yl)phenyl]ethyl; cyclopentyl; cyclohexyl; 4-methyl-cyclohexyl; 1-(3-methoxyphenyl)ethyl; 2-(4- chlorophenyl)ethyl; 2,2-dimethyl-propyl; 4,4,4-trifluorobutan-2-yl; 1 -cyclopropylpropan-2-yl; 2-methylbutan- 2-yl; 4-methylpentan-2-yl, hydrogen.
More particularly, still even more preferred compounds of formula (I) according to the invention are those wherein one of R1 and R2 represents hydrogen, and the other substituents being selected among the herein-mentioned preferred representations..
Other preferred compounds of formula (I) according to the invention are those wherein R3 represents a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tr^CrCs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3- C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non- substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (CrC6-alkoxyimino)-CrC6- alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-CrC6-alkyl, a substituted or non- substituted (C2-C6-alkynyloxyimino)-CrC6-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC6- alkyl, a substituted or non-substituted aryl-[CrC8]-alkyl, a substituted or non-substituted aryl-carbonyl, cyano, a substituted or non-substituted CrC8-alkyl-amino, a substituted or non-substituted di-CrC8-alkyl- amino, a substituted or non-substituted CrCs-halogenoalkyl-amino, a substituted or non-substituted di-Cr C8-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di- aryl-amino, a substituted or non-substituted CrC8-alkyl-oxy, a substituted or non-substituted CrC8-alkyl- oxyalkyl-oxy, a substituted or non-substituted CrC8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, hydroxy, a substituted or non-substituted CrC8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, or halogen. Other more preferred compounds of formula (I) according to the invention are those wherein represents R3 represents a substituted or non-substituted CrC4-alkyl, a substituted or non-substituted tri(CrC4- alkyl)silyl-CrC4-alkyl, a substituted or non-substituted C3-C4-cycloalkyl, a substituted or non-substituted tnXCrQ-alkylJsilyl-Cs-C^cycloalkyl, a substituted or non-substituted CrC4-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C4-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC4-alkyl group, a substituted or non-substituted (CrC4- alkoxyimino)-CrC4-alkyl, a substituted or non-substituted (C2-C4-alkenyloxyimino)-CrC4-alkyl, a substituted or non-substituted (C2-C4-alkynyloxyimino)-CrC4-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC4-alkyl, a substituted or non-substituted aryl-[CrC4]-alkyl, halogen.
Other even more preferred compounds of formula (I) according to the invention are those wherein R3 represents F, Cl, Br, I, in particular Br; a substituted or non-substituted CrC4-alkyl in particular methyl, C2- C8-alkynyl in particular ethynyl, CF3, cyclopropyl, benzyl.
Other preferred compounds of formula (I) according to the invention are those wherein R4 and R5 independently represent a substituted or non-substituted CrC8-alkyl-(N-alkyl)-imidoyl, a substituted or non-substituted CrC8-alkyl-(N-alkoxy)-imidoyl, a substituted or non-substituted aryl-(N-alkyl)-imidoyl, a substituted or non-substituted aryl-(N-alkoxy)-imidoyl, formamidino, amino-(N-alkyl)-imidoyl, amino-(N- alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(N-alkyl)-imidoyl, a substituted or non- substituted aryl-amino-(N-alkoxy)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(N-alkyl)- imidoyl, a substituted or non-substituted C1-C8-alkyl-amino-(N-alkoxy)-imidoyl, hydroxy-(N-alkyl)-imidoyl, hydroxy-(N-alkoxy)-imidoyl, a substituted or non-substituted C1-C8-alkoxy-(N-alkyl)-imidoyl, a substituted or non-substituted CrC8-alkoxy-(N-alkoxy)-imidoyl, a substituted or non-substituted CrC8-aryloxy-(N- alkyl)-imidoyl, a substituted or non-substituted CrC8-aryloxy-(N-alkoxy)-imidoyl, formyl, amino-carbonyl, a substituted or non-substituted aryl-amino-carbonyl, a substituted or non-substituted CrC8-alkyl- carbamoyl, a substituted or non-substituted CrC8-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkoxy-carbonyl, a substituted or non-substituted aryloxy-carbonyl , a substituted or non-substituted CrC8-alkyl-thiocarbonyl, a substituted or non-substituted CrC8- halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl- thiocarbonyl, amino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted CrC8-alkyl-carbamothioyl, a substituted or non-substituted CrC8-halogenoalkyl- carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted CrC8-alkoxy-thiocarbonyl, a substituted or non-substituted CrC8-thioalkyl- thiocarbonyl, a substituted or non-substituted thioaryl-thiocarbonyl, hydrogen, a substituted or non- substituted CrC8-alkyl-amino, a substituted or non-substituted di-CrC8-alkyl-amino, a substituted or non- substituted CrC8-halogenoalkyl-amino, a substituted or non-substituted di-CrC8-halogenoalkyl-amino, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, a substituted or non-substituted aryl- amino-sulphonyl, a substituted or non-substituted CrCValkyl-amino-sulphonyl, a substituted or non- substituted CrCs-halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, a substituted or non- substituted aryloxy-sulphonyl, a substituted or non-substituted CrC8-alkoxy-sulphonyl, hydroxy-sulphonyl, a group selected in the list consisting of A1 to A68.
Other more preferred compounds of formula (I) according to the invention are those wherein R4 and R5 independently represent formyl, hydrogen, a group selected in the list consisting of A1 to A8, in particular a non substituted phenyl or a phenyl, substituted with 1 to 3 fluorine atoms, methyloxy, ethyloxy or trifluoromehtyl.
The above mentioned preferences with regard to the substituents of the compounds of formula (I) according to the invention can be combined in various manners. These combinations of preferred features thus provide sub-classes of compounds according to the invention. Examples of such sub-classes of preferred compounds according to the invention can combine: - preferred features of R1 with preferred features of one or more of R2, R3, R4 and R5; preferred features of R2 with preferred features of one or more of R1, R3, R4 and R5; preferred features of R3 with preferred features of one or more of R1, R2, R4 and R5; preferred features of R4 with preferred features of one or more of R1, R2, R3 and R5; preferred features of R5 with preferred features of one or more of R1, R2, R3 and R4 In these combinations of preferred features of the substituents of the compounds of formula (I) according to the invention, the said preferred features can also be selected among the more preferred features of each of R1, R2, R3, R4 and R5 so as to form most preferred subclasses of compounds according to the invention.
The preferred features of the other substituents of the compounds according to the invention can also be part of such sub-classes of preferred compounds according to the invention, notably the groups of substituents Z1 to Z6 and K1 and K2.
The present invention also relates to a process for the preparation of compounds of formula (I). The process according to the invention can be carried according to the following schemes and reaction conditions. Specific steps and particular conditions can be adapted by the skilled person in order to prepare the compounds of formula (I) according to the invention.
Preparation of 5-methyl-thiazolyl derivatives of formula (I) according to the invention:
Figure imgf000018_0001
Preparation of 5-substituted-thiazolyl derivatives of formula (I) according to the invention:
Figure imgf000019_0001
A) Preparation of N-(4-fluorophenyl)-5-methyl-2-[(4-phenoxyphenyl)aminol-1 ,3-thiazole-4-carboxamide (compound example 103)
Figure imgf000019_0002
Step A.1 : Preparation of the 3-bromo-2-oxobutanoic acid :
Figure imgf000019_0003
2-keto-butyric acid (30 g) is dissolved in chloroform (500 ml) and cooled down to 00C. AIBN (120 mg) is added then bromine (51 ,658 g dropwise). After 1 hour at 00C, the reaction mixture is stirred at room temperature for 20 hours. The solvent is evaporated. The crude product is triturated in pentane (200 ml) and filtered to give 3-bromo-2-oxobutanoic acid (yield: 74%).
Step A.2: Preparation of the 5-methyl-2-[(4-phenoxyphenyl)aminol-1 ,3-thiazole-4-carboxylic acid:
Figure imgf000019_0004
3-bromo-2-oxobutanoic acid (3 g) is dissolved in DMF (40 ml). A solution of 4-phenoxyphenyl thiourea (4,175 g) in DMF (20 ml) is then added. An exothermic behaviour is observed. The reaction mixture is then heated at 80°C for 3 hours. The solvent is evaporated at 80% then poured onto ice water (100 ml). The precipitate is then filtered, washed with water and dried. The crude solid is triturated in a mixture di- isopropyl-ether / AcOEt. The desired compound 5-methyl-2-[(4-phenoxyphenyl)amino]-1 ,3-thiazole-4- carboxylic acid is obtained after filtration and drying (yield: 91 %). Step A.3: Preparation of the N-(4-fluorophenyl)-5-methyl-2-[(4-phenoxyphenyl)aminol-1 ,3-thiazole-4- carboxamide:
Figure imgf000020_0001
5-methyl-2-[(4-phenoxyphenyl)amino]-1 ,3-thiazole-4-carboxylic acid (250 mg) is dissolved in DMF (8 ml). TBTU (245 mg), DIPEA (148,5 mg) and 4-fluoro-aniline (85 mg) are added at room temperature. After stirring at room temperature for 20 hours, AcOEt is added and the organic phase is washed with water, HCI 1 N and dried with MgSO4. After concentration and purification on silica gel chromatography, N-(4- fluorophenyl)-5-methyl-2-[(4-phenoxyphenyl)amino]-1 ,3-thiazole-4-carboxamide is obtained (yield: 62%)
B) Preparation of the 2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide (compound example 177)
Figure imgf000020_0002
Step B.1 : Preparation of the 2-[(tert-butoxycarbonyl)aminol-5-methyl-1 ,3-thiazole-4-carboxylic acid:
Figure imgf000020_0003
3-bromo-2-oxobutanoic acid (20,5 g) is dissolved in DMF (80 ml). Triethylamine (11 ,5 g) is then added dropwise. A solution of N-Boc-thiourea (20 g) in DMF (40 ml) is finally added dropwise. The reaction mixture is stirred at 800C for 3 hours. 4g of 3-bromo-2-oxobutanoic acid and 3 ml of triethylamine are added to complete the reaction. After 2 hours at 800C, the reaction mixture is poured onto ice water and filtered, washed with water, dried with MgSO4.
The crude solid is triturated in lsopropyl ether, filtered and dried to give 2-[(tert-butoxycarbonyl)amino]-5- methyl-1 ,3-thiazole-4-carboxylic acid (yield: 47%).
Step B.2: Preparation of the tert-butyl (4-[(4-fluorophenyl)carbamoyll-5-methyl-1 ,3-thiazol-2-yl)carbamate:
Figure imgf000020_0004
2-[(tert-butoxycarbonyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid (600 mg) is dissolved in DMF (8 ml). TBTU (746 mg) and DIPEA (450 mg) are added at room temperature. After stirring for 15 minutes, 4- fluoro-aniline (258 mg) is added.
After stirring at room temperature for 20 hours, AcOEt is added and the organic phase washed with water, HCI 1 N and dried with MgSO4. After concentration, the crude solid is chromatographed on silica gel to give tert-butyl {4-[(4-fluorophenyl)carbamoyl]-5-methyl-1 ,3-thiazol-2-yl}carbamate (yield: 72%)
Step B.3: Preparation of the 2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide:
Figure imgf000021_0001
tert-butyl {4-[(4-fluorophenyl)carbamoyl]-5-methyl-1 ,3-thiazol-2-yl}carbamate (540 mg) is dissolved in dichloromethane (15 ml). Trifluoroacetic acid (1 ,18 ml) is added at room temperature. After overnight stirring at room temperature, the reaction mixture is concentrated. Water is added onto this crude solid. After raising the pH until 12 with a 30% solution of sodium hydroxide, 3 extractions are performed with AcOEt. The organic phase is dried with MgSO4 and concentrated to give 2-amino-N-(4-fluorophenyl)-5- methyl-1 ,3-thiazole-4-carboxamide (yield: 97%).
Step B.4: Preparation of the 2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide:
Figure imgf000021_0002
2-amino-N-(4-fluorophenyl)-5-methyl-1 ,3-thiazole-4-carboxamide (190 mg) is dissolved in toluene (10 ml). Formb acid (0,285 ml) is added at room temperature. After stirring at reflux for 6 hours, the solvent is concentrated. The crude solid is triturated in ethyl ether and filtrated. After drying, N-(4-fluorophenyl)-2- (formylamino)-5-methyl-1 ,3-thiazole-4-carboxamide is obtained (yield: 69%).
C) Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-5-(trifluoromethyl)-1 ,3-thiazole-4-carboxamide (compound example 639)
Figure imgf000021_0003
Step C.1 : Preparation of the 2-[(3-chlorophenyl)aminol-1 ,3-thiazole-4-carboxylic acid:
Figure imgf000022_0001
3-bromo-2-oxopropanoic acid (5,080 g) is dissolved in DMF (5,5 ml). A solution of 3-chloro-phenyl- thiourea (4,870 g) in DMF (4 ml) is added at room temperature. After stirring at 800C for 1 hour, a precipitate is present in the reaction mixture. After cooling down and adding water, this precipitate is filtered, washed with water, Et20 then dried with MgSO4. The desired compound 2-[(3- chlorophenyl)amino]-1 ,3-thiazole-4-carboxylic acid is obtained (yield: 80%). Step C.2: Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-1 ,3-thiazole-4-carboxamide:
Figure imgf000022_0002
2-[(3-chlorophenyl)amino]-1 ,3-thiazole-4-carboxylic acid (494 mg) is dissolved in DMF (12 ml). HOBt (275 mg), DIPEA (752 mg) then tert-butylamine (142 mg) and 1 ,3-dicyclohexylcarbodiimide (430 mg) are added at room temperature. After overnight stirring at room temperature, the DMF is evaporated. The crude solid is dissolved in AcOEt and washed with LiCI sat., water, NaHCO3 sat. After concentration and drying with MgSO4, N-tert-butyl-2-[(3-chlorophenyl)amino]-1 ,3-thiazole-4-carboxamide is obtained (yield:
88%)
Step C.3: Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-5-iodo-1 ,3-thiazole-4-carboxamide:
Figure imgf000022_0003
N-tert-butyl-2-[(3-chlorophenyl)amino]-1 ,3-thiazole-4-carboxamide (595 mg) is dissolved in DMF (6,2 ml) and cooled down at 00C. NIS (616 mg) is then added (orange coloration). After 15 minutes at 0°C, AcOEt is added and several washes are performed: LiCI sat., water, NaHCO3 sat.. After concentration and drying with MgSO4, N-tert-butyl^-p-chlorophenylJaminoJ-δ-iodo-I .S-thiazole^-carboxamide is obtained
(yield: 95%)
Step C.4: Preparation of the N-tert-butyl-2-[(3-chlorophenyl)aminol-5-(trifluoromethyl)-1 ,3-thiazole-4- carboxamide:
Figure imgf000022_0004
N-tert-butyl^-KS-chlorophenylJaminol-δ-iodo-I .S-thiazole^-carboxamide (191 mg) is dissolved in DMF/NMP 1/1 (0.4 ml). Copper (I) iodide (114 mg) is added at room temperature. A solution of triethyl(trifluoromethyl)silane (2,226 g) and Potassium fluoride (695 mg) in DMF/NMP 1/1 (0,4 ml) is then added to the reaction mixture. After stirring for 20 minutes at 800C and 1 hour at room temperature, AcOEt is added and several washes with NaCI sat. are performed. The organic phase is concentrated and dried with MgSO4. The crude solid is purified by silica gel chromatography to give N- tert-butyl-2-[(3-chlorophenyl)amino]-5-(trifluoromethyl)-1 ,3-thiazole-4-carboxamide (yield: 3,5 %).
D) Preparation of the 5-bromo-2-(formylamino)-N-(3-iodophenyl)-1 ,3-thiazole-4-carboxamide (compound example 731 )
Figure imgf000023_0001
Step D.1 : Preparation of the 2-amino-5-bromo-1 ,3-thiazole-4-carboxylic acid:
Figure imgf000023_0002
2-aminothiazole-4-carboxylic acid (205 mg) is dissolved in DMF (4,6 ml). NBS (253 mg) is added at 00C. After stirring at 00C for 40 minutes, the DMF is evaporated. The crude solid is triturated in AcOEt and filtered. Another trituration in acetone is performed to give, after filtration and drying, the desired compound 2-amino-5-bromo-1 ,3-thiazole-4-carboxylic acid (yield: 48%). Step D.2: Preparation of the 2-amino-5-bromo-N-(3-iodophenyl)-1 ,3-thiazole-4-carboxamide:
Figure imgf000023_0003
2-amino-5-bromo-1 ,3-thiazole-4-carboxylic acid (1 ,129 g) is dissolved in DMF (20 ml). TBTU (1 ,463 g), DIPEA (1 ,178 g) and 3-iodo-aniline (1 ,018 g) are added at room temperature. After overnight stirring at room temperature, DMF is evaporated. The crude solid is dissolved in AcOEt and washed with NaHCO3 sat., water, LiCI sat.. After concentration and drying, a silica gel chromatography gives the desired compound 2-amino-5-bromo-N-(3-iodophenyl)-1 ,3-thiazole-4-carboxamide (yield: 28%). Step D.3: Preparation of the 5-bromo-2-(formylamino)-N-(3-iodophenyl)-1 ,3-thiazole-4<:arboxamide:
Figure imgf000024_0001
2-amino-5-bromo-N-(3-iodophenyl)-1 ,3-thiazole-4-carboxamide (252 mg) is dissolved in toluene (6,7 ml). Formb acid (0,322 ml) is added at room temperature. After stirring at reflux for 10 hours, toluene is evaporated. The crude solid is dissolved in AcOEt. The organic phase is washed with water, NaHCO3 sat., dried with MgSO4 and concentrated. Dichloromethane is added and the remaining insoluble impurities are filtered out. After evaporation of dichloromethane, 5-bromo-2-(formylamino)-N-(3- iodophenyl)-1 ,3-thiazole-4-carboxamide is obtained (yield: 30%).
E) Preparation of 2-anilino-5-ethvnyl-N-(1-phenylethyl)-1 ,3-thiazole-4-carboxamide (compound example 2726)
Figure imgf000024_0002
Step E.1 : Preparation of 2-anilino-5-iodo-N-(1 -phenylethyl)-1 ,3-thiazole-4-carboxamide (compound example 722):
Figure imgf000024_0003
2-Anilino-N-(1-phenylethyl)-1 ,3-thiazole-4-carboxamide (4.85 g) is dissolved in DMF (75 ml). NIS (4.05 g) is added at 200C. After stirring at 500C for 60 minutes the mixture is cooled down and 400 ml of AcOEt and 400 ml of water is added. The organic layer is separated and dryed with magnesium chloride. After filtration and the removal of the solvent under reduced pressure the crude product is chromatographed on silica gel by using AcOEt / cyclohexane 1 :1 to give the desired compound 2-anilino-5-iodo-N-(1-phenyl- ethyl)-1 ,3-thiazole-4-carboxamide (yield: 54%).
Step E.2: Preparation of 2-anilino-N-(1-phenylethvπ-5-[(trimethylsilvπethvnyll-1 ,3-thiazole-4-carboxamide (compound example 2735):
Figure imgf000025_0001
2-Anilino-5-iodo-N-(1 -phenylethyl)-1 ,3-thiazole-4-carboxamide (1 .2O g) is dissolved in DMF (25 ml). Ethinyl-trimethylsilan (253 mg), Triethylamin (0.51 g), copper(l) iodide (10 mg) and Bis-triphenylphosphin- palladium-dichloride (35 mg) is added at 200C. After stirring at 600C for 90 minutes the mixture is cooled down and 200 ml of AcOEt and 50 ml of saturated sodium chloride solution is added. The pH of the mixture is set to 3 by using 1 N hydrochloric acid. The organic layer is separated, washed with saturated sodium bicarbonate solution, water, saturated sodium chloride solution and dryed with magnesium chloride. After filtration and the removal of the solvent under reduced pressure the crude product is chromatographed on silica gel by using AcOEt / cyclohexane 1 :1 to give the desired compound 2-anilino- N-(1-phenylethyl)-5-[(trimethylsilyl)ethynyl]-1 ,3-thiazole-4-carboxamide (yield: 30%). Step E.3: Preparation of the 2-anilino-5-ethvnyl-N-(1 -phenylethyl)-1 ,3-thiazole-4-carboxamide:
Figure imgf000025_0002
2-Anilino-N-(1-phenylethyl)-5-[(trimethylsilyl)ethynyl]-1 ,3-thiazole-4-carboxamide (420 mg) is dissolved in methanol (5 ml) and potassium carbonate (3.96 g) is added at 00C. After stirring at 00C for 45 minutes 50 ml of AcOEt is added and the mixture is washed with 10 ml saturated sodium chloride solution. The organic layer is dryed with magnesium chloride, filtrated and the solvent is removed under reduced pressure. After chromatography on silica gel with AcOEt / cyclohexane 1 :1 the desired compound 2-anilino-N-(1-phenylethyl)-5-[(trimethylsilyl)ethynyl]-1 ,3-thiazole-4-carboxamide is obtained (yield: 15 %).
F) Preparation of 2-anilino-5-(methylsulfanyl)-N-(1-phenylethyl)-1 ,3-thiazole-4-carboxamide (compound example 2400)
Figure imgf000025_0003
Step F.1 : Preparation of methyl 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylate:
Figure imgf000026_0001
Methyl 2-anilino-5-bromo-1 ,3-thiazole-4-carboxylate (6.3 g) is dissolved in THF (100 ml), sodium methane- thiolate (1.40 g) is added at 200C. After stirring at 00C for 40 minutes, the THF is evaporated. The crude solid is triturated in dichloromethane and filtered. The solvent of the filtrate is removed under reduced pressure and the residue is chromatographed on silica gel by using AcOEt / cyclohexane 1 :1 to give the desired compound methyl 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylate (yield: 10%). Step F.2: Preparation of 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylic acid:
Figure imgf000026_0002
A solution of methyl 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylate (2.4O g) in THF (10 ml) is added to a solution of sodium hydroxide (0.1 1 g) in water (20 ml), at 200C. After stirring at 20°C for 16 hours, is evaporated and the residue is acidified with concentrated hydrochloric acid. The crude solid dissolved in dichloromethane and dryed with magnesium chloride. The solvent is removed under reduced pressure to give the desired compound 2-anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylic acid which is used without further purification (yield: 23%).
Step F.3: Preparation of the 2-anilino-5-(methylsulfanvπ-N-(1-phenylethvπ-1 ,3-thiazole-4-carboxamide:
Figure imgf000026_0003
2-Anilino-5-(methylsulfanyl)-1 ,3-thiazole-4-carboxylic acid (1.06 g) is dissolved in DMF (25 ml). TBTU (1.28 g), DIPEA (0.78 g) and 1-phenylethanamine (0.49 g) are added at room temperature. After stirring at room temperature for 20 hours, the mixture is poured into water and dichloromethane is added. The organic phase is washed with water, hydrochloric acid (1 N) and dried with MgSO4. After concentration and purification on silica gel chromatographywith AcOEt / cyclohexane (1 :1 ) 2-anilino-5-(methylsulfanyl)- N-(1-phenylethyl)-1 ,3-thiazole-4-carboxamide is obtained (yield: 17%)
For the process of preparation of the compounds according to the invention, the following abbreviations have the associated meanings:
- AIBN: azo-bis-isobutyronitrile; - DMF: N,N-dimethylformamide;
- Boc: tert-butoxycarbonyl;
- TBTU: O-(Benzotriazol-1-yl)-N,N,N',N'-tetramethyluronium tetrafluoroborate;
- HOBt: N-Hydroxybenzotriazole; - TFA: trifluoroacetic acid;
- NMP: 1 -methyl-2-pyrrolidinone;
- DIPEA: diisopropylethylamine;
- AcOEt: ethyl acetate;
- THF: tetrahydrofurane; - NBS: N-bromosuccinimide;
- NIS: N-iodosuccinimide.
Suitable solvents for carrying out processes according to the invention are customary inert organic solvents. Preference is given to using optionally halogenated aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin ; chlorobenzene, dichlorobenzene, dichloromethane, chloroform, carbon tetrachloride, dichlorethane or trichlorethane ; ethers, such as diethyl ether, diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether, dioxane, tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole ; nitriles, such as acetonitrile, propionitrile, N- or iso-butyronitrile or benzonitrile ; amides, such as N,N- dimethylformamide, N,N-dimethylacetamide, N-methylformanilide, N-methylpyrrolidone or hexamethylphosphoric triamide ; esters, such as methyl acetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide or sulphones, such as sulpholane.
Suitable bases for carrying out processes according to the invention are inorganic and organic bases which are customary for such reactions. Preference is given to using alkaline earth metal, alkali metal hydride, alkali metal hydroxides or alkali metal alkoxides, such as sodium hydroxide, sodium hydride, calcium hydroxide, potassium hydroxide, potassium tert-butoxide or other ammonium hydroxide, alkali metal carbonates, such as sodium carbonate, potassium carbonate, potassium bicarbonate, sodium bicarbonate, cesium carbonate, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate and also tertiary amines, such as trimethylamine, triethylamine, diisopropylethylamine, tributylamine, N,N-dimethylaniline, pyridine, N-methylpiperidine, N,N-dimethyl- aminopyridine, 1 ,4-diazabicyclo[2.2.2]octane (DABCO), 1 ,5-diazabicyclo[4.3.0]non-5-ene (DBN) or 1 ,8- diazabicyclo[5.4.0]undec-7-ene (DBU).
If carrying out process according to the invention, the reaction temperature can independently be varied within a relatively wide range. Generally, the process according to the invention is carried out at temperatures between -200C and 1600C. Process according to the invention is generally independently carried out under atmospheric pressure. However, it is also possible to operate under elevated or reduced pressure.
Work-up is carried out by customary methods. Generally, the reaction mixture is treated with water and the organic phase is separated off and, after drying, concentrated under reduced pressure. If appropriate, the remaining residue can be freed by customary methods, such as chromatography or recrystallization, from any impurities that can still be present.
Still in a further aspect, the present invention relates to compounds of formula (II) useful as intermediate compounds or materials for the process of preparation according to the invention. The present invention thus provides compounds of formula (II)
Figure imgf000028_0001
(H) wherein
• R3 represents a substituted or non-substituted CrC8-alkyl, a substituted or non-substituted tri(Cr Cs-alkylJsilyl-CrCs-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non- substituted tri(C1-C8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted C1-C8- halogenoalkyl having 1 to 5 halogen atoms, a substituted or non -substituted C3-C8- halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl,
C3-C8-cycloalkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (C1-C6-BIkOXyImInO)-C1-C6- alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-C1-C6-alkyl, a substituted or non- substituted (C2-C6-alkynyloxyimino)-C1-C6-alkyl, a substituted or non-substituted (benzyloxyimino)- C-i-Cg-alkyl, a substituted or non-substituted aryl-[ CrC8]-alkyl, cyano, halogen;
• R4 and R5 independently represent a substituted or non-substituted C1-C8-alkyl-(n-alkyl)-imidoyl, a substituted or non-substituted C1-C8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- (n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, hydrazino- imidoyl, a substituted or non-substituted aryl-hydrazino-imidoyl, a substituted or non-substituted CrCs-alkyl-hydrazino-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- amino-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(n-alkoxy)-imidoyl, hydroxy-(n-alkyl)-imidoyl, hydroxy-(n-alkoxy)-imidoyl, a substituted or non-substituted C1-C8- alkoxy-(n-alkyl)-imidoyl, a substituted or non-substituted C1-C8-alkoxy-(n-alkoxy)-imidoyl, a substituted or non-substituted C1-C8-aryloxy-(n-alkyl)-imidoyl, a substituted or non-substituted C1- C8-aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrCs-thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, formyl, hydrazino-carbonyl, N-hydroxy-carbamoyl, a substituted or non-substituted aryl-hydrazino-carbonyl, a substituted or non-substituted aryloxy- carbamoyl, a substituted or non-substituted CrCValkoxy-carbamoyl, a substituted or non- substituted CrCValkyl-hydrazino-carbonyl, a substituted or non-substituted CrC8-thioalkyl- carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted Cr C8-alkyl-thiocarbonyl, a substituted or non-substituted CrCs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non- substituted aryl-hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non-substituted CrCs-alkoxy-carbamothioyl, a substituted or non-substituted C1-C8- alkyl-hydrazino-thiocarbonyl, a substituted or non-substituted CrCs-alkyl-carbamothioyl, a substituted or non-substituted CrCs-halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted CrC8-alkoxy- thiocarbonyl, a substituted or non-substituted CrC8-thioalkyl-thiocarbonyl, a substituted or non- substituted thioaryl-thiocarbonyl, cyano, hydrogen, a substituted or non-substituted CrC8-alkyl- amino, a substituted or non-substituted di-CrC8-alkyl-amino, a substituted or non-substituted C1- C8-halogenoalkyl-amino, a substituted or non-substituted di-CrC8-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl-amino, amino- carbonyl-amino, formyl-amino, a substituted or non-substituted aryl-amino-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted CrC8-alkyl- carbamoyl-amino, a substituted or non-substituted CrC8-alkyl-carbonyl-amino, hydroxy-carbonyl- amino, amino-thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted C1-C8- alkoxy-thiocarbonyl-amino, a substituted or non-substituted CrC8-alkylamino-thiocarbonyl-amino, a substituted or non-substituted CrC8-alkyl-thiocarbonyl-amino, amino, a substituted or non- substituted aryloxy-amino, a substituted or non-substituted CrC8-alkoxy-amino, amino-sulfonyl- amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non-substituted Ci-C8-alkylamino-sulfonyl-amino, a substituted or non-substituted CrC8-alkyl-sulfonyl-amino, a substituted or non-substituted C1-C8- alkyl-oxy, a substituted or non-substituted CrC8-alkyl-oxyalkyl-oxy, a substituted or non- substituted CrC8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, formamidino-oxy, amino-carbonyl-oxy, formyl-oxy, a substituted or non-substituted aryl-carbonyl-oxy, a substituted or non-substituted CrC8-alkyl-carbonyl-oxy, hydrazino-carbonyl-oxy, a substituted or non- substituted aryl-amino-carbonyl-oxy, a substituted or non-substituted aryloxy-carbonyl-oxy, a substituted or non-substituted CrC8-alkoxy-carbonyl-oxy, a substituted or non-substituted C1-C8- alkyl-amino-carbonyl-oxy, a substituted or non-substituted CrC8-thioalkyl-carbonyl-oxy, a substituted or non-substituted thioaryl-carbonyl-oxy, hydroxy-thiocarbonyl-oxy, a substituted or non-substituted aryl-thiocarbonyl-oxy, a substituted or non-substituted CrC8-alkyl-thiocarbonyl- oxy, amino-thiocarbonyl-oxy, a substituted or non-substituted arylamino-thiocarbonyl-oxy, a substituted or non-substituted aryloxy-thiocarbonyl-oxy, a substituted or non-substituted C1-C8- alkoxy-thiocarbonyl-oxy, a substituted or non-substituted CrCs-alkyl-carbamothioyl-oxy, a substituted or non-substituted CrC8-thioalkyl-thiocarbonyl-oxy, a substituted or non-substituted thioaryl-thiocarbonyl-oxy, hydroxy, a substituted or non-substituted aryl-silyloxy, a substituted or non-substituted CrC8-alkyl-silyloxy, , a substituted or non-substituted CrC8-alkyl-silyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non-substituted CrC8-alkyl-hydrazino-sulfonyl, a substituted or non-substituted aryl- hydrazino-sulfonyl, a substituted or non-substituted CrCs-alkyl-amino-sulfamoyl, a substituted or non-substituted CrCs-alkyl-amino-sulphonyl, a substituted or non-substituted C1-C8- halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, a group independently selected in the list consisting of A1 to A68 as defined for R1, R2 or R3 ; provided that at least one of R4 and R5 does not represent hydrogen ; provided that it does not represent
■ 2-[(4-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid; ■ 2-[(2-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(4-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(2-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-(phenylamino)-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid; ■ 2-(foιmylamino)-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(4-chloro-3-methoxyphenyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3,4-dimethoxyphenyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(4-chlorophenyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid;
■ 5-propyl-2-({[2'-(1 H-tetrazol-5-yl)biphenyl-4-yl]methyl}amino)-1 ,3-thiazole-4-carboxylic acid; ■ 5-ethyl-2-({[2'-(1 H-tetrazol-5-yl)biphenyl-4-yl]methyl}amino)-1 ,3-thiazole-4-carboxylic acid.
Preferred intermediate compounds of formula (II) according to the invention are defined by the combinations of preferred features of R3, R4 and R5 as herein-defined for the compounds of formula (I).
In a further aspect, the present invention also relates to a fungicide, acaricide and/or insecticide composition comprising an effective and non-phytotoxic amount of an active compound of formula (I).
The expression "effective and non-phytotoxic amount" means an amount of composition according to the invention which is sufficient to control or destroy the fungi, acarids or insects present or liable to appear on the crops and which does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the fungus, acarids or insect to be controlled, the type of crop, the climatic conditions and the compounds included in the fungicide, acaricide and/or insecticide composition according to the invention. This amount can be determined by systematic field trials, which are within the capabilities of a person skilled in the art.
Thus, according to the invention, there is provided a fungicide, acaricide and/or insecticide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) as herein defined and an agriculturally acceptable support, carrier or filler.
According to the invention, the term "support" denotes a natural or synthetic organic or inorganic compound with which the active compound of formula (I) is combined or associated to make it easier to apply, notably to the parts of the plant. This support is thus generally inert and should be agriculturally acceptable. The support can be a solid or a liquid. Examples of suitable supports include clays, natural or synthetic silicates, silica, resins, waxes, solid fertilisers, water, alcohols, in particular butanol organic solvents, mineral and plant oils and derivatives thereof. Mixtures of such supports can also be used.
The composition according to the invention can also comprise additional components. In particular, the composition can further comprise a surfactant. The surfactant can be an emulsifier, a dispersing agent or a wetting agent of ionic or non-ionic type or a mixture of such surfactants. Mention can be made, for example, of polyacrylic acid salts, lignosulphonic acid salts, phenolsulphonic or naphthalenesulphonic acid salts, polycondensates of ethylene oxide with fatty alcohols or with fatty acids or with fatty amines, substituted phenols (in particular alkylphenols or arylphenols), salts of sulphosuccinic acid esters, taurine derivatives (in particular alkyl taurates), phosphoric esters of polyoxyethylated alcohols or phenols, fatty acid esters of polyols and derivatives of the above compounds containing sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential if the active compound and/or the inert support are water-insoluble and if the vector agent for the application is water. Preferably, surfactant content can be comprised from 5% to 40% by weight of the composition.
Optionally, additional components can also be included, e.g. protective colloids, adhesives, thickeners, thixotropic agents, penetration agents, stabilisers, sequestering agents. More generally, the active compounds can be combined with any solid or liquid additive, which complies with the usual formulation techniques.
In general, the composition according to the invention can contain from 0.05 to 99% by weight of active compound, preferably 10 to 70% by weight. Compositions according to the invention can be used in various forms such as aerosol dispenser, capsule suspension, cold fogging concentrate, dustable powder, emulsifiable concentrate, emulsion oil in water, emulsion water in oil, encapsulated granule, fine granule, flowable concentrate for seed treatment, gas (under pressure),gas generating product, granule, hot fogging concentrate, macrogranule, microgranule, oil dispersible powder, oil miscible flowable concentrate, oil miscible liquid, paste, plant rodlet, powder for dry seed treatment, seed coated with a pesticide, soluble concentrate, soluble powder, solution for seed treatment, suspension concentrate (flowable concentrate), ultra low volume (ULV) liquid, ultra low volume (ULV) suspension, water dispersible granules or tablets, water dispersible powder for slurry treatment, water soluble granules or tablets, water soluble powder for seed treatment and wettable powder. These compositions include not only compositions which are ready to be applied to the plant or seed to be treated by means of a suitable device, such as a spraying or dusting device, but also concentrated commercial compositions which must be diluted before application to the crop.
The compounds according to the invention can also be mixed with one or more insecticide, fungicide, bactericide, attractant, acaricide or pheromone active substance or other compounds with biological activity. The mixtures thus obtained have a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous. The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous.
According to another object of the present invention, there is provided a method for controlling the phytopathogenic fungi, acarids, and/or insects of plants, crops or seeds, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a pesticide composition according to the invention is applied as seed treatment, foliar application, stem application, drench or drip application (chemigation) to the seed, the plant or to the fruit of the plant or to soil or to inert substrate (e.g. inorganic substrates like sand, rockwool, glasswool; expanded minerals like perlite, vermiculite, zeolite or expanded clay), Pumbe, Pyroclastic materials or stuff, synthetic organic substrates (e.g. polyurethane) organic substrates (e.g. peat, composts, tree waste products like coir, wood fibre or chips, tree bark) or to a liquid substrate (e.g. floating hydroponic systems, Nutrient Film Technique, Aeroponics) wherein the plant is growing or wherein it is desired to grow.
The expression "are applied to the plants to be treated" is understood to mean, for the purposes of the present invention, that the pesticide composition which is the subject of the invention can be applied by means of various methods of treatment such as:
• spraying onto the aerial parts of the said plants a liquid comprising one of the said compositions, • dusting, the incorporation into the soil of granules or powders, spraying, around the said plants and in the case of trees injection or daubing,
• coating or film-coating the seeds of the said plants with the aid of a plant-protection mixture comprising one of the said compositions. The method according to the invention can either be a curing, preventing or eradicating method. In this method, a composition used can be prepared beforehand by mixing the two or more active compounds according to the invention.
According to an alternative of such a method, it is also possible to apply simultaneously, successively or separately compounds (A) and (B) so as to have the conjugated (A)/(B) effects, of distinct compositions each containing one of the two or three active ingredients (A) or (B).
Treatment according to the invention of the plants and plant parts with the active compounds is carried out directly or by allowing the compounds to act on the surroundings, habitat or storage space by the customary treatment methods, for example by immersion, spraying, evaporation, fogging, scattering, painting on, injection and, in the case of propagation material, in particular in the case of seeds, also by applying one or more coats.
The dose of active compound usually applied in the method of treatment according to the invention is generally and advantageously • for foliar treatments: from 0.1 to 10,000 g/ha, preferably from 10 to 1 ,000 g/ha, more preferably from 50 to 300g/ha; in case of drench or drip application, the dose can even be reduced, especially while using inert substrates like rockwool or perlite;
• for seed treatment: from 2 to 200 g per 100 kilogram of seed, preferably from 3 to 150 g per 100 kilogram of seed; • for soil treatment: from 0.1 to 10,000 g/ha, preferably from 1 to 5,000 g/ha.
The doses herein indicated are given as illustrative Examples of method according to the invention. A person skilled in the art will know how to adapt the application doses, notably according to the nature of the plant or crop to be treated. Under specific conditions, for example according to the nature of the phytopathogenic fungus to be treated or controlled, a lower dose can offer adequate protection. Certain climatic conditions, resistance or other factors like the nature of the phytopathogenic fungi or the degree of infestation, for example, of the plants with these fungi, can require higher doses of combined active ingredients. The optimum dose usually depends on several factors, for example on the type of phytopathogenic fungus to be treated, on the type or level of development of the infested plant, on the density of vegetation or alternatively on the method of application.
Without it being limiting, the crop treated with the pesticide composition or combination according to the invention is, for example, grapevine, but this could be cereals, vegetables, lucerne, soybean, market garden crops, turf, wood, tree or horticultural plants. The method of treatment according to the invention can also be useful to treat propagation material such as tubers or rhizomes, but also seeds, seedlings or seedlings pricking out and plants or plants pricking out. This method of treatment can also be useful to treat roots. The method of treatment according to the invention can also be useful to treat the over-ground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
Among the plants that can be protected by the method according to the invention, mention can be made of cotton; flax; vine; fruit or vegetable crops such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, almonds and peaches), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantins), Rubiaceae sp., Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons oranges and grapefruit); Solanaceae sp. (for instance tomatoes), Liliaceae sp., Asteraceae sp. (for instance lettuces), Umbelliferae sp., Cruciferae sp., Chenopodiaceae sp., Cucurbitaceae sp., Papilionaceae sp. (for instance peas), Rosaceae sp. (for instance strawberries); major crops such as Graminae sp. (for instance maize, lawn or cereals such as wheat, rice, barley and triticale), Asteraceae sp. (for instance sunflower), Cruciferae sp. (for instance colza), Fabacae sp. (for instance peanuts), Papilionaceae sp. (for instance soybean), Solanaceae sp. (for instance potatoes), Chenopodiaceae sp. (for instance beetroots); horticultural and forest crops; as well as genetically modified homologues of these crops.
According to the invention all plants and plant parts can be treated. By plants is meant all plants and plant populations such as desirable and undesirable wild plants, cultivars and plant varieties (whether or not protectable by plant variety or plant breeder's rights). Cultivars and plant varieties can be plants obtained by conventional propagation and breeding methods which can be assisted or supplemented by one or more biotechnological methods such as by use of double haploids, protoplast fusion, random and directed mutagenesis, molecular or genetic markers or by bioengineering and genetic engineering methods. By plant parts is meant all above ground and below ground parts and organs of plants such as shoot, leaf, blossom and root, whereby for example leaves, needles, stems, branches, blossoms, fruiting bodies, fruits and seed as well as roots, corms and rhizomes are listed. Crops and vegetative and generative propagating material, for example cuttings, corms, rhizomes, runners and seeds also belong to plant parts.
Among the plants that can be protected by the method according to the invention, mention may be made of major field crops like corn, soybean, cotton, Brassica oilseeds such as Brassta napus (e.g. canola), Brassica rapa, B. juncea (e.g. mustard) and Brassica carinata, rice, wheat, sugarbeet, sugarcane, oats, rye, barley, millet, triticale, flax, vine and various fruits and vegetables of various botanical taxa such as Rosaceae sp. (for instance pip fruit such as apples and pears, but also stone fruit such as apricots, cherries, almonds and peaches, berry fruits such as strawberries), Ribesioidae sp., Juglandaceae sp., Betulaceae sp., Anacardiaceae sp., Fagaceae sp., Moraceae sp., Oleaceae sp., Actinidaceae sp., Lauraceae sp., Musaceae sp. (for instance banana trees and plantings), Rubiaceae sp. (for instance coffee), Theaceae sp., Sterculiceae sp., Rutaceae sp. (for instance lemons, oranges and grapefruit) ; Solanaceae sp. (for instance tomatoes, potatoes, peppers, eggplant), Liliaceae sp., Compositiae sp. (for instance lettuce, artichoke and chicory - including root chicory, endive or common chicory), Umbelliferae sp. (for instance carrot, parsley, celery and celeriac), Cucurbitaceae sp. (for instance cucumber - including pickling cucumber, squash, watermelon, gourds and melons), Alliaceae sp. (for instance onions and leek), Cruciferae sp. (for instance white cabbage, red cabbage, broccoli, cauliflower, brussel sprouts, pak choi, kohlrabi, radish, horseradish, cress, Chinese cabbage), Leguminosae sp. (for instance peanuts, peas and beans beans - such as climbing beans and broad beans), Chenopodiaceae sp. (for instance mangold, spinach beet, spinach, beetroots), Malvaceae (for instance okra), Asparagaceae (for instance asparagus); horticultural and forest crops; ornamental plants; as well as genetically modified homologues of these crops.
The method of treatment according to the invention can be used in the treatment of genetically modified organisms (GMOs), e.g. plants or seeds. Genetically modified plants (or transgenic plants) are plants of which a heterologous gene has been stably integrated into genome. The expressbn "heterologous gene" essentially means a gene which is provided or assembled outside the plant and when introduced in the nuclear, chloroplastic or mitochondrial genome gives the transformed plant new or improved agronomic or other properties by expressing a protein or polypeptide of interest or by downregulating or silencing other gene(s) which are present in the plant (using for example, antisense technology, cosuppression technology or RNA interference - RNAi - technology). A heterologous gene that is located in the genome is also called a transgene. A transgene that is defined by its particular location in the plant genome is called a transformatbn or transgenic event.
Depending on the plant species or plant cultivars, their location and growth conditions (soils, climate, vegetation period, diet), the treatment according to the invention may also result in superadditive ("synergistic") effects. Thus, for example, reduced application rates and/or a widening of the activity spectrum and/or an increase in the activity of the active compounds and compositions which can be used according to the invention, better plant growth, increased tolerance to high or low temperatures, increased tolerance to drought or to water or soil salt content, increased flowering performance, easier harvesting, accelerated maturation, higher harvest yields, bigger fruits, larger plant height, greener leaf color, earlier flowering, higher quality and/or a higher nutritional value of the harvested products, higher sugar concentration within the fruits, better storage stability and/or processability of the harvested products are possible, which exceed the effects which were actually to be expected.
At certain application rates, the active compound combinations according to the invention may also have a strengthening effect in plants. Accordingly, they are also suitable for mobilizing the defense system of the plant against attack by unwanted microorganisms. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the inventbn, for example against fungi. Plant- strengthening (resistance-inducing) substances are to be understood as meaning, in the present context, those substances or combinations of substances which are capable of stimulating the defense system of plants in such a way that, when subsequently inoculated with unwanted microorganisms, the treated plants display a substantial degree of resistance to these microorganisms. In the present case, unwanted microorganisms are to be understood as meaning phytopathogenb fungi, bacteria and viruses. Thus, the substances according to the invention can be employed for protecting plants against attack by the abovementioned pathogens within a certain period of time after the treatment. The period of time within which protection is effected generally extends from 1 to 10 days, preferably 1 to 7 days, after the treatment of the plants with the active compounds.
Plants and plant cultivars which are preferably to be treated according to the invention include all plants which have genetic material which impart particularly advantageous, useful traits to these plants (whether obtained by breeding and/or biotechnological means). Plants and plant cultivars which are also preferably to be treated according to the invention are resistant against one or more biotic stresses, i.e. said plants show a better defense against animal and microbial pests, such as against nematodes, insects, mites, phytopathogenic fungi, bacteria, viruses and/or viroids. Plants and plant cultivars which may also be treated according to the invention are those plants which are resistant to one or more abiotic stresses. Abiotic stress conditions may include, for example, drought, cold temperature exposure, heat exposure, osmotic stress, flooding, increased soil salinity, increased mineral exposure, ozone exposure, high light exposure, limited availability of nitrogen nutrients, limited availability of phosphorus nutrients, shade avoidance.
Plants and plant cultivars which may also be treated according to the invention, are those plants characterized by enhanced yield characteristics. Increased yield in said plants can be the result of, for example, improved plant physiology, growth and development, such as water use efficiency, water retention efficiency, improved nitrogen use, enhanced carbon assimilation, improved photosynthesis, increased germination efficiency and accelerated maturation. Yield can furthermore be affected by improved plant architecture (under stress and non-stress conditions), including but not limited to, early flowering, flowering control for hybrid seed production, seedling vigor, plant size, internode number and distance, root growth, seed size, fruit size, pod size, pod or ear number, seed number per pod or ear, seed mass, enhanced seed filling, reduced seed dispersal, reduced pod dehiscence and lodging resistance. Further yield traits include seed composition, such as carbohydrate content, protein content, oil content and composition, nutritional value, reduction in anti-nutritional compounds, improved processability and better storage stability. Examples of plants with the above-mentioned traits are non-exhaustively listed in Table A.
Plants that may be treated according to the invention are hybrid plants that already express the characteristic of heterosis or hybrid vigor which results in generally higher yield, vigor, health and resistance towards biotic and abiotic stresses). Such plants are typically made by crossing an inbred male-sterile parent line (the female parent) with another inbred male-fertile parent line (the male parent). Hybrid seed is typically harvested from the male sterile plants and sold to growers. Male sterile plants can sometimes (e.g. in corn) be produced by detasseling, i.e. the mechanical removal of the male reproductive organs (or males flowers) but, more typically, male sterility is the result of genetic determinants in the plant genome. In that case, and especially when seed is the desired product to be harvested from the hybrid plants it is typically useful to ensure that male fertility in the hybrid plants is fully restored. This can be accomplished by ensuring that the male parents have appropriate fertility restorer genes which are capable of restoring the male fertility in hybrid plants that contain the genetic determinants responsible for male-sterility. Genetic determinants for male sterility may be located in the cytoplasm. Examples of cytoplasmic male sterility (CMS) were for instance described in Brassica species (WO 92/05251 , WO 95/09910, WO 98/27806, WO 05/002324, WO 06/021972 and US 6,229,072). However, genetic determinants for male sterility can also be located in the nuclear genome. Male sterile plants can also be obtained by plant biotechnology methods such as genetic engineering. A particularly useful means of obtaining male-sterile plants is described in WO 89/10396 in which, for example, a ribonuclease such as barnase is selectively expressed in the tapetum cells in the stamens. Fertility can then be restored by expression in the tapetum cells of a ribonuclease inhibitor such as barstar (e.g. WO 91/02069).
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may be treated according to the invention are herbicide-tolerant plants, i.e. plants made tolerant to one or more given herbicides. Such plants can be obtained either by genetic transformation, or by selection of plants containing a mutation imparting such herbicide tolerance.
Herbicide-resistant plants are for example glyphosate-tolerant plants, i.e. plants made tolerant to the herbicide glyphosate or salts thereof. Plants can be made tolerant to glyphosate through different means. For example, glyphosate-tolerant plants can be obtained by transforming the plant with a gene encoding the enzyme 5-enolpyruvylshikimate-3-phosphate synthase (EPSPS). Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., 1983, Science 221 , 370-371 ), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., 1992, Curr. Topics Plant Physiol. 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., 1986, Science 233, 478-481 ), a Tomato EPSPS (Gasser et al., 1988, J. Biol. Chem. 263, 4280-4289), or an Eleusine EPSPS (WO 01/66704). It can also be a mutated EPSPS as described in for example EP 0837944, WO 00/66746, WO 00/66747 or WO02/26995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in U.S. Patent Nos. 5,776,760 and 5,463,175. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate acetyl transferase enzyme as described in for example WO 02/36782, WO 03/092360, WO 05/012515 and WO 07/024782. Glyphosate-tolerant plants can also be obtained by selecting plants containing naturally-occurring mutations of the above-mentioned genes, as described in for example WO 01/024615 or WO 03/013226.
Other herbicide resistant plants are for example plants that are made tolerant to herbicides inhibiting the enzyme glutamine synthase, such as bialaphos, phosphinothricin or glufosinate. Such plants can be obtained by expressing an enzyme detoxifying the herbicide or a mutant glutamine synthase enzyme that is resistant to inhibition. One such efficient detoxifying enzyme is an enzyme encoding a phosphinothricin acetyltransferase (such as the bar or pat protein from Streptomyces species). Plants expressing an exogenous phosphinothricin acetyltransferase are for example described in U.S. Patent Nos. 5,561 ,236; 5,648,477; 5,646,024; 5,273,894; 5,637,489; 5,276,268; 5,739,082; 5,908,810 and 7,112,665. Further herbicide-tolerant plants are also plants that are made tolerant to the herbicides inhibiting the enzyme hydroxyphenylpyruvatedioxygenase (HPPD). Hydroxyphenylpyruvatedioxygenases are enzymes that catalyze the reaction in which para-hydroxyphenylpyruvate (HPP) is transformed into homogentisate. Plants tolerant to HPPD-inhibitors can be transformed with a gene encoding a naturally-occurring resistant HPPD enzyme, or a gene encoding a mutated HPPD enzyme as described in WO 96/38567, WO 99/24585 and WO 99/24586. Tolerance to HPPD-inhibitors can also be obtained by transforming plants with genes encoding certain enzymes enabling the formation of homogentisate despite the inhibition of the native HPPD enzyme by the HPPD-inhibitor. Such plants and genes are described in WO 99/34008 and WO 02/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate deshydrogenase in addition to a gene encoding an HPPD-tolerant enzyme, as described in WO 2004/024928. Still further herbicide resistant plants are plants that are made tolerant to acetolactate synthase (ALS) inhibitors. Known ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pryimidinyoxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides. Different mutations in the ALS enzyme (also known as acetohydroxyacid synthase, AHAS) are known to confer tolerance to different herbicides and groups of herbicides, as described for example in Tranel and Wright (2002, Weed Science 50:700-712), but also, in U.S. Patent No. 5,605,011 , 5,378,824, 5,141 ,870, and 5,013,659. The production of sulfonylurea-tolerant plants and imidazolinone-tolerant plants is described in U.S. Patent Nos. 5,605,011 ; 5,013,659; 5,141 ,870; 5,767,361 ; 5,731 ,180; 5,304,732; 4,761 ,373; 5,331 ,107; 5,928,937; and 5,378,824; and international publication WO 96/33270. Other imidazolinone-tolerant plants are also described in for example WO 2004/040012, WO 2004/106529, WO 2005/020673, WO 2005/093093, WO 2006/007373, WO 2006/015376, WO 2006/024351 , and WO 2006/060634. Further sulfonylurea- and imidazolinone-tolerant plants are also described in for example WO 07/024782.
Other plants tolerant to imidazolinone and/or sulfonylurea can be obtained by induced mutagenesis, selection in cell cultures in the presence of the herbicide or mutation breeding as described for example for soybeans in U.S. Patent 5,084,082, for rice in WO 97/41218, for sugar beet in U.S. Patent 5,773,702 and WO 99/057965, for lettuce in U.S. Patent 5,198,599, or for sunflower in WO 01/065922.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are insect-resistant transgenic plants, i.e. plants made resistant to attack by certain target insects. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such insect resistance. An "insect-resistant transgenic plant", as used herein, includes any plant containing at least one transgene comprising a coding sequence encoding:
1 ) an insecticidal crystal protein from Bacillus thuringiensis or an insecticidal portion thereof, such as the insecticidal crystal proteins listed by Crickmore et al. (1998, Microbiology and Molecular Biology Reviews, 62: 807-813), updated by Crickmore et al. (2005) at the Bacillus thuringiensis toxin nomenclature, online at: http://www.lifesci.sussex.ac.uk/Home/Neil_Crickmore/Bt/), or insecticidal portions thereof, e.g., proteins of the Cry protein classes CrylAb, CryiAc, Cry1 B, Cry1C, Cry1 D, Cry1 F, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof (e.g. EP 1999141 and WO 2007/107302); or
2) a crystal protein from Bacillus thuringiensis or a portion thereof which is insecticidal in the presence of a second other crystal protein from Bacillus thuringiensis or a portion thereof, such as the binary toxin made up of the Cry34 and Cry35 crystal proteins (Moellenbeck et al. 2001 , Nat. Biotechnol. 19: 668-72; Schnepf et al. 2006, Applied Environm. Microbiol. 71 , 1765-1774) or the binary toxin made up of the Cry1A or Cry1 F proteins and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Appl. No. 12/214,022 and EP 08010791.5); or
3) a hybrid insecticidal protein comprising parts of different insecticidal crystal proteins from Bacillus thuringiensis, such as a hybrid of the proteins of 1 ) above or a hybrid of the proteins of 2) above, e.g., the Cry1A.1O5 protein produced by corn event MON89034 (WO 2007/027777); or 4) a protein of any one of 1 ) to 3) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation, such as the Cry3Bb1 protein in corn events MON863 or MON88017, or the Cry3A protein in corn event MIR604; or 5) an insecticidal secreted protein from Bacillus thuringiensis or Bacillus cereus, or an insecticidal portion thereof, such as the vegetative insecticidal (VIP) proteins listed at: http://www.lifesci.sussex.ac.uk/home/Neil Crickmore/Bt/vip.html, e.g., proteins from the VIP3Aa protein class; or
6) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a second secreted protein from Bacillus thuringiensis or B. cereus, such as the binary toxin made up of the VIPIA and VIP2A proteins (WO 94/21795); or
7) a hybrid insecticidal protein comprising parts from different secreted proteins from Bacillus thuringiensis or Bacillus cereus, such as a hybrid of the proteins in 1 ) above or a hybrid of the proteins in 2) above; or 8) a protein of any one of 5) to 7) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT102; or 9) a secreted protein from Bacillus thuringiensis or Bacillus cereus which is insecticidal in the presence of a crystal protein from Bacillus thuringiensis, such as the binary toxin made up of VIP3 and Cry1A or Cry1 F (US Patent Appl. No. 61/126083 and 61/195019), or the binary toxin made up of the VIP3 protein and the Cry2Aa or Cry2Ab or Cry2Ae proteins (US Patent Appl. No. 12/214,022 and EP 08010791.5).
10) a protein of 9) above wherein some, particularly 1 to 10, amino acids have been replaced by another amino acid to obtain a higher insecticidal activity to a target insect species, and/or to expand the range of target insect species affected, and/or because of changes introduced into the encoding DNA during cloning or transformation (while still encoding an insecticidal protein)
Of course, an insect-resistant transgenic plant, as used herein, also includes any plant comprising a combination of genes encoding the proteins of any one of the above classes 1 to 10. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 10, to expand the range of target insect species affected when using different proteins directed at different target insect species, or to delay insect resistance development to the plants by using different proteins insecticidal to the same target insect species but having a different mode of action, such as binding to different receptor binding sites in the insect.
An "insect-resistant transgenic plant", as used herein, further includes any plant containing at least one transgene comprising a sequence producing upon expression a double-stranded RNA which upon ingestion by a plant insect pest inhibits the growth of this insect pest, as described e.g. in WO 2007/080126.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are tolerant to abiotic stresses. Such plants can be obtained by genetic transformation, or by selection of plants containing a mutation imparting such stress resistance. Particularly useful stress tolerance plants include: 1 ) plants which contain a transgene capable of reducing the expression and/or the activity of poly(ADP-ribose) polymerase (PARP) gene in the plant cells or plants as described in WO
00/04173, WO/2006/045633, EP 04077984.5, or EP 06009836.5.
2) plants which contain a stress tolerance enhancing transgene capable of reducing the expression and/or the activity of the PARG encoding genes of the plants or plants cells, as described e.g. in WO 2004/090140.
3) plants which contain a stress tolerance enhancing transgene coding for a plant-functional enzyme of the nicotineamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphorybosyltransferase as described e.g. in EP 04077624.7, WO 2006/133827,
PCT/EP07/002433, EP 1999263, or WO 2007/107326.
Plants or plant cultivars (obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention show altered quantity, quality and/or storage-stability of the harvested product and/or altered properties of specific ingredients of the harvested product such as :
1 ) transgenic plants which synthesize a modified starch, which in its physical-chembal characteristics, in particular the amylose content or the amylose/amylopectin ratio, the degree of branching, the average chain length, the side chain distribution, the viscosity behaviour, the gelling strength, the starch grain size and/or the starch grain morphology, is changed in comparison with the synthesised starch in wild type plant cells or plants, so that this is better suited for special applications. Said transgenic plants synthesizing a modified starch are disclosed, for example, in EP 0571427, WO 95/04826, EP 0719338, WO 96/15248, WO 96/19581 , WO 96/27674, WO 97/11188, WO 97/26362, WO 97/32985, WO 97/42328, WO
97/44472, WO 97/45545, WO 98/27212, WO 98/40503, WO99/58688, WO 99/58690, WO 99/58654, WO 00/08184, WO 00/08185, WO 00/08175, WO 00/28052, WO 00/77229, WO 01/12782, WO 01/12826, WO 02/101059, WO 03/071860, WO 2004/056999, WO 2005/030942, WO 2005/030941 , WO 2005/095632, WO 2005/095617, WO 2005/095619, WO 2005/095618, WO 2005/123927, WO 2006/018319, WO 2006/103107, WO 2006/108702, WO 2007/009823,
WO 00/22140, WO 2006/063862, WO 2006/072603, WO 02/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1 , EP 07090009.7, WO 01/14569, WO 02/79410, WO 03/33540, WO 2004/078983, WO 01/19975, WO 95/26407, WO 96/34968, WO 98/20145, WO 99/12950, WO 99/66050, WO 99/53072, US 6,734,341 , WO 00/11192, WO 98/22604, WO 98/32326, WO 01/98509, WO 01/98509, WO 2005/002359, US 5,824,790, US 6,013,861 , WO
94/04693, WO 94/09144, WO 94/11520, WO 95/35026, WO 97/20936
2) transgenic plants which synthesize non starch carbohydrate polymers or which synthesize non starch carbohydrate polymers with altered properties in comparison to wild type plants without genetic modification. Examples are plants producing polyfructose, especially of the inulin and levan-type, as disclosed in EP 0663956, WO 96/01904, WO 96/21023, WO 98/39460, and WO
99/24593, plants producing alpha-1 ,4-glucans as disclosed in WO 95/31553, US 2002031826, US 6,284,479, US 5,712,107, WO 97/47806, WO 97/47807, WO 97/47808 and WO 00/14249, plants producing alpha-1 ,6 branched alpha-1 ,4-glucans, as disclosed in WO 00/73422, plants producing alternan, as disclosed in e.g. WO 00/47727, WO 00/73422, EP 06077301.7, US 5,908,975 and EP 0728213,
3) transgenic plants which produce hyaluronan, as for example disclosed in WO 2006/032538, WO 2007/039314, WO 2007/039315, WO 2007/039316, JP 2006304779, and WO 2005/012529.
4) transgenic plants or hybrid plants, such as onions with characteristics such as 'high soluble solids content', 'low pungency' (LP) and/or 'long storage' (LS), as described in US Patent Appl. No. 12/020,360 and 61/054,026.
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as cotton plants, with altered fiber characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered fiber characteristics and include: a) Plants, such as cotton plants, containing an altered form of cellulose synthase genes as described in WO 98/00549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO 2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO 01/17333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO 02/45485 e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.g. through downregulation of fiber-selective β-1 ,3-glucanase as described in WO 2005/017157, or as described in EP 08075514.3 or US Patent Appl. No. 61/128,938 f) Plants, such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acetylglucosaminetransferase gene including nodC and chitin synthase genes as described in WO 2006/136351
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered oil profile characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered oil profile characteristics and include: a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g. in US 5,969,169, US 5,840,946 or US 6,323,392 or US 6,063,947 b) Plants such as oilseed rape plants, producing oil having a low linolenic acid content as described in US 6,270,828, US 6,169,190 or US 5,965,755 c) Plant such as oilseed rape plants, producing oil having a low level of saturated fatty acids as described e.g. in US Patent No. 5,434,283
Plants or plant cultivars (that can be obtained by plant biotechnology methods such as genetic engineering) which may also be treated according to the invention are plants, such as oilseed rape or related Brassica plants, with altered seed shattering characteristics. Such plants can be obtained by genetic transformation, or by selection of plants contain a mutation imparting such altered seed shattering characteristics and include plants such as oilseed rape plants with delayed or reduced seed shattering as described in US Patent Appl. No. 61/135,230 and EP 08075648.9. Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are the subject of petitions for non- regulated status, in the United States of America, to the Animal and Plant Health Inspection Service (APHIS) of the United States Department of Agriculture (USDA) whether such petitions are granted or are still pending. At any time this information is readily available from APHIS (4700 River Road Riverdale, MD 20737, USA), for instance on its internet site (URL http://www.aphis.usda.gov/brs/not_reg.html). On the filing date of this application the petitions for nonregulated status that were pending with APHIS or granted by APHIS were those listed in table B which contains the following information:
Petition : the identification number of the petition. Technical descriptions of the transformation events can be found in the individual petition documents which are obtainable from APHIS, for example on the APHIS website, by reference to this petition number. These descriptions are herein incorporated by reference.
Extension of Petition : reference to a previous petition for which an extension is requested.
Institution : the name of the entity submitting the petition.
Regulated article : the plant species concerned.
Transgenic phenotype : the trait conferred to the plants by the transformation event. - Transformation event or line : the name of the event or events (sometimes also designated as lines or lines) for which nonregulated status is requested.
APHIS documents : various documents published by APHIS in relation to the Petition and which can be requested with APHIS.
Additional particularly useful plants containing single transformation events or combinations of transformation events are listed for example in the databases from various national or regional regulatory agencies (see for example http://qmoinfo.irc.it/qmp browse. aspx and http://www.agbios.com/dbase.php).
The composition according to the invention can also be used against fungal diseases liable to grow on or inside timber. The term "timber" means all types of species of wood and all types of working of this wood intended for construction, for example solid wood, high-density wood, laminated wood and plywood. The method for treating timber according to the invention mainly consists in contacting one or more compounds according to the invention or a composition according to the invention; this includes for example direct application, spraying, dipping, injection or any other suitable means.
Among the diseases of plants or crops that can be controlled by the method according to the invention, mention can be made of :
• Powdery mildew diseases such as : Blumeria diseases, caused for example by Blumeria graminis ;
Podosphaera diseases, caused for example by Podosphaera leucothcha ;
Sphaerotheca diseases, caused for example by Sphaerotheca fuliginea ;
Uncinula diseases, caused for example by Uncinula necator ; • Rust diseases such as :
Gymnosporangium diseases, caused for example by Gymnosporangium sabinae ;
Hemileia diseases, caused for example by Hemileia vastatήx ;
Phakopsora diseases, caused for example by Phakopsora pachyrhizi or Phakopsora meibomiae ;
Puccinia diseases, caused for example by Puccinia recondita ; Uromyces diseases, caused for example by Uromyces appendiculatus ;
• Oomycete diseases such as :
Albugo diseases caused for example by Albugo Candida;
Bremia diseases, caused for example by Bremia lactucae ;
Peronospora diseases, caused for example by Peronospora pisi or P. brassicae ; Phytophthora diseases, caused for example by Phytophthora infestans ;
Plasmopara diseases, caused for example by Plasmopara viticola ;
Pseudoperonospora diseases, caused for example by Pseudoperonospora humuli or
Pseudoperonospora cubensis ;
Pythium diseases, caused for example by Pythium ultimum ; • Leafspot, leaf blotch and leaf blight diseases such as :
Alternaria diseases, caused for example by Alternaria solani ;
Cercospora diseases, caused for example by Cercospora beticola ;
Cladiosporum diseases, caused for example by Cladiosporium cucumerinum ;
Cochliobolus diseases, caused for example by Cochliobolus sativus ; Colletotrichum diseases, caused for example by Colletotrichum lindemuthanium ;
Cycloconium diseases, caused for example by Cycloconium oleaginum ;
Diaporthe diseases, caused for example by Diaporthe citri ;
Drechslera, Syn: Helminthosporium) or Cochliobolus miyabeanus;
Elsinoe diseases, caused for example by Elsinoe fawcettii ; Gloeosporium diseases, caused for example by Gloeospoήum laeticolor ;
Glomerella diseases, caused for example by Glomerella cingulata ;
Guignardia diseases, caused for example by Guignardia bidwelli ;
Leptosphaeria diseases, caused for example by Leptosphaeria maculans ; Leptosphaeria nodorum ;
Magnaporthe diseases, caused for example by Magnaporthe grisea ; Mycosphaerella diseases, caused for example by Mycosphaerella graminicola ; Mycosphaerella arachidtola ; Mycosphaerella fiβensis ;
Phaeosphaeria diseases, caused for example by Phaeosphaeήa nodorum ;
Pyrenophora diseases, caused for example by Pyrenophora teres ; Ramularia diseases, caused for example by Ramularia collo-cygni ; Rhynchosporium diseases, caused for example by Rhynchosporium secalis ; Septoria diseases, caused for example by Septoria apii or Septoria lycopercisi ; Typhula diseases, caused for example by Typhula incarnata ; Venturia diseases, caused for example by Venturia inaequalis ;
• Root and stem diseases such as :
Corticium diseases, caused for example by Corticium graminearum ;
Fusarium diseases, caused for example by Fusaήum oxysporum ;
Gaeumannomyces diseases, caused for example by Gaeumannomyces graminis ; Rhizoctonia diseases, caused for example by Rhizoctonia solani ;
Sarocladium diseases caused for example by Sarocladium oryzae;
Sclerotium diseases caused for example by Sclerotium oryzae;
Tapesia diseases, caused for example by Tapesia acuformis ;
Thielavbpsis diseases, caused for example by Thielaviopsis basicola ; • Ear and panicle diseases including maize cob, such as :
Alternaria diseases, caused for example by Alternaria spp. ;
Aspergillus diseases, caused for example by Aspergillus flavus ;
Cladosporium diseases, caused for example by Cladosporium spp. ;
Claviceps diseases, caused for example by Claviceps purpurea ; Fusarium diseases, caused for example by Fusarium culmorum ;
Gibberella diseases, caused for example by Gibberella zeae ;
Monographella diseases, caused for example by Monographella nivalis ;
• Smut and bunt diseases such as :
Sphacelotheca diseases, caused for example by Sphacelotheca reiliana ; Tilletia diseases, caused for example by Tilletia caries ;
Urocystis diseases, caused for example by Urocystis occulta ; Ustilago diseases, caused for example by Ustilago nuda ;
• Fruit rot and mould diseases such as : Aspergillus diseases, caused for example by Aspergillus flavus ; Botrytis d iseases, caused for example by Botrytis cinerea ;
Penicillium diseases, caused for example by Penicillium expansum ;
Rhizopus diseases caused by example by Rhizopus stolonifer
Sclerotinia diseases, caused for example by Sclerotinia sclerotiorum ;
Verticilium diseases, caused for example by Verticilium alboatrum ; • Seed and soil borne decay, mould, wilt, rot and dampingoff diseases such as :
Alternaria diseases, caused for example by Alternaria brassicicola
Aphanomyces diseases, caused for example by Aphanomyces euteiches
Ascochyta diseases, caused for example by Ascochyta lentis Aspergillus diseases, caused for example by Aspergillus flavus
Cladosporium diseases, caused for example by Cladosporium herbarum
Cochliobolus diseases, caused for example by Cochliobolus sativus
(Conidiaform: Drechslera, Bipolaris Syn: Helminthosporium); Colletotrichum diseases, caused for example by Colletotrichum coccodes;
Fusarium diseases, caused for example by Fusaήum culmorum;
Gibberella diseases, caused for example by Gibberella zeae;
Macrophomina diseases, caused for example by Macrophomina phaseolina
Monographella diseases, caused for example by Monographella nivalis; Penicillium diseases, caused for example by Penicillium expansum
Phoma diseases, caused for example by Phoma lingam
Phomopsis diseases, caused for example by Phomopsis sojae;
Phytophthora diseases, caused for example by Phytophthora cactorum;
Pyrenophora diseases, caused for example by Pyrenophora graminea Pyricularia diseases, caused for example by Pyricularia oryzae;
Pythium diseases, caused for example by Pythium ultimum;
Rhizoctonia diseases, caused for example by Rhizoctonia solani;
Rhizopus diseases, caused for example by Rhizopus oryzae
Sclerotium diseases, caused for example by Sclerotium rolfsii; Septoria diseases, caused for example by Septoria nodorum;
Typhula diseases, caused for example by Typhula incarnata;
Verticillium diseases, caused for example by Verticillium dahliae ;
• Canker, broom and dieback diseases such as : Nectria diseases, caused for example by Nectria galligena ; • Blightdiseases such as :
Monilinia diseases, caused for example by Monilinia laxa ;
• Leaf blister or leaf curl diseases such as :
Exobasidium diseases caused for nexample by Exobasidium vexans;
Taphrina diseases, caused for example by Taphrina deformans ; • Decline diseases of wooden plants such as :
Esca diseases, caused for example by Phaemoniella clamydospora, Phaeomoniella clamydospora,
Phaeoacremonium aleophilum and Fomitiporia mediterranea ;
Eutypa dyeback, caused for example by Eutypa lata ;
Dutch elm disease, caused for example by Ceratocystsc ulmi ; Ganoderma diseases caused by example by Ganoderma boninense;
• Diseases of flowers and Seeds such as : Botrytis diseases, caused for example by Botrytis cinerea ;
• Diseases of tubers such as : Rhizoctonia diseases, caused for example by Rhizoctonia solani Helminthosporium diseases, caused for example by Helminthospohum solani.
• D iseases of Tu bers such as
Rhizoctonia diseases caused for example by Rhizoctonia solani ; Helminthosporium diseases caused for example by Helminthospohum solani ;
• Club root diseases such as
Plasmodiophora diseases, caused for example by Plamodiophora brassicae ;
• Diseases caused by Bacterial Organisms such as Xanthomanas species for example Xanthomonas campestήs pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans;
Erwinia species for example Erwinia amylovora.
The active compounds of the invention, in combination with good plant tolerance and favourable toxicity to warm-blooded animals and being tolerated well by the environment, are suitable for protecting plants and plant organs, for increasing the harvest yields, for improving the quality of the harvested material and/or for controlling animal pests, in particular insects, arachnids, helminths, nematodes and molluscs, which are encountered in agriculture, in horticulture, in animal husbandry, in forests, in gardens and leisure facilities, in the protection of stored products and of materials, and in the hygiene sector. They may be preferably employed as plant protection agents. They are active against normally sensitive and resistant species and against all or some stages of development. The abovementioned pests include:
From the order of the Anoplura (Phthiraptera), for example, Damalinia spp., Haematopinus spp., Linognathus spp., Pediculus spp., Trichodectes spp.
From the class of the Arachnida, for example, Acarus siro, Aceria sheldoni, Aculops spp., Aculus spp., Amblyomma spp., Argas spp., Boophilus spp., Brevipalpus spp., Bryobia praetiosa, Chorioptes spp., Dermanyssus gallinae, Eotetranychus spp., Epitrimerus pyri, Eutetranychus spp., Eriophyes spp., Hemitarsonemus spp., Hyalomma spp., Ixodes spp., Latrodectus mactans, Metatetranychus spp., Oligonychus spp., Ornithodoros spp., Panonychus spp., Phyllocoptruta oleivora, Polyphagotarsonemus latus, Psoroptes spp., Rhipicephalus spp., Rhizoglyphus spp., Sarcoptes spp., Scorpio maurus, Stenotarsonemus spp., Tarsonemus spp., Tetranychus spp., Vasates lycopersici.
From the class of the Bivalva, for example, Dreissena spp.
From the order of the Chilopoda, for example, Geophilus spp., Scutigera spp.
From the order of the Coleoptera, for example, Acanthoscelides obtectus, Adoretus spp., Agelastica alni,
Agriotes spp., Amphimallon solstitialis, Anobium punctatum, Anoplophora spp., Anthonomus spp., Anthrenus spp., Apogonia spp., Atomaria spp., Attagenus spp., Bruchidius obtectus, Bruchus spp., Ceuthorhynchus spp., Cleonus mendicus, Conoderus spp., Cosmopolites spp., Costelytra zealandica, Curculio spp., Cryptorhynchus lapathi, Dermestes spp., Diabrotica spp., Epilachna spp., Faustinus cubae, Gibbium psylloides, Heteronychus arator, Hylamorpha elegans, Hylotrupes bajulus, Hypera postica, Hypothenemus spp., Lachnosterna consanguinea, Leptinotarsa decemlineata, Lissorhoptrus oryzophilus, Lixus spp., Lyctus spp., Meligethes aeneus, Melolontha melolontha, Migdolus spp., Monochamus spp., Naupactus xanthographus, Niptus hololeucus, Oryctes rhinoceros, Oryzaephilus surinamensis, Otiorrhynchus sulcatus, Oxycetonia jucunda, Phaedon cochleariae, Phyllophaga spp., Popillia japonica, Premnotrypes spp., Psylliodes chrysocephala, Ptinus spp., Rhizobius ventralis, Rhizopertha dominica, Sitophilus spp., Sphenophorus spp., Sternechus spp., Symphyletes spp., Tenebrio molitor, Tribolium spp., Trogoderma spp., Tychius spp., Xylotrechus spp., Zabrus spp.
From the order of the Collembola, for example, Onychiurus armatus.
From the order of the Dermaptera, for example, Forficula auricularia.
From the order of the Diplopoda, for example, Blaniulus guttulatus.
From the order of the Diptera, for example, Aedes spp., Anopheles spp., Bibio hortulanus, Calliphora erythrocephala, Ceratitis capitata, Chrysomyia spp., Cochliomyia spp., Cordylobia anthropophaga, Culex spp., Cuterebra spp., Dacus oleae, Dermatobia hominis, Drosophila spp., Fannia spp., Gastrophilus spp., Hylemyia spp., Hyppobosca spp., Hypoderma spp., Liriomyza spp., Lucilia spp., Musca spp., Nezara spp., Oestrus spp., Oscinella frit, Pegomyia hyoscyami, Phorbia spp., Stomoxys spp., Tabanus spp., Tannia spp., Tipula paludosa, Wohlfahrtia spp.
From the class of the Gastropoda, for example, Arion spp., Biomphalaria spp., Bulinus spp., Deroceras spp., Galba spp., Lymnaea spp., Oncomelania spp., Succinea spp.
From the class of the helminths, for example, Ancylostoma duodenale, Ancylostoma ceylanicum, Acylostoma braziliensis, Ancylostoma spp., Ascaris lubricoides, Ascaris spp., Brugia malayi, Brugia timori, Bunostomum spp., Chabertia spp., Clonorchis spp., Cooperia spp., Dicrocoelium spp, Dictyocaulus filaria, Diphyllobothrium latum, Dracunculus medinensis, Echinococcus granulosus, Echinococcus multilocularis, Enterobius vermicularis, Faciola spp., Haemonchus spp., Heterakis spp., Hymenolepis nana, Hyostrongulus spp., Loa Loa, Nematodirus spp., Oesophagostomum spp., Opisthorchis spp., Onchocerca volvulus, Ostertagia spp., Paragonimus spp., Schistosomen spp., Strongyloides fuelleborni, Strongyloides stercoralis, Stronyloides spp., Taenia saginata, Taenia solium, Trichinella spiralis, Trichinella nativa, Trichinella britovi, Trichinella nelsoni, Trichinella pseudopsiralis, Trichostrongulus spp., Trichuris trichuria, Wuchereria bancrofti. It is furthermore possible to control protozoa, such as Eimeria.
From the order of the Heteroptera, for example, Anasa tristis, Antestiopsis spp., Blissus spp., Calocoris spp., Campylomma livida, Cavelerius spp., Cimex spp., Creontiades dilutus, Dasynus piperis, Dichelops furcatus, Diconocoris hewetti, Dysdercus spp., Euschistus spp., Eurygaster spp., Heliopeltis spp., Horcias nobilellus, Leptocorisa spp., Leptoglossus phyllopus, Lygus spp., Macropes excavatus, Miridae, Nezara spp., Oebalus spp., Pentomidae, Piesma quadrata, Piezodorus spp., Psallus seriatus, Pseudacysta persea, Rhodnius spp., Sahlbergella singularis, Scotinophora spp., Stephanitis nashi, Tibraca spp., Triatoma spp.
From the order of the Homoptera, for example, Acyrthosipon spp., Aeneolamia spp., Agonoscena spp., Aleurodes spp., Aleurolobus barodensis, Aleurothrixus spp., Amraca spp., Anuraphis cardui, Aonidiella spp., Aphanostigma piri, Aphis spp., Arboridia apicalis, Aspidiella spp., Aspidiotus spp., Atanus spp., Aulacorthum solani, Bemisia spp., Brachycaudus helichrysii, Brachycolus spp., Brevicoryne brassicae, Calligypona marginata, Carneocephala fulgida, Ceratovacuna lanigera, Cercopidae, Ceroplastes spp., Chaetosiphon fragaefolii, Chionaspis tegalensis, Chlorita onukii, Chromaphis juglandicola, Chrysomphalus ficus, Cicadulina mbila, Coccomytilus halli, Coccus spp., Cryptomyzus ribis, Dalbulus spp., Dialeurodes spp., Diaphorina spp., Diaspis spp., Doralis spp., Drosicha spp., Dysaphis spp., Dysmboccus spp., Empoasca spp., Eriosoma spp., Erythroneura spp., Euscelis bilobatus, Geococcus coffeae, Homalodisca coagulata, Hyalopterus arundinis, lcerya spp., ldiocerus spp., ldioscopus spp., Laodelphax striatellus, Lecanium spp., Lepidosaphes spp., Lipaphis erysimi, Macrosiphum spp., Mahanarva fimbriolata, Melanaphis sacchari, Metcalfiella spp., Metopolophium dirhodum, Monellia costalis, Monelliopsis pecanis, Myzus spp., Nasonovia ribisnigri, Nephotettix spp., Nilaparvata lugens, Oncometopia spp., Orthezia praelonga, Parabemisia myricae, Paratrioza spp., Parlatoria spp., Pemphigus spp., Peregrinus maidis, Phenacoccus spp., Phloeomyzus passerinii, Phorodon humuli, Phylloxera spp., Pinnaspis aspidistrae, Planococcus spp., Protopulvinaria pyriformis, Pseudaulacaspis pentagona, Pseudococcus spp., Psylla spp., Pteromalus spp., Pyrilla spp., Quadraspidiotus spp., Quesada gigas, Rastrococcus spp., Rhopalosiphum spp., Saissetia spp., Scaphoides titanus, Schizaphis graminum, Selenaspidus articulatus, Sogata spp., Sogatella furcifera, Sogatodes spp., Stictocephala festina, Tenalaphara malayensis, Tinocallis caryaefoliae, Tomaspis spp., Toxoptera spp., Trialeurodes vaporariorum, Trioza spp., Typhlocyba spp., Unaspis spp., Viteus vitifolii.
From the order of the Hymenoptera, for example, Diprion spp., Hoplocampa spp., Lasius spp., Mono- morium pharaonis, Vespa spp.
From the order of the Isopoda, for example, Armadillidium vulgare, Oniscus asellus, Porcellio scaber.
From the order of the Isoptera, for example, Reticulitermes spp., Odontotermes spp. From the order of the Lepidoptera, for example, Acronicta major, Aedia leucomelas, Agrotis spp., Alabama argillacea, Anticarsia spp., Barathra brassicae, Bucculatrix thurberiella, Bupalus piniarius, Cacoecia podana, Capua reticulana, Carpocapsa pomonella, Cheimatobia brumata, Chilo spp., Choristoneura fumiferana, Clysia ambiguella, Cnaphalocerus spp., Earias insulana, Ephestia kuehniella, Euproctis chrysorrhoea, Euxoa spp., Feltia spp., Galleria mellonella, Helicoverpa spp., Heliothis spp., Hofmannophila pseudospretella, Homona magnanima, Hyponomeuta padella, Laphygma spp., Lithocolletis blancardella, Lithophane antennata, Loxagrotis albicosta, Lymantria spp., Malacosoma neustria, Mamestra brassicae, Mocis repanda, Mythimna separata, Oria spp., Oulema oryzae, Panolis flammea, Pectinophora gossypiella, Phyllocnistis citrella, Pieris spp., Plutella xylostella, Prodenia spp., Pseudaletia spp., Pseudoplusia includens, Pyrausta nubilalis, Spodoptera spp., Thermesia gemmatalis, Tinea pellionella, Tineola bisselliella, Tortrix viridana, Trichoplusia spp.
From the order of the Orthoptera, for example, Acheta domesticus, Blatta orientalis, Blattella germanba, Gryllotalpa spp., Leucophaea maderae, Locusta spp., Melanoplus spp., Periplaneta americana, Schistocerca gregaria.
From the order of the Siphonaptera, for example, Ceratophyllus spp., Xenopsylla cheopis.
From the order of the Symphyla, for example, Scutigerella immaculata.
From the order of the Thysanoptera, for example, Baliothrips biformis, Enneothrips flavens, Frankliniella spp., Heliothrips spp., Hercinothrips femoralis, Kakothrips spp., Rhipiphorothrips cruentatus, Scirtothrips spp., Taeniothrips cardamoni, Thrips spp.
From the order of the Thysanura, for example, Lepisma saccharina.
The phytoparasitic nematodes include, for example, Anguina spp., Aphelenchoides spp., Belonoaimus spp., Bursaphelenchus spp., Ditylenchus dipsaci, Globodera spp., Heliocotylenchus spp., Heterodera spp., Longidorus spp., Meloidogyne spp., Pratylenchus spp., Radopholus similis, Rotylenchus spp., Trichodorus spp., Tylenchorhynchus spp., Tylenchulus spp., Tylenchulus semipenetrans, Xiphinema spp.
The compounds according to the invention can also be used for the preparation of composition useful to curatively or preventively treat human or animal fungal diseases such as, for example, mycoses, dermatoses, trichophyton diseases and candidiases or diseases caused by Aspergillus spp., for example Aspergillus fumigatus.
The active compounds according to the invention act not only against plant, hygiene and stored product pests, but also in the veterinary medicine sector against animal parasites (ecto- and endoparasites), such as hard ticks, soft ticks, mange mites, leaf mites, flies (biting and licking), parasitic fly larvae, lice, hair lice, feather lice and fleas. These parasites include:
From the order of the Anoplurida, for example, Haematopinus spp., Linognathus spp., Pediculus spp., Phtirus spp., Solenopotes spp.
From the order of the Mallophagida and the suborders Amblycerina and Ischnocerina, for example, Trimenopon spp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp., Lepikentron spp., Damalina spp., Trichodectes spp., Felicola spp.
From the order of the Diptera and the suborders Nematocerina and Brachycerina, for example, Aedes spp., Anopheles spp., Culex spp., Simulium spp., Eusimulium spp., Phlebotomus spp., Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp., Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp., Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp., Haematobia spp., Morellia spp., Fannia spp., Glossina spp., Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia spp., Sarcophaga spp., Oestrus spp., Hypoderma spp., Gasterophilus spp., Hippobosca spp., Lipoptena spp., Melophagus spp.
From the order of the Siphonapterida, for example, Pulex spp., Ctenocephalides spp., Xenopsylla spp., Ceratophyllus spp.
From the order of the Heteropterida, for example, Cimex spp., Triatoma spp., Rhodnius spp., Panstrongylus spp.
From the order of the Blattarida, for example, Blatta orientalis, Periplaneta americana, Blattela germanba, Supella spp.
From the subclass of the Acari (Acarina) and the orders of the Meta- and Mesostigmata, for example, Argas spp., Ornithodorus spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp., Dermacentor spp., Haemophysalis spp., Hyalomma spp., Rhipicephalus spp., Dermanyssus spp., Raillietia spp., Pneumonyssus spp., Sternostoma spp., Varroa spp.
From the order of the Actinedida (Prostigmata) and Acaridida (Astigmata), for example, 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., Laminosioptes spp. The active compounds of the formula (I) according to the invention are also suitable for controlling arthropods which infest agricultural productive livestock, such as, for example, cattle, sheep, goats, horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys, ducks, geese and bees, other pets, such as, for example, dogs, cats, caged birds and aquarium fish, and also so-called test animals, such as, for example, hamsters, guinea pigs, rats and mice. By controlling these arthropods, cases of death and reduction in productivity (for meat, milk, wool, hides, eggs, honey etc.) should be diminished, so that more economic and easier animal husbandry is possible by use of the active compounds according to the invention.
The active compounds according to the invention are used in the veterinary sector and in animal husbandry in a known manner by enteral administration in the form of, for example, tablets, capsules, potions, drenches, granules, pastes, boluses, the feed-through process and suppositories, by parenteral administration, such as, for example, by injection (intramuscular, subcutaneous, intravenous, intraperitoneal and the like), implants, by nasal administration, by dermal use in the form, for example, of dipping or bathing, spraying, pouring on and spotting on, washing and powdering, and also with the aid of moulded articles containing the active compound, such as collars, ear marks, tail marks, limb bands, halters, marking devices and the like.
When used for cattle, poultry, pets and the like, the active compounds of the formula (I) can be used as formulations (for example powders, emulsions, free-flowing compositions), which comprise the active compounds in an amount of 1 to 80% by weight, directly or after 100 to 10 000-fold dilution, or they can be used as a chemical bath.
It has furthermore been found that the compounds according to the invention also have a strong insecticidal action against insects which destroy industrial materials.
The following insects may be mentioned as examples and as preferred - but without any limitation: Beetles, such as Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum, Xestobium rufovillosum, Ptilinus pecticornis, Dendrobium pertinex, Ernobius mollis, Priobium carpini, Lyctus brunneus, Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus spec. Tryptodendron spec. Apate monachus, Bostrychus capucins, Heterobostrychus brunneus, Sinoxylon spec. Dinoderus minutus;
Hymenopterons, such as Sirexjuvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus augur;
Termites, such as Kalotermes flavicollis, Cryptotermes brevis, Heterotermes indicola, Reticulitermes flavipes, Reticulitermes santonensis, Reticulitermes lucifugus, Mastotermes darwiniensis, Zootermopsis nevadensis, Coptotermes formosanus; Bristletails, such as Lepisma saccharina.
Industrial materials in the present connection are to be understood as meaning non-living materials, such as, preferably, plasties, adhesives, sizes, papers and cardboards, leather, wood and processed wood products and coating compositions.
In the following table, M+1 means the molecular ion peak, plus 1 am.u. (atomic mass unit), as observed in mass spectroscopy.
Figure imgf000054_0001
Table 1
ho
Figure imgf000054_0002
Figure imgf000055_0001
Figure imgf000056_0001
Figure imgf000057_0001
Figure imgf000058_0001
Figure imgf000059_0001
Figure imgf000060_0001
CD
Figure imgf000061_0001
O
Figure imgf000062_0001
Figure imgf000063_0001
Figure imgf000064_0001
Figure imgf000065_0001
Figure imgf000066_0001
Figure imgf000067_0001
Figure imgf000068_0001
Figure imgf000069_0001
Figure imgf000070_0001
CD
Figure imgf000071_0001
O
Figure imgf000072_0001
Figure imgf000073_0001
ho
Figure imgf000074_0001
OO
Figure imgf000075_0001
Figure imgf000076_0001
Figure imgf000077_0001
Figure imgf000078_0001
Figure imgf000079_0001
Figure imgf000080_0001
CD
Figure imgf000081_0001
Figure imgf000082_0001
Figure imgf000083_0001
ho
Figure imgf000084_0001
Figure imgf000085_0001
Figure imgf000086_0001
Figure imgf000087_0001
Figure imgf000088_0001
Figure imgf000089_0001
Figure imgf000090_0001
Figure imgf000091_0001
Figure imgf000092_0001
CD
Figure imgf000093_0001
CD
Figure imgf000094_0001
Figure imgf000095_0001
CD
Figure imgf000096_0001
CD
Figure imgf000097_0001
CD
Figure imgf000098_0001
CD
Figure imgf000099_0001
Figure imgf000100_0001
Figure imgf000101_0001
O O
Figure imgf000102_0001
Figure imgf000103_0001
O
Figure imgf000104_0001
Figure imgf000105_0001
O
Figure imgf000106_0001
O
Figure imgf000107_0001
O
Figure imgf000108_0001
O
Figure imgf000109_0001
Figure imgf000110_0001
Figure imgf000111_0001
Figure imgf000112_0001
Figure imgf000113_0001
hO
Figure imgf000114_0001
Figure imgf000115_0001
Figure imgf000116_0001
Figure imgf000117_0001
Figure imgf000118_0001
Figure imgf000119_0001
Figure imgf000120_0001
CD
Figure imgf000121_0001
ho
O
Figure imgf000122_0001
ho
Figure imgf000123_0001
ho
Figure imgf000124_0001
ho
Figure imgf000125_0001
ho
Figure imgf000126_0001
ho
Figure imgf000127_0001
ho
Figure imgf000128_0001
ho
Figure imgf000129_0001
ho
Figure imgf000130_0001
ho
Figure imgf000131_0001
Figure imgf000132_0001
Figure imgf000133_0001
Figure imgf000134_0001
Figure imgf000135_0001
Figure imgf000136_0001
Figure imgf000137_0001
Figure imgf000138_0001
Figure imgf000139_0001
Figure imgf000140_0001
Figure imgf000141_0001
O
Figure imgf000142_0001
Figure imgf000143_0001
Figure imgf000144_0001
Figure imgf000145_0001
Figure imgf000146_0001
Figure imgf000147_0001
Figure imgf000148_0001
Figure imgf000149_0001
Figure imgf000150_0001
CD
Figure imgf000151_0001
[S] Stereochemistry
We define: Chirality specification in the R-Group R1 + R2 is the specification of chirality in NR1R2:
en
O
Figure imgf000152_0001
For all other chiral R-Groups we define: The stereochemistry of the R-group ist the stereochemistry of a virtual compound, which we generate by 5 combination of the RGroup with 1.S.δ-triazine^-carboxylic acid at position 2 of the triazinecarboxylic acid.
Measurement of logP values was performed according EEC directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on reversed phase columns with the following methods:
10 Measurement of LC-MS was done at pH 2,7 with 0,1 % formic acid in water and with acetonitrile (contains 0,1 % formic acid) as eluent with a linear gradient from 10 % acetonitrle to 95 % acetonitrile.
Measurement was done at pH 2.3 with 0,1 % phosphoric acid and acetonitrile as eluent.
Measurement with LC-MS was done at pH 7.8 with 0,001 molar ammonium hydrogen carbonate solution in water as eluent with a linear gradient from 10 % acetonitrile to 95 % acetonitrile.
5
Calibration was done with not branched alkan2-ones (with 3 to 16 carbon atoms) with known logP-values (measurement of logP values using retention times with linear interpolation between successive alkanones).. lambda-maX-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
10 In table 1 , M+H (or M H) means the molecular ion peak, plus or minus 1 a.m.u. (atomb mass unit) respectively, as observed in mass spectroscopy and M (Apcl+) means the molecular ion peak as it was found via positive atmospheric pressure chemical ionisation in mass spectroscopy Molecular Weight measurement, Method:
Standard HCOOH £;
15 [m2] UPLC - LCT
[ml] LCT - ESI
The following examples illustrate in a non-limiting manner the efficacy of the compounds of formula (I) according to the invention.
Example A: In vivo protective test on Venturia inaepualis in apples Solvent 24,5 parts by weight of acetone
24,5 parts by weight of dimethylacetamide Emulsifier 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are inoculated with an aqueous conidia suspension of the causal agent of apple scab (Venturia inaequalis) and then remain for 1 day in an incubation cabinet at approximately 2O0C and a relative atmospheric humidity of 100 %.
The plants are then placed in a greenhouse at approximately 210C and a relative atmospheric humidity of approximately 90 %.
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of IOOppm of active ingredient: Examples Nr. 1 , 2, 13, 1 18, 121 , 201 , 228, 235, 236, 238, 239, 250, 255, 256, 263, 265, 267, 270, 272, 315, 328, 330, 345, 357, 362, 370, 448, 453, 457, 464, 483, 502, 515, 602, 604, 610, 614, 619, 647, 648, 649, 650, 699, 716, 717, 732, 733, 734, 745, 748, 752, 753, 754, 756, 757, 758, 760, 761 , 762, 763, 764, 765, 769, 771, 780, 781, 782, 786, 788, 790, 799, 800, 801, 802, 803, 814, 815, 816, 820, 822, 823, 824, 825, 866, 868, 1617, 1654, 1661, 1711, 1716, 1726, 1729, 1730, 1769, 1771, 1777, 1778, 1783, 1788, 1793, 1794, 1795, 1797, 1798, 1799, 1800, 1803, 1804, 1810, 1814, 1815, 1816, 1817, 1819, 1821, 1822, 1823, 1825, 1826, 1847, 1852, 1857, 1859, 1867, 1870, 1898, 1900, 1902, 1903, 1910, 1911, 1912, 1913, 1916, 1917, 1918, 1947, 1957, 1959, 1963, 1974, 1979, 1980, 1982, 1983, 1986, 1987, 1989, 1994, 1996, 2001, 2009, 2010, 2012, 2013, 2020, 2023, 2024, 2025, 2026, 2027, 2050, 2053, 2148, 2155, 2183, 2211, 2215, 2228, 2231, 2235, 2244, 2267, 2271, 2275, 2324, 2325, 2442, 2448, 2452, 2453, 2454, 2455, 2456, 2457, 2458, 2459, 2460, 2465, 2467, 2468, 2469, 2474, 2475, 2477, 2478, 2480, 2487, 2489, 2505, 2593, 2594, and 2595. Example B: In vivo protective test on Botrytis cinerea in beans Solvent 24,5 parts by weight of acetone
24,5 parts by weight of dimethylacetamide Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound. After the spray coating has dried on, 2 small pieces of agar covered with growth of Botrytis cinerea are placed on each leaf. The inoculated plants are placed in a darkened chamber at 2O0C and a relative atmospheric humidity of 100%.
2 days after the inoculation, the size of the lesions on the leaves is evaluated. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of 250ppm of active ingredient: Examples Nr. 1 , 2, 13, 73, 118, 121 , 228, 235, 236, 238, 250, 255, 256, 267, 270, 272, 315, 328, 357, 362, 370, 450, 453, 475, 502, 515, 604, 619, 647, 648, 649, 650, 716, 717, 732, 733, 748, 752, 753, 754, 756, 757, 758, 760, 761 , 763, 764, 765, 769, 778, 780, 781 , 782, 786, 788, 799, 801 , 802, 803, 804, 813, 816, 822, 824, 825, 868, 1654, 1716, 1726, 1729, 1730, 1769, 1771 , 1777, 1783, 1788, 1793, 1794, 1795, 1797, 1798, 1799, 1800, 1803, 1804, 1806, 1810, 1814, 1815, 1816, 1817, 1821 , 1822, 1823, 1826, 1844, 1847, 1850, 1852, 1859, 1864, 1867, 1870, 1871 , 1875, 1898, 1900, 1902, 1903, 1910, 1911 , 1912, 1913, 1914, 1916, 1917, 1918, 1947, 1959, 1967, 1974, 1982, 1983, 1984, 1986, 1987, 1989, 1996, 2001 , 2009, 2010, 2011 , 2012, 2013, 2020, 2023, 2025, 2027, 2029, 2036, 2041 , 2050, 2053, 2148, 2183, 2211 , 2215, 2228, 2231 , 2235, 2267, 2271 , 2275, 2324, 2325, 2442, 2448, 2452, 2453, 2454, 2455, 2456, 2457, 2458, 2459, 2460, 2465, 2467, 2468, 2469, 2474, 2475, 2477, 2480, 2487, 2489, 2593, 2594, and 2595.
Example C: In vivo protective test on Sphaerotheca fuliginea. in cucumber Solvent 49 parts by weight of N, N - Dimethylformamide
Emulsifier 1 part by weight of Alkylarylpolyglycolether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for preventive activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after this treatment, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. Then the plants are placed in a greenhouse at approximately 230C and a relative atmospheric humidity of approximately 70 %. The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of 500ppm of active ingredient: Examples. Nr. 1 , 2, 4, 6, 10, 13, 17, 18, 19, 20, 21 , 48, 56, 64, 65, 70, 71 , 89, 92, 97, 106, 107, 109, 152, 228, 235, 236, 238, 239, 242, 250, 251 , 252, 256, 262, 263, 265, 267, 270, 272, 286, 328, 330, 362, 367, 370, 442, 449, 451 , 453, 455, 457, 466, 467, 474, 475, 483, 488, 489, 515, 524, 584, 585, 592, 594, 602, 604, 605, 607, 608, 610, 611 , 612, 614, 619, 620, 628, 629, 631 , 632, 633, 634, 635, 636, 637, 638, 647, 648, 649, 650, 658, 660, 661 , 706, 716, 717, 719, 720, 722, 723, 725, 726, 727, 732, 733, 735, 736, 745, 747, 748, 749, 751 , 752, 753, 754, 755, 756, 757, 758, 760, 761 , 762, 763, 764, 765, 766, 769, 771, 772, 773, 774, 776, 778, 779, 780, 781, 782, 783, 786, 787, 788, 790, 791, 792, 793, 799, 800, 801, 802, 803, 804, 806, 813, 814, 815, 816, 818, 820, 822, 823, 824, 825, 829, 832, 845, 847, 866, 868, 870, 874, 1608, 1625, 1665, 1707, 1711, 1713, 1714, 1726, 1729, 1730, 1737, 1762, 1769, 1771, 1773, 1777, 1778, 1785, 1788, 1793, 1794, 1795, 1797, 1798, 1799, 1800, 1803, 1804, 1805, 1806, 1807, 1810, 1811, 1814, 1815, 1816, 1817, 1819, 1821, 1822, 1825, 1826, 1828, 1832, 1833, 1842, 1844, 1845, 1846, 1847, 1849, 1850, 1851, 1852, 1855, 1857, 1859, 1860, 1861, 1862, 1864, 1866, 1867, 1870, 1871, 1872, 1874, 1875, 1897, 1898, 1900, 1902, 1903, 1907, 1908, 1909, 1910, 1911, 1912, 1913, 1915, 1916, 1917, 1918, 1925, 1934, 1946, 1947, 1948, 1950, 1954, 1956, 1957, 1959, 1960, 1961, 1962, 1963, 1964, 1966, 1967, 1972, 1974, 1977, 1980, 1983, 1984, 1986, 1987, 1989, 1990, 1991, 1994, 1996, 1997, 1998, 2001, 2004, 2007, 2008, 2009, 2010, 2011, 2012, 2014, 2018, 2020, 2021, 2023, 2025, 2026, 2027, 2029, 2033, 2036, 2041, 2044, 2045, 2050, 2051, 2052, 2053, 2069, 2077, 2078, 2079, 2081, 2101, 2108, 2145, 2146, 2147, 2148, 2155, 2183, 2184, 2190, 2191, 2196, 2208, 2211, 2215, 2224, 2227, 2228, 2230, 2231, 2232, 2233, 2234, 2235, 2241, 2244, 2245, 2252, 2255, 2258, 2260, 2261, 2262, 2263, 2264, 2265, 2266, 2267, 2268, 2269, 2270, 2271, 2272, 2273, 2274, 2275, 2277, 2278, 2279, 2281, 2283, 2287, 2297, 2314, 2324, 2325, 2404, 2419, 2420, 2423, 2442, 2443, 2444, 2445, 2446, 2448, 2449, 2450, 2451, 2452, 2453, 2454, 2455, 2456, 2457, 2458, 2459, 2460, 2461, 2462, 2463, 2465, 2466, 2467, 2468, 2469, 2474, 2475, 2477, 2478, 2479, 2480, 2481, 2482, 2483, 2484, 2485, 2486, 2487, 2488, 2489, 2490, 2491, 2494, 2496, 2498, 2500, 2502, 2505, 2507, 2513, 2518, 2523, 2529, 2533, 2539, 2543, 2549, 2553, 2557, 2559, 2564, 2582, 2586, 2589, 2591, 2593, 2594, 2595, 2604, 2607, 2616, 2622, 2625, 2626, 2628, 2630, 2632, 2634, 2635, 2636, 2637, 2641 , 2644, 2645, 2646,
2648, 2649, 2669, 2670, and 2671.
Example D: In vivo protective test on Leptosphaeria nodorum. in wheat
Solvent: 50 parts by weight of n,n-dinnethylacetannid Emulsifier 1 part by weight of alkylaryl polyglycol ether
To produce a suitable preparation of active compound, 1 part by weight of active compound or the compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with a preparation of active compound or active compound combination at the stated rate of application. After the spray coating has dried on, the plants are sprayed with a spore suspension of Leptosphaeria nodorum. The plants remain for
48 hours in an incubation cabinet at 2O0C and a relative atmospheric humidity of 100%.
The plants are placed in a greenhouse at a temperature of approximately 150C and a relative atmospheric humidity of approximately 80%. The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed.
In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of IOOOppm of active ingredient: Examples Nr. 1 , 2, 13, 73, 228, 247,
250, 251 , 263, 265, 267, 272, 362, 649, 650, 732, 868, 870, 1714, 1798, 1803, 1825, 1870, 1912, 1914, 1918, 1979, 1982, 1987, 2012, 2211 , 2261 , 2324, 2455, and 2466.
Example E: In vivo protective test on Pyrenophora teres, in barley
Solvent: 50 parts by weight of N, N-dimethylacetamide
Emulsifier 1 part by weight of alkylaryl polyglycol ether To produce a suitable preparation of active compound, 1 part by weight of active compound or the compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with a preparation of active compound at the stated rate of application. After the spray coating has dried on, the plants are sprayed with a conidia suspension of Pyrenophora teres. The plants remain for 48 hours in an incubation cabinet at 2O0C and a relative atmospheric humidity of 100%.
The plants are placed in a greenhouse at a temperature of approximately 2O0C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 10 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 70% or even higher at a concentration of IOOOppm of active ingredient: Examples Nr. 2, 4, 73, 118, 119, 120, 121 , 228, 238, 247, 256, 262, 263, 265, 272, 302, 345, 355, 357, 362, 444, 649, 650, 710, 804, 813, 1617, 1633, 1654, 1714, 1769, 1798, 1804, 1810, 1821 , 1870, 1909, 1918, 1982, 1983, 1989, 1994, 2009, 2020, 2023, 2024, 2027, 2211 , and 2266.
Example F: In vivo protective test on Pyricularia oryzae. in rice
Solvent: 28,5 parts by weight of acetone
Emulsifier 1 ,5 parts by weight of polyoxyethylene alkyl phenyl ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of rice blast Pyricularia oryzae The plants are then placed in an incubator at approximately 250C and a relative atmospheric humidity of approximately 100% for 1 day.
The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient: Examples Nr. 1 , 2, 4, 19, 73, 1 18, 1 19, 120, 121 , 228, 238, 241 , 242, 250, 251 , 262, 267, 270, 272, 273, 449, 453, 467, 483, 605, 607, 608, 609, 610, 612, 622, 699, 717, 718, 719, 725, 752, 753, 754, 755, 756, 757, 758, 760, 761 , 762, 766, 769, 790, 799, 800, 802, 803, 804, 806, 813, 814, 822, 868, 887, 914, 915, 1630, 1707, 1716, 1726, 1762, 1766, 1769, 1777, 1793, 1797, 1798, 1799, 1800, 1803, 1804, 1821 , 1856, 1867, 1898, 1902, 1903, 1907, 1912, 1913, 1914, 1974, 1975, 1976, 1977, 1979, 1980, 1981 , 1982, 1984, 1986, 1987, 1989, 1990, 1994, 1996, 1997, 1998, 2012, 2016, 2021 , 2027, 2071 , 2147, 2148, 2149, 2155, 2183, 2191 , 2224, 2227, 2228, 2231 , 2234, 2235, 2261 , 2267, 2454, 2455, 2456, 2459, 2461 , 2500, and 2518.
Example G: In vivo protective test on Rhizoctonia solani. in rice
Solvent: 28,5 parts by weight of acetone
Emulsifier 1 ,5 parts by weight of polyoxyethylene alkyl phenyl ether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with a hypha of the causal agent of rice sheath blight Rhizoctonia solani. The plants are then placed in an incubator at approximately 250C and a relative atmospheric humidity of approximately 100%. The test is evaluated 4 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient : Examples Nr. 1 , 124, 887, 1867, 1976, 1981 , 1982, 1984, 1986, and 2015.
Example H: In vivo protective test on Cochliobolus miyabeanus. in rice Solvent 28,5 parts by weight of acetone
Emulsifier 1 ,5 parts by weight of polyoxyethylene alkyl phenyl ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of rice brown spot Cochliobolus miyabeanus. The plants are then placed in an incubator at approximately 250C and a relative atmospheric humidity of approximately 100% for 1 day. The test is evaluated 4 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compound according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient: Example Nr. 2.
Example I: In vivo protective test on Phakopsora pachyrhizi. in rice Solvent 28,5 parts by weight of acetone
Emulsifier 1 ,5 parts by weight of polyoxyethylene alkyl phenyl ether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration. To test for protective activity, young plants are sprayed with the preparation of active compound at the stated rate of application. One day after spraying, the plants are inoculated with an aqueous spore suspension of the causal agent of soybean rust Phakopsora pachyrhizi. The plants are then placed in a greenhouse at approximately 2O0C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 11 days after the inoculation. 0% means an efficacy which corresponds to that of the control, while an efficacy of 100% means that no disease is observed. In this test the following compounds according to the invention showed efficacy of 80% or even higher at a concentration of 250ppm of active ingredient: Examples Nr. 1 , 267, 1771 , 1959, 1987, 2009, and 2026.
Example J: Lucillia cuprina - test (LUCICU)
Solvent: dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with water to the desired concentration.
Approximately 20 -30 (Lucilia cuprina larvae) are transferred into a test tube containing 1cm3 of minced horse meat and 0.5 ml aqueous dilution of test compound.
After 2 days mortality in % is determined. 100 % means that all the larvae have been killed;
0 % means that none of the larvae have been killed. In this test for example, the following compounds from the preparation examples showed
100 % activity at 100 pm rate:
Ex no : 335
Example K: Boophilus microplus - test (BOOPMI Injection) Solvent: dimethyl sulfoxide
To produce a suitable preparation of active compound, 10 mg of active compound are dissolved in 0.5 ml solvent, and the concentrate is diluted with solvent to the desired concentration. Five adult engorged female ticks (Boophilus microplus) are injected with compound solution into the abdomen. Ticks are transferred into replica plates and incubated in a climate chamber for a period of time. Egg deposition of fertile eggs is monitored.
After 7 days mortality in % is determined. 100 % means that all eggs are infertile; 0 % means that all eggs are fertile.
In this test for example, the following compounds from the preparation examples showed
80 % activity at 20μg / animal: Ex no : 267, 804, 813 In this test for example, the following compounds from the preparation examples showed 100 % activity at 20μg / animal: Ex no : 453
Example L: Mvzus persicae - test; (MYZUPE spray application)
Solvent: 78.0 parts by weight acetone
1.5 parts by weight dimethylformamide
Emulsifier: 0.5 parts by weight alkylarylpolyglycolether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Chinese cabbage (Brassica pekinesis) leaf-disks infected with all instars of the green peach aphid (Myzus persicae), are sprayed with a preparation of the active ingredient at the desired concentration.
After 6 days mortality in % is determined. 100% means that all aphids have been killed; 0% means that none of the aphids have been killed.
In this test for example, the following compounds from the preparation examples showed
80 % activity at a rate of 500 g/ha :
Ex no : 73, 1837, 1916, 2269, 2273, 2570, 2595, 292, 866, 2420
In this test for example, the following compounds from the preparation examples showed 90 % activity at a rate of 500 g/ha :
Ex no : 2558
In this test for example, the following compounds from the preparation examples showed
100 % activity at a rate of 500 g/ha :
Ex no: 991, 1822, 2414, 2539, 2569, 2607
Example M: Phaedon cochleariae - test; (PHAECO spray application) Solvent: 78.0 parts by weight of acetone
1.5 parts by weight of dimethylformamide Emulsifier: 0.5 parts by weight of alkylaryl polyglycolether To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Chinese cabbage (Brassica pekinesis) leaf-disks are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf disks are infested with mustard beetle larvae (Phaedon cochleariae). After 7 days mortality in % is determined. 100 % means that all beetle larvae have been killed and 0 % means that none of the beetle larvae have been killed.
In this test for example, the following compounds from the preparation examples showed 83 % activity at application rate of 500 g/ha: Ex no : 1759, 1764, 1841 , 359
In this test for example, the following compounds from the preparation examples showed
100 % activity at application rate of 500 g/ha:
Ex no : 1710, 2190, 2406, 2414, 335, 336, 341 , 360
Example N: Spodoptera fruqiperda -test (SPODFR spray application)
Solvent: 78.0 parts by weight acetone
1.5 parts by weight dimethylformamide
Emulsifier: 0.5 parts by weight alkylarylpolyglycolether
To produce a suitable preparation of the active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is dilutes with emulsifier-containing water to the desired concentration. Maize (Zea mais) leaf sections are sprayed with a preparation of the active ingredient of the desired concentration. Once dry, the leaf sections are infested with fall armyworm larvae (Spodoptera frugiperda).
After 7 days mortality in % is determined. 100% means that all caterpillars have been killed and 0% means that none of the caterpillars have been killed.
In this test for example, the following compounds from the preparation examples showed
83 % activity at application rate of 500 g/ha:
Ex no : 120, 341 , 359
In this test for example, the following compounds from the preparation examples showed 100 % activity at application rate of 500 g/ha:
Ex no : 163, 335, 613, 1716
Example O: Tetranvchus urticae - test: OP-resistant (TETRUR spray application) Solvent: 78.0 parts by weight acetone 1.5 parts by weight dimethylformamide
Emulsifier: 0.5 parts by weight alkylarylpolyglycolether
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. French beans (Phaseolus vulgaris) which are heavily infested with all stages of the two spotted spidermite (Tetranychus urticae), are sprayed with a preparation of the active ingredient at the desired concentration. After 6 days mortality in % is determined. 100% means that all spider mites have been killed and 0% means that none of the spider mites have been killed. In this test for example, the following compounds from the preparation examples showed 80 % activity at application rate of 500 g/ha: Ex no : 1832, 2423
In this test for example, the following compounds from the preparation examples showed 85 % activity at application rate of 500 g/ha: Ex no : 2607
In this test for example, the following compounds from the preparation examples showed 95 % activity at application rate of 500 g/ha: Ex no : 1710
Example P: Meloidoqvne test (MELGIN)
Solvent: 80.0 parts by weight of acetone
To produce a suitable preparation of active compound, 1 part by weight of active compound is mixed with the stated amount of solvent, and the concentrate is diluted with emulsifier- containing water to the desired concentration .Vessels are filled with sand, a solution of the active ingredient, a suspension containing eggs and larvae of Meloidogyne incognita and salad seeds. The salad seeds germinate and the seedlings grow. Galls develop in the roots. After 14 days the nematicidal activity is determined on the basis of the percentage of gall formation. 100% means that no galls were found; 0% means that the number of galls found on the roots of the treated plants was equal to that in untreated control plants. In this test for example, the following compounds from the preparation examples showed 90 % activity at application rate of 20 ppm: Ex no : 1764
In this test for example, the following compounds from the preparation examples showed 90 % activity at application rate of 20 ppm: Ex no : 1730, 1759
Example Q: Mvzus-Test; oral (MYZUPE O) Solvent: 80.0 parts by weight of acetone
To produce a suitable preparation of active compound, 1 part by weight of active compound ist mixed with the stated amount of solvent and emulsifier, and the concentrate is diluted with emulsifier-containing water to the desired concentration. Containers are infested with a mixed population of the green peach aphid (Myzus persicae), the aphids suck on a preparation of the active compound at the desired concentration.
After 5 days mortality in % is determined. 100 % means that all aphids have been killed; 0 % means that none of the aphids have been killed.
In this test for example, the following compounds from the preparation examples showed
100 % activity at application rate of 100 ppm:
Ex no : 2420, 314

Claims

1. A compound of formula (I)
Figure imgf000165_0001
(I) wherein
• R1, R2 and R3 independently represent hydrogen, a substituted or non-substituted Cr C8-alkyl, a substituted or non-substituted tri(C1-C8-alkyl)silyl-Ci-C8-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3- C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, C3-C8-cycloalkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (CrC6-alkoxyimino)- d-Ce-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-CrC6-alkyl, a substituted or non- substituted (benzyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted aryl-[ CrC8]- alkyl, a substituted or non-substituted Ci-C8-alkyl-(n-alkyl)-imidoyl, a substituted or non- substituted Ci-C8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-(n-alkyl)- imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, amino-(n- alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(n- alkyl)-imidoyl, a substituted or non-substituted aryl-amino-(n-alkoxy)-imidoyl, a substituted or non-substituted Ci-C8-alkyl-amino-(n-alkyl)-imidoyl, a substituted or non- substituted Ci-C8-alkyl-amino-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8- alkoxy-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8-alkoxy-(n-alkoxy)- imidoyl, a substituted or non-substituted CrC8-aryloxy-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8-aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted C1-C8- thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, a substituted or non- substituted d-Cs-alkyl-carbonyl, a substituted or non-substituted CrC8-halogenoalkyl- carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, amino-carbonyl, hydrazino-carbonyl, a substituted or non-substituted aryl-amino- carbonyl, a substituted or non-substituted d-Cs-alkyl-carbamoyl, a substituted or non- substituted d-Cs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted d-C8-alkoxy- carbonyl, a substituted or non-substituted d-Cs-thioalkyl-carbonyl, a substituted or non- substituted thioaryl-carbonyl, a substituted or non-substituted d-Cs-alkyl-thiocarbonyl, a substituted or non-substituted d-Cs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino-thiocarbonyl, a substituted or non- substituted aryloxy-carbamothioyl, a substituted or non-substituted d-C8-alkoxy- carbamothioyl, a substituted or non-substituted d-Cs-alkyl-hydrazino-thiocarbonyl, a substituted or non-substituted d-Cs-alkyl-carbamothioyl, a substituted or non- substituted d-Cs-halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, hydroxy- thiocarbonyl, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non- substituted d-C8-alkoxy-thiocarbonyl, a substituted or non-substituted d-C8-thioalkyl- thiocarbonyl, a substituted or non-substituted thioaryl-thiocarbonyl, cyano, a substituted or non-substituted d-C8-alkyl-amino, a substituted or non-substituted di-d-C8-alkyl- amino, a substituted or non-substituted d-drhalogenoalkyl-amino, a substituted or non-substituted di-d-drhalogenoalkyl-amino, a substituted or non-substituted aryl- amino, a substituted or non-substituted di-aryl-amino, amino-carbonyl-amino, formyl- amino, a substituted or non-substituted aryl-amino-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted d-C8-alkyl- carbamoyl-amino, a substituted or non-substituted d-Cs-alkyl-carbonyl-amino, amino- thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl- amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non- substituted d-Cs-alkoxy-thiocarbonyl-amino, a substituted or non-substituted C1-C8- alkylamino-thiocarbonyl-amino, a substituted or non-substituted d-C8-alkyl- thiocarbonyl-amino, amino, a substituted or non-substituted aryl-hydrazino, a substituted or non-substituted d-C8-alkyl-hydrazino, hydroxy-amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted d-C8-alkoxy-amino, a substituted or non-substituted alkyl-sulphenyl-amino, a substituted or non-substituted aryl-sulphenyl-amino, a substituted or non-substituted Ci-C8-alkyl-amino-silyl, a substituted or non-substituted di-Ci-C8-alkyl-amino-silyl, a substituted or non-substituted alkyl-sulphinyl-amino, a substituted or non-substituted aryl-sulphinyl-amino, amino- sulphinyl-amino, a substituted or non-substituted CrC8-alkoxy-sulfonyl-annino, hydroxy- sulfonyl-amino, a substituted or non-substituted aryloxy-sulfonyl-amino, amino-sulfonyl- amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non- substituted aryl-sulfonyl-amino, a substituted or non-substituted d-C8-alkylamino- sulfonyl-amino, a substituted or non-substituted d-C8-alkyl-sulfonyl-annino, nitro, nitroso, a substituted or non-substituted d-C8-alkyl-oxy, a substituted or non- substituted d-Cs-alkyl-oxyalkyl-oxy, a substituted or non-substituted C1-C8- halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, formamidino-oxy, amino- carbonyl-oxy, formyl-oxy, a substituted or non-substituted aryl-carbonyl-oxy, a substituted or non-substituted d-Cs-alkyl-carbonyl-oxy, hydroxy-thiocarbonyl-oxy, a substituted or non-substituted aryl-thiocarbonyl-oxy, a substituted or non-substituted C1- C8-alkyl-thiocarbonyl-oxy, hydroxy, amino-oxy, a substituted or non-substituted aryl- amino-oxy, a substituted or non-substituted C-rCs-alkyl-amino-oxy, a substituted or non- substituted aryl-silyloxy, a substituted or non-substituted CrC8-alkyl-silyloxy, , a substituted or non-substituted CrC8-alkyl-sulfonyl-oxy, a substituted or non-substituted d-C8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, thiol, a substituted or non-substituted Ci-C8-alkyl-silyl, a substituted or non-substituted C1-C8- alkyl-sulphinyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non- substituted Ci-C8-alkyl-sulphonyl, a substituted or non-substituted d-C8-halogenoalkyl- sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-amino- sulphonyl, a substituted or non-substituted d-Cs-alkyl-hydrazino-sulfonyl, a substituted or non-substituted d-C8-alkyl-amino-sulphonyl, a substituted or non-substituted C1-C8- halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, hydroxy-sulphonyl, a substituted or non-substituted aryloxy-sulphonyl, a substituted or non-substituted C1-C8- alkoxy-sulphonyl, halogen, a group selected in the list consisting of A1 to A68
Figure imgf000167_0001
Figure imgf000168_0001
Figure imgf000169_0001
Figure imgf000170_0001
o wherein Z1, Z2, Z3, Z4, Z5 and Z6 independently represent a substituted or non- substituted C-rCs-alkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C"rC8- alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non- substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted C-rCs-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non- substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-Ci-C6-alkyl group, a substituted or non-substituted (Ci-C6-alkoxyimino)-Ci-C6-alkyl, a substituted or non- substituted (C2-C6-alkenyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted (benzyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted aryl-[ CrC8]-alkyl, a substituted or non-substituted Ci-C8-alkyl-(n-alkyl)-imidoyl, a substituted or non- substituted Ci-C8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-(n- alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(n-alkyl)-imidoyl, a substituted or non-substituted aryl- amino-(n-alkoxy)-imidoyl, a substituted or non-substituted d-C8-alkyl-amino-(n- alkyl)-imidoyl, a substituted or non-substituted CrC8-alkyl-amino-(n-alkoxy)- imidoyl, hydroxy-(n-alkyl)-imidoyl, hydroxy-(n-alkoxy)-imidoyl, a substituted or non-substituted Ci-C8-alkoxy-(n-alkyl)-innidoyl, a substituted or non-substituted Ci-C8-alkoxy-(n-alkoxy)-innidoyl, a substituted or non-substituted CrC8-aryloxy- (n-alkyl)-imidoyl, a substituted or non-substituted d-C8-aryloxy-(n-alkoxy)- imidoyl, a substituted or non-substituted Ci-C8-thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, a substituted or non-substituted CrC8-alkyl- carbonyl, a substituted or non-substituted d-Cs-halogenoalkyl-carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, amino- carbonyl, hydrazino-carbonyl, N-hydroxy-carbamoyl, a substituted or non- substituted aryl-amino-carbonyl, a substituted or non-substituted aryl-hydrazino- carbonyl, a substituted or non-substituted d-Cs-alkyl-hydrazino-carbonyl, a substituted or non-substituted d-Cs-alkyl-carbamoyl, a substituted or non- substituted d-Cs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, hydroxy-carbonyl, a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted d-C8-alkoxy-carbonyl, a substituted or non-substituted C1-C8- thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted d-Cs-alkyl-thiocarbonyl, a substituted or non-substituted C1- Cs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non- substituted aryl-thiocarbonyl, amino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl-hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non- substituted d-Cs-alkoxy-carbamothioyl, a substituted or non-substituted C1-C8- alkyl-hydrazino-thiocarbonyl, a substituted or non-substituted d-C8-alkyl- carbamothioyl, a substituted or non-substituted d-C8-halogenoalkyl- carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted d-Cs-alkoxy-thiocarbonyl, a substituted or non-substituted d-Cs-thioalkyl-thiocarbonyl, a substituted or non- substituted thioaryl-thiocarbonyl, cyano, hydrogen, a substituted or non- substituted d-C8-alkyl-amino, a substituted or non-substituted di-d-C8-alkyl- amino, a substituted or non-substituted d-C8-halogenoalkyl-amino, a substituted or non-substituted di-d-C8-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl-amino, a substituted or non- substituted aryl-(n-alkyl)-imidoyl-amino, a substituted or non-substituted aryl-(n- alkoxy)-imidoyl-amino, a substituted or non-substituted d-C8-alkyl-(n-alkyl)- imidoyl-amino, a substituted or non-substituted Ci-C8-alkyl-(n-alkoxy)-imidoyl- amino, amino-carbonyl-amino, formyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted aryloxy-carbonyl-amino, a substituted or non-substituted C-i-Cs-alkoxy-carbonyl-amino, a substituted or non- substituted C-i-Cs-alkyl-carbonyl-amino, amino-thiocarbonyl-amino, hydroxy- thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl- amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted C1- Cs-alkoxy-thiocarbonyl-amino, a substituted or non-substituted C-rCs-alkylamino- thiocarbonyl-amino, a substituted or non-substituted CrC8-alkyl-thiocarbonyl- amino, amino, hydrazino, a substituted or non-substituted aryl-hydrazino, a substituted or non-substituted CrC8-alkyl-hydrazino, hydroxy-amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted C1- Cs-alkoxy-amino, a substituted or non-substituted alkyl-sulphenyl-amino, a substituted or non-substituted aryl-sulphenyl-amino, a substituted or non- substituted CrC8-alkyl-amino-silyl, a substituted or non-substituted di-CrC8-alkyl- amino-silyl, amino-sulphinyl-amino, a substituted or non-substituted alkyl- sulphinyl-amino, a substituted or non-substituted aryl-sulphinyl-amino, amino- sulfonyl-amino, hydroxy-sulfonyl-amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non-substituted aryloxy-sulfonyl- amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non- substituted Ci-C8-alkoxy-sulfonyl-amino, a substituted or non-substituted C1-C8- alkyl-sulfonyl-amino, nitro, nitroso, a substituted or non-substituted CrC8-alkyl- oxy, a substituted or non-substituted CrC8-alkyl-oxyalkyl-oxy, a substituted or non-substituted d-C8-halogenoalkyl-oxy, a substituted or non-substituted aryl- oxy, a substituted or non-substituted aryl-(n-alkyl)-imidoyl-oxy, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl-oxy, a substituted or non-substituted C1- C8-(n-alkyl)-alkyl-imidoyl-oxy, a substituted or non-substituted CrC8-(n-alkoxy)- alkyl-imidoyl-oxy, formyl-oxy, a substituted or non-substituted aryl-carbonyl-oxy, a substituted or non-substituted C-rCs-alkyl-carbonyl-oxy, hydroxy, amino-oxy, a substituted or non-substituted aryl-am ino-oxy, a substituted or non-substituted C-rCs-alkyl-amino-oxy, a substituted or non-substituted aryl-silyloxy, a substituted or non-substituted CrC8-alkyl-silyloxy, amino-sulphonyl-oxy, a substituted or non- substituted arylamino-sulphonyl-oxy, a substituted or non-substituted aryl- sulphonyl-oxy, a substituted or non-substituted C-i-Cs-alkylamino-sulphonyl-oxy, a substituted or non-substituted CrC8-alkyl-sulfonyl-oxy, a substituted or non- substituted Ci-C8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, thiol, a substituted or non-substituted Ci-C8-alkyl-silyl, a substituted or non- substituted d-Cs-alkyl-sulphinyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non-substituted Ci-C8-alkyl-sulphonyl, a substituted or non- substituted d-C8-halogenoalkyl-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino- sulfonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non-substituted aryl-hydrazino-sulfonyl, a substituted or non-substituted C1-C8- alkyl-amino-sulfamoyl, a substituted or non-substituted d-C8-alkyl-hydrazino- sulfonyl, a substituted or non-substituted CrC8-alkyl-amino-sulphonyl, a substituted or non-substituted d-Cs-halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, hydroxy-sulphonyl, a substituted or non-substituted aryloxy- sulphonyl, a substituted or non-substituted CrC8-alkoxy-sulphonyl, halogen; K1 and K2 independently represent a hydrogen atom, a formyl group, a substituted or non-substituted carbaldehyde O-(CrC8-alkyl)oxime, a carbamoyl group, a N-hydroxycarbamoyl group, a formylamino group, a substituted or non- substituted Ci-C8-alkyl, a substituted or non-substituted tri(d-C8-alkyl)silyl-d-C8- alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non- substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted Ci-C8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non- substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a C2-C8- alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non- substituted Ci-C8-alkylamino, a substituted or non-substituted di-d-C8- alkylamino, a substituted or non-substituted d-C8-alkoxy, a substituted or non- substituted d-C8-halogenoalkoxy having 1 to 5 halogen atoms, a substituted or non-substituted C2-C8-alkenyloxy, a substituted or non-substituted C2-C8- halogenoalkenyloxy having 1 to 5 halogen atoms, a substituted or non- substituted C2-C8-alkynyloxy, a substituted or non-substituted C2-C8- halogenoalkynyloxy having 1 to 5 halogen atoms, a substituted or non-substituted d-Cs-alkylcarbonyl, a substituted or non-substituted N-(d-C8-alkoxy)-d-C8- alkanimidoyl, a substituted or non-substituted N -(C1 -C8-a IkOXy)-C1 -C8- halogenoalkanimidoyl having 1 to 5 halogen atoms, a substituted or non- substituted d-C8-halogenoalkylcarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted d-C8-alkylcarbamoyl, a substituted or non- substituted di-d-Cs-alkylcarbamoyl, a substituted or non-substituted N-C1-C8- alkyloxycarbamoyl, a substituted or non-substituted d-Cs-alkoxycarbamoyl, a substituted or non-substituted N-Ci-C8-alkyl-Ci-C8-alkoxycarbannoyl, a substituted or non-substituted d-C8-alkoxycarbonyl, a substituted or non- substituted d-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted d-Cs-alkylcarbamothioyl, a substituted or non- substituted di-d-Cs-alkylcarbannothioyl, a substituted or non-substituted N-CrC8- alkyloxycarbamothioyll, a substituted or non-substituted CrC8- alkoxycarbamothioyl, a substituted or non-substituted N-CrC8-alkyl-CrC8- alkoxycarbamothioyl, a substituted or non-substituted CrC8-alkylsulphinyl, a substituted or non-substituted CrC8-halogenoalkylsulphinyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkylsulphonyl, a substituted or non-substituted CrC8-halogenoalkylsulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted CrC8-alkylaminosulfamoyl, a substituted or non- substituted di-CrCs-alkylaminosulfamoyl, a substituted or non-substituted aryl, a substituted or non-substituted aryl-[ CrC8]-alkyl ; provided that R3 does not represent hydrogen and provided that R1 and R2 do not simultaneously represent hydrogen ; R4 and R5 independently represent a substituted or non-substituted d-C8-alkyl-(n- alkyl)-imidoyl, a substituted or non-substituted d-C8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, hydrazino-imidoyl, a substituted or non-substituted aryl-hydrazino-imidoyl, a substituted or non-substituted d-C8-alkyl-hydrazino-imidoyl, amino-(n-alkyl)-imidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl- amino-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-amino-(n-alkoxy)-imidoyl, a substituted or non-substituted d-C8-alkyl-amino-(n-alkyl)-imidoyl, a substituted or non- substituted Ci-C8-alkyl-amino-(n-alkoxy)-imidoyl, hydroxy-(n-alkyl)-imidoyl, hydroxy-(n- alkoxy)-imidoyl, a substituted or non-substituted d-C8-alkoxy-(n-alkyl)-imidoyl, a substituted or non-substituted d-C8-alkoxy-(n-alkoxy)-imidoyl, a substituted or non- substituted d-C8-aryloxy-(n-alkyl)-imidoyl, a substituted or non-substituted CrC8- aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted d-C8-thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, formyl, amino-carbonyl, hydrazino- carbonyl, a substituted or non-substituted aryl-amino-carbonyl, N-hydroxy-carbamoyl, a substituted or non-substituted aryl-hydrazino-carbonyl, a substituted or non-substituted aryloxy-carbamoyl, a substituted or non-substituted d-Cs-alkoxy-carbamoyl, a substituted or non-substituted d-Cs-alkyl-hydrazino-carbonyl, a substituted or non- substituted d-Cs-alkyl-carbamoyl, a substituted or non-substituted CrC8- halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted d-Cs-alkoxy-carbonyl, a substituted or non-substituted d-Cs-thioalkyl-carbonyl, a substituted or non-substituted thioaryl- carbonyl, a substituted or non-substituted d-Cs-alkyl-thiocarbonyl, a substituted or non- substituted d-Cs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino-thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted aryl- hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non-substituted d-Cs-alkoxy-carbamothioyl, a substituted or non- substituted d-Cs-alkyl-hydrazino-thiocarbonyl, a substituted or non-substituted C1-C8- alkyl-carbamothioyl, a substituted or non-substituted d-Cs-halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted d-C8-alkoxy-thiocarbonyl, a substituted or non- substituted d-Cs-thioalkyl-thiocarbonyl, a substituted or non-substituted thioaryl- thiocarbonyl, cyano, hydrogen, a substituted or non-substituted d-C8-alkyl-amino, a substituted or non-substituted di-d-C8-alkyl-amino, a substituted or non-substituted d- Cs-halogenoalkyl-amino, a substituted or non-substituted di-d-C8-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl- amino, amino-carbonyl-amino, formyl-amino, a substituted or non-substituted aryl- amino-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted d-C8-alkyl-carbamoyl-amino, a substituted or non- substituted Ci-C8-alkyl-carbonyl-amino, hydro xy-carbonyl-amino, amino-thiocarbonyl- amino, hydro xy-thiocarbonyl-amino, a substituted or non-substituted arylamino- thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted d-C8-alkoxy-thiocarbonyl-amino, a substituted or non-substituted d-C8-alkylamino- thiocarbonyl-amino, a substituted or non-substituted d-C8-alkyl-thiocarbonyl-amino, amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted d-C8-alkoxy-amino, amino-sulfonyl-amino, a substituted or non-substituted arylamino- sulfonyl-amino, a substituted or non-substituted aryl-sulfonyl-amino, a substituted or non-substituted Ci-C8-alkylamino-sulfonyl-amino, a substituted or non-substituted d- C8-alkyl-sulfonyl-annino, a substituted or non-substituted d-C8-alkyl-oxy, a substituted or non-substituted Ci-C8-alkyl-oxyalkyl-oxy, a substituted or non-substituted CrC8- halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, formamidino-oxy, amino- carbonyl-oxy, formyl-oxy, a substituted or non-substituted aryl-carbonyl-oxy, a substituted or non-substituted d-Cs-alkyl-carbonyl-oxy, hydrazino-carbonyl-oxy, a substituted or non-substituted aryl-amino-carbonyl-oxy, a substituted or non-substituted aryloxy-carbonyl-oxy, a substituted or non-substituted d-Cs-alkoxy-carbonyl-oxy, a substituted or non-substituted d-Cs-alkyl-amino-carbonyl-oxy, a substituted or non- substituted d-Cs-thioalkyl-carbonyl-oxy, a substituted or non-substituted thioaryl- carbonyl-oxy, hydroxy-thiocarbonyl-oxy, a substituted or non-substituted aryl- thiocarbonyl-oxy, a substituted or non-substituted d-Cs-alkyl-thiocarbonyl-oxy, amino- thiocarbonyl-oxy, a substituted or non-substituted arylamino-thiocarbonyl-oxy, a substituted or non-substituted aryloxy-thiocarbonyl-oxy, a substituted or non-substituted d-Cs-alkoxy-thiocarbonyl-oxy, a substituted or non-substituted d-C8-alkyl- carbamothioyl-oxy, a substituted or non-substituted d-Cs-thioalkyl-thiocarbonyl-oxy, a substituted or non-substituted thioaryl-thiocarbonyl-oxy, hydroxy, a substituted or non- substituted aryl-silyloxy, a substituted or non-substituted d-C8-alkyl-silyloxy, , a substituted or non-substituted d-C8-alkyl-silyl, a substituted or non-substituted aryl- sulphinyl, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, hydrazino- sulfonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non- substituted d-Cs-alkyl-hydrazino-sulfonyl, a substituted or non-substituted aryl- hydrazino-sulfonyl, a substituted or non-substituted d-C8-alkyl-annino-sulfannoyl, a substituted or non-substituted d-C8-alkyl-annino-sulphonyl, a substituted or non- substituted d-drhalogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, a group independently selected in the list consisting of A1 to A68 as defined for R1, R2 or R3 ; provided that at least one of R4 and R5 does not represent hydrogen ; as well as salts, N-oxides, metallic complexes and metalloidic complexes thereof.
2. A compound according to claim 1 wherein R1 and R2 independently represent hydrogen, a substituted or non-substituted d-C8-alkyl, a substituted or non-substituted tri(d- C8-alkyl)silyl-d-C8-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non- substituted tri(d-C8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted C1-C8- halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8- halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8- alkenyl, a substituted or non-substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-d-C6-alkyl group, a substituted or non-substituted (d-C6-alkoxyimino)-d-C6- alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-d-C6-alkyl, a substituted or non- substituted (C2-C6-alkynyloxyimino)-d-C6-alkyl, a substituted or non-substituted (benzyloxyimino)-CrC6-alkyl, a substituted or non-substituted aryl-[d-C8]-alkyl, a substituted or non-substituted d-Cs-alkyl-carbonyl, a substituted or non-substituted Ci-C8-halogenoalkyl- carbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-carbonyl, formyl, a substituted or non-substituted d-Cs-alkyl-carbamoyl, a substituted or non-substituted CrC8- halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non-substituted d-C8- alkyl-amino, a substituted or non-substituted di-CrC8-alkyl-amino, a substituted or non- substituted d-Cs-halogenoalkyl-amino, a substituted or non-substituted di-d-C8-halogenoalkyl- amino, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl- amino, formyl-amino, a substituted or non-substituted d-Cs-Alkyl-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted aryloxy-carbonyl-amino, a substituted or non-substituted d-Cs-alkoxy-carbonyl-amino, a substituted or non-substituted d-C8-alkyl-oxy, a substituted or non-substituted d-C8-alkyl-oxyalkyl-oxy, a substituted or non- substituted d-C8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, a substituted or non-substituted d-C8-alkyl-sulphenyl, a substituted or non-substituted aryl-sulphenyl, a substituted or non-substituted d-C8-Alkyl-silyl, a substituted or non-substituted d-C8-alkyl- sulphinyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non-substituted C1-C8- alkyl-sulphonyl, a substituted or non-substituted Ci-C8-halogenoalkyl-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-sulphonyl, a group A1.
3. A compound according to claim 2 wherein R1 and R2 independently represent a substituted or non-substituted Ci-C8-alkyl, a substituted or non-substituted tri(d-C8-alkyl)silyl- Ci-C8-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tri(d-C8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted Ci-C8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non- substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-d-C6-alkyl group, a substituted or non-substituted (d-C6-alkoxyinnino)-d-C6-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-d-C6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)- d-C6-alkyl, a substituted or non-substituted (benzyloxyimino)-d-C6-alkyl, a substituted or non- substituted aryl-[d-C8]-alkyl, hydrogen, a substituted or non-substituted aryl-amino, a substituted or non-substituted di-aryl-amino, a group A1.
4. A compound according to claim 3 wherein R1 and R2 independently represent a substituted or non-substituted alpha substituted benzyl, a substituted or non-substituted alkoxy- aryl, a substituted or non-substituted aryloxy-aryl, hydrogen, substituted or non-substituted cycloalkyl, halogenoalkyl, substituted or non-substituted 2-phenylethyl, and substituted or non- substituted alpha substituted alkyl.
5. A compound according to claims 1 to 4 wherein R1 and R2 independently represent 1- cyclopropylpropan-2-yl; 1-phenylethyl; 2-phenylethyl; 1-cyclohexylethyl; 1-ethylpropyl; 4-[4-
(trifluoromethyl)phenoxy]phenyl; 1 -cyclopropylpropan-2-yl; dicyclopropylmethyl; 1- cyclopropylethyl; 1-(4-ethoxyphenyl)ethyl; 1-(4-ethylphenyl)ethyl; 1-(4-methoxyphenyl)ethyl; 1- [4-(propan-2-yl)phenyl]ethyl; cyclopentyl; cyclohexyl; 4-methyl-cyclohexyl; 1-(3- methoxyphenyl)ethyl; 2-(4-chlorophenyl)ethyl; 2,2-dimethyl-propyl; 4,4,4-trifluorobutan-2-yl; 1- cyclopropylpropan-2-yl; 2-methylbutan-2-yl; 4-methylpentan-2-yl, hydrogen.
6. A compound according to claims 1 to 5 wherein one of R1 and R2 represents hydrogen.
7. A compound according to claims 1 to 6 wherein R3 represents a substituted or non- substituted CrC8-alkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-CrC8-alkyl, a substituted or non-substituted C3-C8-cycloalkyl, a substituted or non-substituted tri(d-C8- alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted CrC8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8- alkynyl, a substituted or non-substituted (hydroxyimino)-Ci-C6-alkyl group, a substituted or non- substituted (Ci-C6-alkoxyimino)-Ci-C6-alkyl, a substituted or non-substituted (C2-C6- alkenyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-d-C6- alkyl, a substituted or non-substituted (benzyloxyimino)-Ci-C6-alkyl, a substituted or non- substituted aryl-[d-C8]-alkyl, a substituted or non-substituted aryl-carbonyl, cyano, a substituted or non-substituted d-C8-alkyl-amino, a substituted or non-substituted di-d-C8-alkyl-amino, a substituted or non-substituted d-C8-halogenoalkyl-amino, a substituted or non-substituted di- d-C8-halogenoalkyl-amino, a substituted or non-substituted aryl-amino, a substituted or non- substituted di-aryl-amino, a substituted or non-substituted d-C8-alkyl-oxy, a substituted or non- substituted d-C8-alkyl-oxyalkyl-oxy, a substituted or non-substituted d-C8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, hydroxy, a substituted or non-substituted d-C8-alkyl- sulphenyl, a substituted or non-substituted aryl-sulphenyl, or halogen.
8. A compound according to claim 7 wherein R3 represents a substituted or non- substituted d-d-alkyl, a substituted or non-substituted tri(C1-C4-alkyl)silyl-C1-C4-alkyl, a substituted or non-substituted C3-C4-cycloalkyl, a substituted or non-substituted tri(d-C4- alkyl)silyl-C3-C4-cycloalkyl, a substituted or non-substituted d-C4-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C4-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, a substituted or non-substituted C2-C8- alkynyl, a substituted or non-substituted (hydroxyimino)-Ci-C4-alkyl group, a substituted or non- substituted (Ci-C4-alkoxyimino)-Ci-C4-alkyl, a substituted or non-substituted (C2-C4- alkenyloxyimino)-Ci-C4-alkyl, a substituted or non-substituted (C2-C4-alkynyloxyimino)-CrC4- alkyl, a substituted or non-substituted (benzyloxyimino)-d-C4-alkyl, a substituted or non- substituted aryl-[Ci-C4]-alkyl, halogen.
9. A compound according to claim 8 wherein R3 represents F, Cl, Br, I, a substituted or non-substituted d-C4-alkyl, C2-C8-alkynyl in particular ethynyl, CF3, cyclopropyl, benzyl.
10. A compound according to claims 1 to 9 wherein R4 and R5 independently represent a substituted or non-substituted CrC8-alkyl-(N-alkyl)-imidoyl, a substituted or non-substituted C1- C8-alkyl-(N-alkoxy)-imidoyl, a substituted or non-substituted aryl-(N-alkyl)-imidoyl, a substituted or non-substituted aryl-(N-alkoxy)-imidoyl, formamidino, amino-(N-alkyl)-imidoyl, amino-(N- alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(N-alkyl)-imidoyl, a substituted or non-substituted aryl-amino-(N-alkoxy)-imidoyl, a substituted or non-substituted d-C8-alkyl- amino-(N-alkyl)-imidoyl, a substituted or non-substituted Ci-C8-alkyl-amino-(N-alkoxy)-imidoyl, hydroxy-(N-alkyl)-imidoyl, hydroxy-(N-alkoxy)-imidoyl, a substituted or non-substituted C1-C8- alkoxy-(N-alkyl)-imidoyl, a substituted or non-substituted Ci-C8-alkoxy-(N-alkoxy)-imidoyl, a substituted or non-substituted Ci-C8-aryloxy-(N-alkyl)-imidoyl, a substituted or non-substituted Ci-C8-aryloxy-(N-alkoxy)-imidoyl, formyl, amino-carbonyl, a substituted or non-substituted aryl- amino-carbonyl, a substituted or non-substituted d-C8-alkyl-carbamoyl, a substituted or non- substituted d-Cs-halogenoalkyl-carbamoyl having 1 to 5 halogen atoms, a substituted or non- substituted d-C8-alkoxy-carbonyl, a substituted or non-substituted aryloxy-carbonyl, a substituted or non-substituted d-Cs-alkyl-thiocarbonyl, a substituted or non-substituted C1-C8- halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl- thiocarbonyl, amino-thiocarbonyl, a substituted or non-substituted aryl-carbamothioyl, a substituted or non-substituted d-Cs-alkyl-carbamothioyl, a substituted or non-substituted C1-C8- halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted d-Cs-alkoxy-thiocarbonyl, a substituted or non-substituted d-Cs-thioalkyl-thiocarbonyl, a substituted or non-substituted thioaryl- thiocarbonyl, hydrogen, a substituted or non-substituted d-C8-alkyl-annino, a substituted or non- substituted di-d-C8-alkyl-annino, a substituted or non-substituted d-C8-halogenoalkyl-annino, a substituted or non-substituted di-C-i-Cs-halogenoalkyl-amino, a substituted or non-substituted aryl-sulphonyl, amino-sulphonyl, a substituted or non-substituted aryl-amino-sulphonyl, a substituted or non-substituted d-Cs-alkyl-annino-sulphonyl, a substituted or non-substituted d- Cs-halogenoalkyl-amino-sulphonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-sulphonyl, a substituted or non-substituted Ci-C8-alkoxy-sulphonyl, hydroxy-sulphonyl, a group selected in the list consisting of A1 to A68.
11. A compound according to claim 10 wherein R4 and R5 independently represent formyl, hydrogen, a group A1, a group selected in the list consisting of A1 to A8, a non substituted phenyl, or a phenyl, substituted with 1 to 3 fluorine atoms, methyloxy, ethyloxy or trifluoromehtyl.
12. A compound of formula (II)
Figure imgf000180_0001
(II)
R3 represents a substituted or non-substituted CrC8-alkyl, a substituted or non- substituted tri(Ci-C8-alkyl)silyl-Ci-C8-alkyl, a substituted or non-substituted C3-C8- cycloalkyl, a substituted or non-substituted tri(CrC8-alkyl)silyl-C3-C8-cycloalkyl, a substituted or non-substituted d-C8-halogenoalkyl having 1 to 5 halogen atoms, a substituted or non-substituted C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms, a substituted or non-substituted a C2-C8-alkenyl, C3-C8-cycloalkenyl, a substituted or non- substituted C2-C8-alkynyl, a substituted or non-substituted (hydroxyimino)-CrC6-alkyl group, a substituted or non-substituted (CrC6-alkoxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkenyloxyimino)-CrC6-alkyl, a substituted or non-substituted (C2-C6-alkynyloxyimino)-Ci-C6-alkyl, a substituted or non-substituted (benzyloxyimino)- CrC6-alkyl, a substituted or non-substituted aryl-[ CrC8]-alkyl, cyano, halogen; R4 and R5 independently represent a substituted or non-substituted d-C8-alkyl-(n- alkyl)-imidoyl, a substituted or non-substituted CrC8-alkyl-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-(n-alkyl)-imidoyl, a substituted or non-substituted aryl-(n-alkoxy)-imidoyl, formamidino, hydrazino-imidoyl, a substituted or non-substituted aryl-hydrazino-imidoyl, a substituted or non-substituted d-C8-alkyl-hydrazino-innidoyl, amino-(n-alkoxy)-imidoyl, a substituted or non-substituted aryl-amino-(n-alkoxy)-innidoyl, a substituted or non-substituted Ci-C8-alkyl-annino-(n-alkoxy)-innidoyl, hydroxy-(n-alkyl)- imidoyl, hydroxy-(n-alkoxy)-imidoyl, a substituted or non-substituted d-C8-alkoxy-(n- alkyl)-imidoyl, a substituted or non-substituted Ci-C8-alkoxy-(n-alkoxy)-innidoyl, a substituted or non-substituted Ci-C8-aryloxy-(n-alkyl)-innidoyl, a substituted or non- substituted Ci-C8-aryloxy-(n-alkoxy)-imidoyl, a substituted or non-substituted CrC8- thioalkyl-imidoyl, a substituted or non-substituted thioaryl-imidoyl, formyl, hydrazino- carbonyl, N-hydroxy-carbamoyl, a substituted or non-substituted aryl-hydrazino- carbonyl, a substituted or non-substituted aryloxy-carbamoyl, a substituted or non- substituted C-rCs-alkoxy-carbamoyl, a substituted or non-substituted d-C8-alkyl- hydrazino-carbonyl, a substituted or non-substituted d-Cs-thioalkyl-carbonyl, a substituted or non-substituted thioaryl-carbonyl, a substituted or non-substituted C1-C8- alkyl-thiocarbonyl, a substituted or non-substituted d-Cs-halogenoalkyl-thiocarbonyl having 1 to 5 halogen atoms, a substituted or non-substituted aryl-thiocarbonyl, amino- thiocarbonyl, hydrazino-thiocarbonyl, a substituted or non-substituted aryl- carbamothioyl, a substituted or non-substituted aryl-hydrazino-thiocarbonyl, a substituted or non-substituted aryloxy-carbamothioyl, a substituted or non-substituted d-Cs-alkoxy-carbannothioyl, a substituted or non-substituted Ci-C8-alkyl-hydrazino- thiocarbonyl, a substituted or non-substituted d-Cs-alkyl-carbamothioyl, a substituted or non-substituted d-Cs-halogenoalkyl-carbamothioyl having 1 to 5 halogen atoms, a substituted or non-substituted aryloxy-thiocarbonyl, a substituted or non-substituted d- C8-alkoxy-thiocarbonyl, a substituted or non-substituted d-Cs-thioalkyl-thiocarbonyl, a substituted or non-substituted thioaryl-thiocarbonyl, cyano, hydrogen, a substituted or non-substituted d-C8-alkyl-amino, a substituted or non-substituted di-d-C8-alkyl- amino, a substituted or non-substituted d-C8-halogenoalkyl-amino, a substituted or non-substituted di-d-C8-halogenoalkyl-amino, a substituted or non-substituted aryl- amino, a substituted or non-substituted di-aryl-amino, amino-carbonyl-amino, formyl- amino, a substituted or non-substituted aryl-amino-carbonyl-amino, a substituted or non-substituted aryl-carbonyl-amino, a substituted or non-substituted d-C8-alkyl- carbamoyl-amino, a substituted or non-substituted d-Cs-alkyl-carbonyl-amino, hydroxy- carbonyl-amino, amino-thiocarbonyl-amino, hydroxy-thiocarbonyl-amino, a substituted or non-substituted arylamino-thiocarbonyl-amino, a substituted or non-substituted aryloxy-thiocarbonyl-amino, a substituted or non-substituted aryl-thiocarbonyl-amino, a substituted or non-substituted d-Cs-alkoxy-thiocarbonyl-amino, a substituted or non- substituted d-Cs-alkylamino-thiocarbonyl-amino, a substituted or non-substituted Cr Cs-alkyl-thiocarbonyl-amino, amino, a substituted or non-substituted aryloxy-amino, a substituted or non-substituted Ci-C8-alkoxy-annino, amino-sulfonyl-amino, a substituted or non-substituted arylamino-sulfonyl-amino, a substituted or non-substituted aryl- sulfonyl-amino, a substituted or non-substituted d-dralkylamino-sulfonyl-amino, a substituted or non-substituted d-dralkyl-sulfonyl-amino, a substituted or non- substituted d-Cs-alkyl-oxy, a substituted or non-substituted d-C8-alkyl-oxyalkyl-oxy, a substituted or non-substituted d-C8-halogenoalkyl-oxy, a substituted or non-substituted aryl-oxy, formamidino-oxy, amino-carbonyl-oxy, formyl-oxy, a substituted or non- substituted aryl-carbonyl-oxy, a substituted or non-substituted d-Cs-alkyl-carbonyl-oxy, hydrazino-carbonyl-oxy, a substituted or non-substituted aryl-am ino-carbonyl-oxy, a substituted or non-substituted aryloxy-carbonyl-oxy, a substituted or non-substituted C1- C8-alkoxy-carbonyl-oxy, a substituted or non-substituted d-C8-alkyl-ann ino-carbonyl- oxy, a substituted or non-substituted d-Cs-thioalkyl-carbonyl-oxy, a substituted or non- substituted thioaryl-carbonyl-oxy, hydroxy-thiocarbonyl-oxy, a substituted or non- substituted aryl-thiocarbonyl-oxy, a substituted or non-substituted d-C8-alkyl- thiocarbonyl-oxy, amino-thiocarbonyl-oxy, a substituted or non-substituted arylamino- thiocarbonyl-oxy, a substituted or non-substituted aryloxy-thiocarbonyl-oxy, a substituted or non-substituted d-Cs-alkoxy-thiocarbonyl-oxy, a substituted or non- substituted d-C8-alkyl-carbannothioyl-oxy, a substituted or non-substituted d-C8- thioalkyl-thiocarbonyl-oxy, a substituted or non-substituted thioaryl-thiocarbonyl-oxy, hydroxy, a substituted or non-substituted aryl-silyloxy, a substituted or non-substituted d-C8-alkyl-silyloxy, , a substituted or non-substituted d-C8-alkyl-silyl, a substituted or non-substituted aryl-sulphinyl, a substituted or non-substituted aryl-sulphonyl, amino- sulphonyl, hydrazino-sulfonyl, a substituted or non-substituted aryl-am ino-sulphonyl, a substituted or non-substituted d-C8-alkyl-hydrazino-sulfonyl, a substituted or non- substituted aryl-hydrazino-sulfonyl, a substituted or non-substituted d-C8-alkyl-amino- sulfamoyl, a substituted or non-substituted d-C8-alkyl-am ino-sulphonyl, a substituted or non-substituted d-C8-halogenoalkyl-am ino-sulphonyl having 1 to 5 halogen atoms, a group independently selected in the list consisting of A1 to A68 as defined for R1, R2 or
R3 ; provided that at least one of R4 and R5 does not represent hydrogen ; provided that it does not represent
■ 2-[(4-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid; ■ 2-[(2-methoxyphenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid; ■ 2-[(4-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(2-chlorophenyl)amino]-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-(phenylamino)-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid; ■ 2-(formylannino)-5-(propan-2-yl)-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(4-chloro-3-methoxyphenyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(3,4-dimethoxyphenyl)amino]-5-methyl-1 ,3-thiazole-4-carboxylic acid;
■ 2-[(4-chlorophenyl)amino]-5-nnethyl-1 ,3-thiazole-4-carboxylic acid;
■ 5-propyl-2-({[2'-(1 H-tetrazol-5-yl)biphenyl-4-yl]methyl}annino)-1 ,3-thiazole-4- carboxylic acid;
■ 5-ethyl-2-({[2'-(1 H-tetrazol-5-yl)biphenyl-4-yl]methyl}amino)-1 ,3-thiazole-4- carboxylic acid.
13. A fungicide, acaricide and/or insecticide composition comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claims 1 to 11 and an agriculturally acceptable support, carrier or filler.
14. A method for controlling phytopathogenic fungi of crops, acaricides and/or insects, characterized in that an agronomical Iy effective and substantially non-phytotoxic quantity of a compound according to claims 1 to 11 or a composition according to claim 13 is applied to the soil where plants grow or are capable of growing, to the leaves and/or the fruit of plants or to the seeds of plants.
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