WO2010130767A2 - Fungicide pyrazole carboxamides derivatives - Google Patents

Fungicide pyrazole carboxamides derivatives Download PDF

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Publication number
WO2010130767A2
WO2010130767A2 PCT/EP2010/056521 EP2010056521W WO2010130767A2 WO 2010130767 A2 WO2010130767 A2 WO 2010130767A2 EP 2010056521 W EP2010056521 W EP 2010056521W WO 2010130767 A2 WO2010130767 A2 WO 2010130767A2
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WO
WIPO (PCT)
Prior art keywords
substituted
alkyl
different
same
plants
Prior art date
Application number
PCT/EP2010/056521
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French (fr)
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WO2010130767A3 (en
Inventor
Guenter Bartels
Angela Becker
Juergen Benting
Christoph-Andreas Braun
Peter Dahmen
Philippe Desbordes
Christophe Dubost
Stéphanie Gary
Ulrich Görgens
Hiroyuki Hadano
Benoît HARTMANN
Thomas Knobloch
Marc Kosten
Norbert Lui
Ruth Meissner
Sergiy Pazenok
Rachel Rama
Arnd Voerste
Ulrike Wachendorff-Neumann
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Bayer Cropscience Ag
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Priority claimed from EP09356035A external-priority patent/EP2251331A1/en
Priority to PL10721444T priority Critical patent/PL2430000T3/en
Priority to NZ595589A priority patent/NZ595589A/en
Priority to KR1020117029950A priority patent/KR101726461B1/en
Priority to CA2761269A priority patent/CA2761269C/en
Priority to BRPI1007645-0A priority patent/BRPI1007645B1/en
Priority to BR122016026450-5A priority patent/BR122016026450B1/en
Priority to JP2012510284A priority patent/JP5824449B2/en
Application filed by Bayer Cropscience Ag filed Critical Bayer Cropscience Ag
Priority to MX2011012012A priority patent/MX2011012012A/en
Priority to DK10721444.7T priority patent/DK2430000T3/en
Priority to US13/319,614 priority patent/US8772266B2/en
Priority to CN201080022007.3A priority patent/CN102421757B/en
Priority to EP10721444.7A priority patent/EP2430000B1/en
Priority to AU2010247385A priority patent/AU2010247385B2/en
Priority to ES10721444.7T priority patent/ES2561215T3/en
Priority to EA201171409A priority patent/EA023111B1/en
Publication of WO2010130767A2 publication Critical patent/WO2010130767A2/en
Priority to UAA201114869A priority patent/UA107794C2/en
Publication of WO2010130767A3 publication Critical patent/WO2010130767A3/en
Priority to ZA2011/09214A priority patent/ZA201109214B/en
Priority to US14/166,773 priority patent/US9398767B2/en
Priority to PH12015501026A priority patent/PH12015501026A1/en
Priority to HRP20160062TT priority patent/HRP20160062T1/en
Priority to US15/188,164 priority patent/US9695126B2/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole 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
    • C07D231/16—Halogen atoms or nitro radicals
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/56—1,2-Diazoles; Hydrogenated 1,2-diazoles
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/02—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings
    • C07D401/12—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing two hetero rings linked by a chain containing hetero atoms as chain links
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
    • C07F7/02—Silicon compounds
    • C07F7/08—Compounds having one or more C—Si linkages
    • C07F7/0803—Compounds with Si-C or Si-Si linkages
    • C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
    • C07F7/0812—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te comprising a heterocyclic ring

Definitions

  • the present invention relates to pyrazole carboxamides derivatives, their process of preparation, their use as fungicide, and/or anti-mycotoxin active agents, and/or insecticide, and/or nematicide, particularly in the form of compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.
  • A represents a carbo-linked, partially saturated or unsaturated, 5-membered heterocyclyl group that can be substituted
  • T represents S or N substituted derivatives
  • Z represents a (un)substituted cycloalkyl.
  • A represents a carbo-linked 5-membered heterocyclyl group that can be substituted and Z 3 represents a substituted or non substituted C 3 .
  • C 7 cycloalkyl represents a substituted or non substituted C 3 .
  • A represents a carbo-linked, unsaturated or partially saturated, 5-mennbered heterocyclyl group that can be substituted and B represents an aromatic 5- or 6-mennbered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring.
  • B represents an aromatic 5- or 6-mennbered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring.
  • Y represents CR 5 or N
  • T represents S or O ;
  • X 1 and X 2 which can be the same or different, represent a chlorine or a fluorine atom ;
  • Z 1 represents a non substituted cyclopropyl or a cyclopropyl substituted by up to 2 atoms or groups which can be the same or different and which can be selected in the list consisting of halogen atoms ; cyano ; Ci-C 8 -alkyl ; or Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ;
  • Z 2 and Z 3 which can be the same or different, represent a hydrogen atom ; substituted or non substituted Ci-C 8 -alkyl ; substituted or non substituted C 2 -C 8 -alkenyl ; substituted or non substituted C 2 -C 8 -alkynyl ; cyano ; isonitrile ; nitro ; a halogen atom ; substituted or non substituted Ci-C 8 -alkoxy ; substituted or non substituted C 2 -C 8 -alkenyloxy ; substituted or non substituted C 2 -C 8 -alkynyloxy ; substituted or non substituted C 3 -C 7 - cycloalkyl ; substituted or non substituted Ci-C 8 -alkylsulfanyl ; substituted or non substituted Ci-C 8 -alkylsulfonyl ; substituted or non substituted Ci-C 8 -alkylsulfinyl
  • Z 3 and R 1 together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5-, 6- or 7-membered, partly saturated, carbo- or hetero- cycle comprising up to 3 heteroatoms and Z 2 is as herein described; or
  • R 1 , R 2 , R 3 , R 4 and R 5 which can be the same or different, represent a hydrogen atom; a halogen atom ; nitro ; cyano ; isonitrile ; hydroxyl ; sulfanyl ; amino ; pentafluoro- ⁇ 6 - sulfanyl ; substituted or non substituted d-C 8 -alkyl ; d-C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted d-C 8 -alkylamino ; substituted or non substituted di-d-C 8 -alkylamino ; substituted or non substituted d-C 8 -alkoxy ; d-C 8 -halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; d-C 8 -alkoxy-Ci-C 8 -al
  • C 8 -alkyl C- ⁇ -C 8 -alkoxy ; C- ⁇ -C 8 -alkylsulfanyl ; C- ⁇ -C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; d-C 8 -halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; tri(Ci-C 8 )alkylsilyl or tri(Ci- C 8 )alkylsilyl-Ci-C 8 -alkyl ;
  • 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 ; nitro ; hydroxyl ; cyano ; isonitrile ; amino ; thio ; a pentafluoro- ⁇ 6 -sulfanyl group ; formyl ; formyloxy ; formylamino ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)-C- ⁇ -C 6 -alkyl ; d-C 8 -alkyl ; a tri(C- ⁇ -C 8 -alkyl)silyl ; C 3 -C 8 -cycloalkyl ; C 1 -C 8 - halogenoalkyl having 1 to 5 halogen atoms ; a C 3 -C 8 -halogenocycloalkyl having 1 to 5 halogen atom
  • 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 that are known per se by the man ordinary skilled in the art.
  • halogen means fluorine, chlorine, bromine or iodine ;
  • heteroatom can be nitrogen, oxygen or sulphur ;
  • any alkyl, alkenyl or alkynyl group can be linear or branched ;
  • aryl means phenyl or naphthyl, optionally substituted ;
  • the two substituents together with the nitrogen atom to which they are linked can form a heterocyclyl group, preferably a 5- to 7-membered heterocyclyl group, that can be substituted or that can include other hetero atoms, for example a morpholino or piperidinyl group.
  • Preferred compounds of formula (I) according to the invention are those wherein Y represents CR 5 .
  • preferred compounds of formula (I) according to the invention are those wherein Z 1 represents a non substituted cyclopropyl.
  • Other preferred compounds of formula (I) according to the invention are those wherein Z 2 and Z 3 independently represent a hydrogen atom or a methyl.
  • More preferred compounds of formula (I) according to the invention are those wherein Z 2 represents a hydrogen atom and Z 3 represents a hydrogen atom or a methyl.
  • R 1 , R 2 , R 3 , R 4 and R 5 which can be the same or different, represent a hydrogen atom ; a halogen atom ; substituted or non substituted C- ⁇ -C 8 -alkyl ; C- ⁇ -C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C 3 -C 7 -cycloalkyl ; tri(C- ⁇ -C 8 -alkyl)silyl ; or substituted or non substituted C- ⁇ -C 8 -alkylsulfanyl.
  • More preferred compounds of formula (I) according to the invention are those wherein the substituent R 1 represents a halogen atom ; Ci-C 8 -alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C 3 -C 7 -cycloalkyl ; tri(Ci-C 8 -alkyl)silyl or d- C 8 -halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
  • R 1 and R 5 which can be the same or different, represent a halogen atom ; Ci-C 8 - alkyl ; Ci-C 8 -halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C 3 -C 7 -cycloalkyl; tri(Ci-C 8 -alkyl)silyl or Ci-C 8 -halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
  • R 5 - preferred features of Z 2 with preferred features of one or more T, X 1 , X 2 , Y, Z 1 , Z 3 , and R 1 to
  • R 5 ; - preferred features of R 1 with preferred features of one or more T, X 1 , X 2 , Y, Z 1 to Z 3 , and R 2 to
  • R 2 with preferred features of one or more T, X 1 , X 2 , Y, Z 1 to Z 3 , R 1 , and R 3 to R 5
  • - preferred features of R 3 with preferred features of one or more T, X 1 , X 2 , Y, Z 1 to Z 3 , R 1 , R 2 , R 4 , and R 5 ;
  • R 5 with preferred features of one or more T, X 1 , X 2 , Y, Z 1 to Z 3 , and R 1 to R 4 ;
  • the said preferred features can also be selected among the more preferred features of each of T, X 1 , X 2 , Y, Z 1 to Z 3 , and R 1 to R 5 ; so as to form most preferred subclasses of compounds according to the invention.
  • the present invention also relates to a process for the preparation of compounds of formula (I).
  • a process P1 for the preparation of compound of formula (Ia) as herein-defined for which T represents a oxygen atom as illustrated by the following reaction scheme :
  • N-Cyclopropylamines of formula are known (WO-2008/037789, WO-2007/087906, WO- 2006/120224 and WO-2009/016218) or can be prepared by known methods
  • Step 1 and 13 of process P1 is performed in the presence of an oxidant, and if appropriate in the presence of a solvent.
  • Steps 2 and 9 of process P1 are performed in the presence of acid halide, and if appropriate in the presence of a solvent.
  • Steps 4, 7 and 10 of process P1 are performed in the presence of an acid binder, and if appropriate in the presence of a solvent.
  • Steps 3 and 8 of process P1 are performed in the presence of a condensing agent, and if appropriate in the presence of a solvent.
  • Step 5 and 12 of process P1 is performed in the presence of a fluorinating agent, and if appropriate in the presence of a solvent.
  • Step 11 of process P1 is performed in the presence of a chlorinating agent and a lewis acid, and if appropriate in the presence of a solvent.
  • Z ⁇ Z 2 , Z 3 , Y, R 1 , R 2 ,R 3 ,R 4 , X 1 and X 2 are as herein-defined ;
  • W 1 represents a halogen atom or a hydroxyl
  • W 2 represents a halogen or a leaving group such as tosylate, mesylate or triflate group.
  • Pyrazoles derivatives of formula (Mh) may be prepared according to process P1.
  • N-cyclopropylamines of formula (IV) and methylene derivatives of formula (V) are known or may be prepared by known methods.
  • Step 1 of process P2 is performed in the presence of an acid binder or a condensing agent, and if appropriate in the presence of a solvent.
  • Step 2 of process P2 is performed in the presence of a solvent and if appropriate in the presence of an acid binder.
  • a process P3 for the preparation of compound of formula (Ib) as herein-defined for which T represent a sulfur atom as illustrated by the following reaction scheme :
  • Z 1 , Z 2 , Z 3 , Y, R 1 , R 2 ,R 3 ,R 4 , X 1 and X 2 are as herein-defined ;
  • Step 1 of process P3 is performed in the presence of a thionating agent and if appropriate in the presence of an acid binder and if appropriate in the presence of solvent.
  • Suitable oxidants for carrying out step 1 or 13 of process P1 according to the invention are in each case all inorganic and organic oxidant which are customary for such reactions. Preference is given to using benzyltriethylammonium permanganate; bromine; chlorine; m- chloroperbenzoic acid; chromic acid; chromium (Vl) oxide; hydrogen peroxide; hydrogen peroxide-boron trifluoride; hydrogen peroxide-urea; 2-hydroxyperoxyhexafluoro-2-propanol; Iodine; oxygen-platinum catalyst, perbenzoic acid; peroxyacetyl nitrate; potassium permanganate; potassium ruthenate; pyridinium dichromate; ruthenium (VIII) oxide; silver (I) oxide; silver (II) oxide; silver nitrite; sodium chlorite; sodium hypochlorite; 2,2,6,6- tetramethylpiperidin-1-oxyl.
  • Suitable acid halides for carrying out steps 2 and 9 of process P1 according to the invention are in each case all organic or inorganic acid halides which are customary for such reactions. Preference is given to using notably phosgene, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide; thionyl chloride; or carbon tetrachloride- triphenylphosphine.
  • Suitable acid binder for carrying out steps 4, 7 and 10 of process P1 , steps 1 and 2 of process P2 and process P3 according to the invention are in each case all inorganic and organic bases which are customary for such reactions.
  • alkaline earth metal alkali metal hydride, alkali metal hydroxides or alkali metal alkoxydes, 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, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate, and also ternary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, di-isopropyl-ethylamine, pyridine, methylethylpyridine,
  • Suitable condensing agent for carrying out steps 3 and 8 of process P1 and step 1 of process P2 according to the invention are in each case all condensing agents which are customary for such reactions.
  • carbodiimides such as N 1 N'- dicyclohexylcarbodiimide (DCC) or other customary condensing agents, notably phosphorous pentoxide, polyphosphoric acid, N,N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1 ,2- dihydroquinoline (EEDQ), triphenylphosphine/tetrachloromethane or bromo- tripyrrolidinophosphonium-hexafluorophosphate.
  • DCC N 1 N'- dicyclohexylcarbodiimide
  • EEDQ 2-ethoxy-N-ethoxycarbonyl-1 ,2- dihydroquinoline
  • triphenylphosphine/tetrachloromethane or
  • Suitable fluorinating agent for carrying out step 5 or 12 of process P1 according to the invention is in each case all fluorinating agents which are customary for such reactions. Preference is given to using cesium fluoride; potassium fluoride; potassium fluoride-calcium difluoride; tetrabutylammonium fluoride.
  • Suitable chlorination agent for carrying out step 1 1 of process P1 according to the invention is in each case all chlorination agents agents which are customary for such reactions (WO- 2007/062776). Preference is given to using tetrachlorosilane /aluminium trichloride, aluminium trichloride .
  • Suitable thionating agents for carrying out process P3 according to the invention can be sulphur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B 2 S 3 ), bis (diethylaluminium) sulfide ((AIEt 2 ) 2 S), ammonium sulfide ((NH 4 ) 2 S), phosphorous pentasulfide (P 2 S 5 ), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1 ,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc. Perkin 1 , (2001 ), 358.
  • S sulphur
  • H2S sulfhydric acid
  • Na2S sodium sulf
  • Suitable solvents for carrying out steps 1 to 13 of process P1 , steps 1 and 2 of process P2 and process P3 according to the invention are in each case all customary inert organic solvents.
  • reaction temperatures can independently be varied within a relatively wide range.
  • processes according to the invention are carried out at temperatures between O 0 C and 16O 0 C, preferably between 1O 0 C and 12O 0 C.
  • a way to control the temperature for the processes according to the invention is to use the micro-waves technology.
  • Steps 1 to 13 of process P1 and steps 1 and 2 of process P2 according to the invention are generally independently carried out under atmospheric pressure. However, in each case, it is also possible to operate under elevated or reduced pressure.
  • step 1 or 13 of process P1 When carrying out step 1 or 13 of process P1 according to the invention, generally 1 mol or other an excess of the oxidant is employed per mole of aldehyde of formula (Ma) or (Ng). It is also possible to employ the reaction components in other ratios.
  • step 2 and 9 of process P1 to the invention generally 1 mol or other an excess of the acid halides is employed per mole of acid of formula (lib) or (Me). It is also possible to employ the reaction components in other ratios.
  • step 5 or 12 of process P1 according to the invention When carrying out step 5 or 12 of process P1 according to the invention, generally 2 moles or other an excess of the fluorinating agent is employed per mole of chlorinated compound of formula (Na) or (lie). It is also possible to employ the reaction components in other ratios.
  • step 11 of process P1 according to the invention generally 0,2 - 0,3 mol of chlorinating agent is employed per mole of acid fluoride formula (Nd). It is also possible to employ the reaction components in other ratios.
  • 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, recrystallization or distillation, from any impurities that may 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 (lib)
  • X 2 represents a chlorine or a fluorine atom, preferably a fluorine atom
  • X 2 represents a chlorine or a fluorine atom, preferably a fluorine atom and W 3 represent a halogen atom preferably a chlorine atom;
  • X 2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
  • X 2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
  • X 2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
  • the present invention also relates to a composition, particularly a fungicide composition, comprising an effective and non-phytotoxic amount of an active compound of formula (I).
  • effective and non-phytotoxic amount means an amount of composition according to the invention that is sufficient to control or destroy the fungi, and/or insects, and/or nematicides, and/or weeds present or liable to appear on or around the crops, and that does not entail any appreciable symptom of phytotoxicity for the said crops.
  • Such an amount can vary within a wide range depending on the target, particularly fungus, to be controlled, the type of crop, the climatic conditions and the compounds included in the composition according to the invention. This amount can be determined by systematic field trials, that are within the capabilities of a person skilled in the art.
  • composition particularly a fungicide 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 that 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.
  • the presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when the vector agent for the application is water.
  • 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, that complies with the usual formulation techniques.
  • 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 that are ready to be applied to the plant or seed to
  • 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 normally a broadened spectrum of activity.
  • the mixtures with other fungicide compounds are particularly advantageous.
  • fungicide mixing partners can be selected in the following lists:
  • Inhibitors of the ergosterol biosynthesis for example (1.1 ) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11 ) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6
  • inhibitors of the respiratory chain at complex I or II for example (2.1 ) bixafen (581809-46-03), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) furametpyr (123572-88-3), (2.9) furmecyclox (60568-05-0), (2.10) isopyrazam (mixture of syn- epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS, 4SR, 9SR) (881685-58-1 ), (2.1 1 ) isopyrazam (anti-epimeric racemate 1 RS, 4SR, 9SR), (2.12) isopyrazam (anti-epimeric enantiomer 1 R,
  • inhibitors of the respiratory chain at complex III for example (3.1 ) amisulbrom (348635-87-0), (3.2) azoxystrobin (131860-33-8), (3.3) cyazofamid (120116-88-3), (3.4) dimoxystrobin (141600- 52-4), (3.5) enestroburin (238410-11-2) (known from WO 2004/058723), (3.6) famoxadone (131807-57-3) (known from WO 2004/058723), (3.7) fenamidone (161326-34-7) (known from WO 2004/058723), (3.8) fluoxastrobin (361377-29-9) (known from WO 2004/058723), (3.9) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.10) metominostrobin (133408-50-1 ) (known from WO 2004/058723), (3.11 ) orysastro
  • Inhibitors of the mitosis and cell division for example (4.1 ) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19-1 ), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11 ) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro- 7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1 ,2,4]triazolo[1 ,5-a]pyrimidine (2147
  • Inhibitors of the amino acid and/or protein biosynthesis for example (7.1 ) andoprim (23951- 85-1 ), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980- 18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7) and (7.7) pyrimethanil (53112-28-0).
  • Inhibitors of the ATP production for example (8.1 ) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9) and (8.4) silthiofam (175217-20-6).
  • Inhibitors of the cell wall synthesis for example (9.1 ) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (1 1113-80-7), (9.7) polyoxorim (22976-86- 9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0).
  • Inhibitors of the lipid and membrane synthesis for example (10.1 ) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1 ), (10.9) propamocarb (25606-41-1 ), (10.10) propamocarb hydrochloride (25606-41-1 ), (10.11 ) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18-6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-m ethyl (57018-04-9).
  • Inhibitors of the melanine biosynthesis for example (11.1 ) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (1 1.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1 ) and (11.6) tricyclazole (41814-78-2).
  • Inhibitors of the nucleic acid synthesis for example (12.1 ) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-
  • Inhibitors of the signal transduction for example (13.1 ) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fludioxonil (131341-86-1 ), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8).
  • composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous.
  • suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
  • the compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops.
  • a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
  • 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 overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
  • cotton Among the plants that may be protected by the method according to the invention, mention may 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
  • Elaeis sp. for instance oil palm
  • Blumeria diseases caused for example by Blumeria graminis ;
  • Podosphaera diseases caused for example by Podosphaera leucotricha ;
  • Sphaerotheca diseases caused for example by Sphaerotheca fuliginea ; Uncinula diseases caused for example by Uncinula necator ;
  • Gymnosporangium diseases caused for example by Gymnosporangium sabinae ; Hemileia diseases caused for example by Hemileia vastatrix ;
  • Phakopsora diseases caused for example by Phakopsora pachyrhizi and Phakopsora meibomiae ;
  • Puccinia diseases caused for example by Puccinia recondita, Puccinia graminis or Puccinia striiformis ;
  • 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 and Peronospora 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 and
  • Pythium diseases caused for example by Pythium ultimum ;
  • Leaf spot, Leaf blotch and Leaf Blight Diseases such as Alternaria diseases caused for example by Alternaria solani ;
  • Cercospora diseases caused for example by Cercospora beticola caused for example by Cercospora beticola ;
  • Cladiosporium diseases caused for example by Cladiosporium cucumerinum ;
  • Cochliobolus diseases caused for example by Cochliobolus sativus (Conidiaform:
  • Drechslera Syn: Helminthosporium) or Cochliobolus miyabeanus ; Colletotrichum diseases caused for example by Colletotrichum lindemuthianum ;
  • Cycloconium diseases caused for example by Cycloconium oleaginum ;
  • Elsinoe diseases caused for example by Elsinoe fawcettii ;
  • Gloeosporium diseases caused for example by Gloeosporium laeticolor ; Glomerella diseases caused for example by Glomerella cingulata ;
  • Leptosphaeria diseases caused for example by Leptosphaeria maculans and Leptosphaeria nodorum ;
  • Phaeosphaeria diseases caused for example by Phaeosphaeria nodorum ;
  • Pyrenophora diseases caused for example by Pyrenophora teres or Pyrenophora tritici repentis ;
  • Ramularia- diseases caused for example by Ramularia collo-cygni or Ramularia areola ;
  • Rhynchosporium diseases caused for example by Rhynchosporium secalis ;
  • Septoria diseases caused for example by Septoria apii and Septoria lycopersici ;
  • Thyphula incarnata a diseases caused for example by Thyphula incarnata ; Venturia diseases caused for example by Venturia inaequalis ;
  • Root-, Sheath and Stem Diseases such as Corticium diseases caused for example by Corticium graminearum ; Fusarium diseases caused for example by Fusarium 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 ; Thielaviopsis 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 Cladiosporium cladosporioides ; Claviceps diseases caused for example by Claviceps purpurea ;
  • 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 ;
  • Botrytis diseases caused for example by Botrytis cinerea ;
  • Penicillium diseases caused for example by Penicillium expansum and Penicillium purpurogenum ;
  • Rhizopus diseases caused by example by Rhizopus stolonifer Sclerotinia diseases caused for example by Sclerotinia sclerotiorum ;
  • Verticillium diseases caused for example by Verticillium alboatrum ;
  • 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 ;
  • Microdochium diseases caused for example by Microdochium nivale ;
  • Monographella diseases caused for example by Monographella nivalis ;
  • Penicillium diseases caused for example by Penicillium expansum ;
  • 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 ;
  • Typhula diseases caused for example by Typhula incarnata ; Verticillium diseases caused for example by Verticillium dahliae ;
  • Nectria diseases caused for example by Nectria galligena ;
  • Exobasidium diseases caused for example by Exobasidium vexans.
  • Taphrina diseases caused for example by Taphrina deformans ;
  • Rhizoctonia diseases caused for example by Rhizoctonia solani ;
  • Helminthosporium diseases caused for example by Helminthosporium solani ;
  • Bacterial Organisms such as Xanthomanas species for example Xanthomonas campestris pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans; Erwinia species for example Erwinia amylovora.
  • the fungicide 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.
  • the dose of active compound usually applied in the methods of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment.
  • the dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 15O g per 100 kg of seed in the case of seed treatment. It is clearly understood that the doses indicated herein are given as illustrative examples of the 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.
  • compositions according to the invention may also be used to reduce the contents of mycotoxins in plants and the harvested plant material and therefore in foods and animal feed stuff made therefrom.
  • Aflatoxines which are caused for example by the following fungal diseases: Fusarium spec, like Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum
  • the present invention therefore relates to the use of compounds of formula (I) as herein- described for the reduction of mycotoxins in plants and part of plants, and to methods of combating phytopathogenic and mycotoxin producing fungi characterized in that compounds of formula (I) as herein-described are applied to these fungi and/or their habitat.
  • the present invention therefore relates to the use of compounds of formula (I) as herein- described as insecticide, and/or nematicide.
  • 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 in which a heterologous gene has been stably integrated into the genome.
  • the expression "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, co suppression 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 transformation 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 phytopathogenic fungi and/ or microorganisms and/or viruses. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, 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 phytopathogenic fungi and/ or microorganisms and/or viruses, the treated plants display a substantial degree of resistance to these unwanted phytopathogenic fungi and/ or microorganisms and/or viruses.
  • unwanted phytopathogenic fungi and/ or microorganisms and/or viruses are to be understood as meaning phytopathogenic 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, ozon 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.
  • 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 stress factors. 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- 1992/005251 WO-1995/009910
  • WO- 1998/27806 WO-2005/002324, WO-2006/021972 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-1989/10396 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-1991/002069).
  • 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-tolerant 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
  • Examples of such EPSPS genes are the AroA gene (mutant CT7) of the bacterium Salmonella typhimurium (Comai et al., Science (1983), 221 , 370-371 ), the CP4 gene of the bacterium Agrobacterium sp.
  • Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in US 5,776,760 and US 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- 2002/036782, WO-2003/092360, WO-2005/012515 and WO-2007/024782.
  • 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-2001/024615 or WO-2003/013226.
  • 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 US 5,561 ,236; US 5,648,477; US 5,646,024; US 5,273,894; US 5,637,489; US 5,276,268; US 5,739,082; US 5,908,810 and US 7,112,665.
  • 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- 1996/038567, WO- 1999/024585 and WO-1999/024586.
  • 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.
  • Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate dehydrogenase 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 acetolactate synthase
  • ALS-inhibitors include, for example, sulfonylurea, imidazolinone, triazolopyrimidines, pyrimidinyloxy(thio)benzoates, and/or sulfonylaminocarbonyltriazolinone herbicides.
  • Different mutations in the ALS enzyme also known as acetohydroxyacid synthase, AHAS
  • AHAS acetohydroxyacid synthase
  • 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-2007/024782.
  • 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 US 5,084,082, for rice in WO-1997/41218, for sugar beet in US 5,773,702 and WO- 1999/057965 , for lettuce in US 5,198,599, or for sunflower in WO- 2001/065922.
  • 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 F, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof; 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., Nat. Biotechnol. (2001 ), 19, 668-72; Schnepf et al., Applied Environm. Microbiol. (2006), 71 , 1765-1774); 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 MON98034 (WO-2007/027777); 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 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 (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT102.
  • 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 8.
  • an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 8, 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.
  • 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:
  • a 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-2000/004173 or WO2006/045633 or PCT/EP07/004142.
  • plants which contain a stress tolerance enhancing transgene coding for a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphoribosyltransferase as described e.g. in WO2006/032469 or WO- 2006/133827 or PCT/EP07/002433.
  • 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-chemical 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-chemical 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-1995/004826, EP 0719338, WO-1996/15248, WO-1996/19581 , WO-1996/27674, WO-1997/11188, WO- 1997/26362, WO-1997/32985, WO-1997/42328, WO-1997/44472, WO-1997/45545, WO-1998/27212, WO-1998/40503, WO99/58688, WO-1999/58690, WO-1999/58654,
  • 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- 1996/001904, WO-1996/021023, WO-1998/039460, and WO-1999/024593, plants producing alpha 1 ,4 glucans as disclosed in WO-1995/031553, US 2002/031826, US 6,284,479, US 5,712,107, WO-1997/047806, WO-1997/047807, WO-1997/047808 and WO-2000/014249, plants producing alpha-1 ,6 branched alpha-1 ,4-glucans, as disclosed in WO-2000/73422, plants producing alternan, as disclosed in WO- 2000/047727, EP 06077301.7, US 5,908,975 and EP 0728213,
  • transgenic plants which produce hyaluronan, as for example disclosed in WO- 2006/032538, WO-2007/039314, WO-2007/039315, WO-2007/039316, JP 2006/304779, and WO-2005/012529.
  • 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-1998/000549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO-2001/017333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO02/45485 e) Plants, such as cotton plants, wherein the timing of the plasmodesmatal gating at the basis of the fiber cell is altered, e.
  • Plants such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acteylglucosaminetransferase gene including nodC and chitinsynthase genes as described in WO2006/136351
  • 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 characteristics and include: a) Plants, such as oilseed rape plants, producing oil having a high oleic acid content as described e.g.
  • transgenic plants which may be treated according to the invention are plants which comprise one or more genes which encode one or more toxins, such as the following which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), BiteGard® (for example maize), Bt-Xtra® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B®(cotton), NatureGard® (for example maize), Protecta® and NewLeaf® (potato).
  • YIELD GARD® for example maize, cotton, soya beans
  • KnockOut® for example maize
  • BiteGard® for example maize
  • Bt-Xtra® for example maize
  • StarLink® for example maize
  • Bollgard® cotton
  • Nucotn® cotton
  • Nucotn 33B® cotton
  • NatureGard® for example maize
  • herbicide- tolerant plants examples include maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize).
  • Herbicide-resistant plants plants bred in a conventional manner for herbicide tolerance
  • Clearfield® for example maize.
  • transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).
  • the compounds or mixtures 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.
  • Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention.
  • M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation.
  • the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below :
  • Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
  • Table 2 provides the NMR data ( 1 H and/or 13 C) of a selected number of compounds from table 1.
  • reaction mixture was stirred at 5O 0 C for 7 hours. Once the reaction mixture was back to room temperature, the two phases were separated and the organic phase was extracted with 100 ml of water. The combined aqueous phases were acidified to pH 2 with aqueous hydrochloric acid. The resulting white precipitate was filtered, washed with 2*20 ml of water, and dried to yield 3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxylic acid as a white solid.
  • Step a synthesis of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbaldehyde (example Ma-D
  • Step b synthesis of 5-fluoro-3-(difluoromethyl)-1-nnethyl-1 H-pyrazole-4-carboxylic acid A suspension of 79.7 g (350 mmol) of periodic acid in 640 ml absolute acetonitrile was stirred for 30 min.
  • Example A in vivo preventive test on Venturia inaegualis (apple scab) 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 untreated control, while an efficacy of 100% means that no disease is observed.
  • Example B in vivo preventive test on Botrytis cinerea (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
  • 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. 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 2O 0 C and a relative atmospheric humidity of 100%.
  • Example C in vivo curative test on Puccinia thticina (wheat)
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound or active 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 sprayed with the preparation of active compound or active compound combination at the stated rate of application.
  • the plants are placed in the greenhouse at a temperature of approximately 2O 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
  • Example D in vivo curative test on Fusahum nivale (wheat)
  • Emulsifier 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound or active 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 the greenhouse at a temperature of approximately 2O 0 C and a relative atmospheric humidity of approximately 80%.
  • the test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
  • Example E in vivo preventive test on Phakopsora pachyrhizi (soybean rust) 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.
  • 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 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.
  • Example F in vivo curative test on Blumeria graminis (wheat) Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • active compound 1 part by weight of active compound or active compound combination 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 or active compound combination is mixed with the stated amounts of solvent and emulsifier, and the concentrate is diluted with water to the desired concentration.
  • young plants are dusted with spores of Blumeria graminis f.sp. tritici and placed then in a greenhouse at a temperature of approximately 18 0 C and a relative atmospheric humidity of approximately 80%.
  • the plants are placed again in a greenhouse at a temperature of approximately 18 0 C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
  • the plants are placed in the greenhouse at a temperature of approximately 18 0 C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
  • the test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
  • Example G in vivo preventive test on Sphaerotheca fuliginea (cucumber)
  • 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.
  • 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
  • total protection (100% of disease control) is observed at a dose of 10 ppm of active ingredient with the following compounds : 1 , 2, 5, 6, 8, 10, 1 1 , 12, 13, 14, 15, 18, 22, 23, 24, 26, 27, 29, 32, 38, 41 , 44a, 47, 49, 50, 52, 54, 62, 68, 70, 72, 73, 80, 81 , 82, 83, 84, 99, 101 , 111 , 112, 113, 115, 116, 117, 118, 119, 120, 121 , 123, 124, 126, 127, 128, 130, 131 , 132, 135, 136, 137, 138, 139, 141 , and 157 according to the invention whereas weak protection (less than 85% of disease control) is observed at a dose of 10 ppm
  • Example H in vivo preventive test on Alternaha solani (tomato) Solvent: 49 parts by weight of N, N - Dimethylformamide
  • Emulsifier 1 part by weight of Alkylarylpolyglycolether
  • 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 test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
  • Example I in vivo preventive test on Leptosphaeria nodorum (wheat) Solvent: 49 parts by weight of n,n-dimethylacetamid Emulsifier: 1 part by weight of alkylaryl polyglycol ether
  • 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 a preparation of active compound at the stated rate of application.
  • the plants are inoculated with an aqueous spore suspension of Leptosphaeria nodorum.
  • the plants remain for 48 hours in an incubation cabinet at 22 0 C and a relative atmospheric humidity of 100%.
  • the plants are placed in a greenhouse at a temperature of approximately 22 0 C and a relative atmospheric humidity of approximately 90%.
  • the test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
  • 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.
  • Example K in vivo preventive test on Pyrenophora teres (barley)
  • 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.
  • Example L in vivo preventive test on Sphaerotheca fuliginea (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 untreated control, while an efficacy of 100% means that no disease is observed.
  • Example M inhibition of Fumonisin FB1 produced by Fusahum proliferatum
  • the amounts of fumonisin FB1 of the samples were analysed per HPLC-MS/MS and results were used to calculate inhibition of FB1 production in comparison to a control without compound.
  • HPLC-MS/MS was done with the following parameters:
  • HPLC column Waters Atlantis T3 (trifunctional C18 bonding, fully endcapped)
  • Solvent A Water+0.1 % HCOOH (v/v)
  • Solvent B Acetonitrile+0.1 % HCOOH (v/v)
  • Example N inhibition of deoxynivalenol (DON) and acetyldeoxynivalenol (Acetyl-DON) produced by Fusarium graminearum
  • the plate was covered and incubated at high humidity at 28 0 C for 7 days.
  • HPLC-MS/MS was done with the following parameters:
  • Solvent A Water/2.5mM NH 4 OAc+0.05% CH 3 COOH (v/v)
  • Solvent B Methanol/2.5mM NH 4 OAc+0.05% CH 3 COOH (v/v)
  • Example O inhibition of aflatoxines produced by Aspergillus parasiticus
  • OD measurement at OD 620nm with multiple read per well (circle: 4 x 4) was taken with an Infinite 1000 (Tecan) to calculate the growth inhibition.
  • bottom fluorescence measurement at Em 360n ,, and Ex 426nm with multiple read per well (square: 3 x 3) was taken to calculate inhibition of aflatoxin formation.
  • Example P injection test on Boophilus microplus Solvent: dimethyl sulfoxide
  • 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 1 ⁇ l 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.
  • Example Q spray application test on Tetranychus urticae Solvent: 78.0 parts by weight acetone
  • 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 are sprayed with a preparation of the active ingredient at the desired concentration.
  • Example R test on Meloidogyne ingognita
  • 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 salade 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.
  • Example 45 disclosed in international patent WO-2006/120224 correspond to N- ⁇ [3-chloro-5-
  • Example 397 disclosed in international patent WO-2007/087906 corresponds to N-[2-chloro-6-
  • Example 414 disclosed in international patent WO-2007/087906 corresponds to N-cyclopropyl-
  • Example 89 disclosed in international patent WO-2009/016221 corresponds to N-cyclopropyl-3- (difluoromethy ⁇ -S-fluoro-i-methyl-N-II ⁇ I-naphthy ⁇ ethyll-I H-pyrazole ⁇ -carboxamide.
  • Example 22 disclosed in international patent WO-2009/016218 corresponds to N-cyclopropyl-5- fluoro-N-(6-isopropoxy-1 ,2,3,4-tetrahydronaphthalen-1-yl)-1 ,3-dimethyl-1 H-pyrazole-4- carboxamide.
  • Example 7 disclosed in international patent WO-2009/016220 corresponds to N-cyclopropyl-5- fluoro-1 ,3-dimethyl-N-[2-(trimethylsilyl)benzyl]-1 H-pyrazole-4-carbothioamide.

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Abstract

The present invention relates to pyrazole carboxamides derivatives of formula (1) wherein Y represents CR5 or N, T represents S or O, X1 and X2 represent a chlorine or a fluorine atom, and Z1 represents a substituted or non-substituted cyclopropyl; Their process of preparation, their use as fungicide, and/or anti-mycotoxin active agents, and/or insecticide, and/or nematicide, particularly in the form of fungicide compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.

Description

FUNGICIDE PYRAZOLE CARBOXAMIDES DERIVATIVES DESCRIPTION
The present invention relates to pyrazole carboxamides derivatives, their process of preparation, their use as fungicide, and/or anti-mycotoxin active agents, and/or insecticide, and/or nematicide, particularly in the form of compositions, and methods for the control of phytopathogenic fungi, notably of plants, using these compounds or compositions.
International patent applications WO-2009/016219, WO-2007/087906, WO-2009/016220, WO- 2009/016218 and WO-2008/037789 generically mention certain amides of the following formulas:
Figure imgf000003_0001
wherein A represents a carbo-linked, partially saturated or unsaturated, 5-membered heterocyclyl group that can be substituted, T represents S or N substituted derivatives, Z represents a (un)substituted cycloalkyl.
However, there is no disclosure or suggestion in these documents of any such derivative wherein A represent a 1-methyl-3-(difluoro or dichloro)methyl-5-(chloro or fluoro)-4-pyrazolyl.
International patent applications WO-2006/120224 generically mentions 2-pyridyl-methylene- carboxamide derivatives of formula :
Figure imgf000003_0002
wherein A represents a carbo-linked 5-membered heterocyclyl group that can be substituted and Z3 represents a substituted or non substituted C3. C7 cycloalkyl. However, there is no disclosure of any derivatives according to the invention.
In international patent applications WO-2009/016221 , certain amides are generically embraced in a broad disclosure of numerous compounds of the following formula:
Figure imgf000003_0003
(I) wherein A represents a carbo-linked, unsaturated or partially saturated, 5-mennbered heterocyclyl group that can be substituted and B represents an aromatic 5- or 6-mennbered, fused heterocyclyl ring comprising up to four heteroatoms, or an aromatic 6-membered fused carbocyclyl ring. However there is no disclosure or suggestion in this document of any such derivative wherein B is a non fused aryl group.
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 that possess the above mentioned effects or advantages.
Accordingly, the present invention provides derivatives of formula (I)
Figure imgf000004_0001
wherein
• Y represents CR5 or N;
• T represents S or O ;
• X1 and X2 which can be the same or different, represent a chlorine or a fluorine atom ;
• Z1 represents a non substituted cyclopropyl or a cyclopropyl substituted by up to 2 atoms or groups which can be the same or different and which can be selected in the list consisting of halogen atoms ; cyano ; Ci-C8-alkyl ; or Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ;
• Z2 and Z3, which can be the same or different, represent a hydrogen atom ; substituted or non substituted Ci-C8-alkyl ; substituted or non substituted C2-C8-alkenyl ; substituted or non substituted C2-C8-alkynyl ; cyano ; isonitrile ; nitro ; a halogen atom ; substituted or non substituted Ci-C8-alkoxy ; substituted or non substituted C2-C8-alkenyloxy ; substituted or non substituted C2-C8-alkynyloxy ; substituted or non substituted C3-C7- cycloalkyl ; substituted or non substituted Ci-C8-alkylsulfanyl ; substituted or non substituted Ci-C8-alkylsulfonyl ; substituted or non substituted Ci-C8-alkylsulfinyl ; amino ; substituted or non substituted Ci-C8-alkylannino ; substituted or non substituted di-Ci-C8-alkylannino ; substituted or non substituted Ci-C8-alkoxycarbonyl ; substituted or non substituted d-Cs-alkylcarbamoyl ; substituted or non substituted di-d-C8- alkylcarbamoyl ; or substituted or non substituted N-d-C8-alkyl-d-C8- alkoxycarbamoyl ; or
Z3 and R1 together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5-, 6- or 7-membered, partly saturated, carbo- or hetero- cycle comprising up to 3 heteroatoms and Z2 is as herein described; or
Z2 and Z3 together with the carbon atom to which they are linked form a substituted or non substituted C3-C7 cycloalkyl ;
R1, R2, R3, R4 and R5, which can be the same or different, represent a hydrogen atom; a halogen atom ; nitro ; cyano ; isonitrile ; hydroxyl ; sulfanyl ; amino ; pentafluoro-λ6- sulfanyl ; substituted or non substituted d-C8-alkyl ; d-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted d-C8-alkylamino ; substituted or non substituted di-d-C8-alkylamino ; substituted or non substituted d-C8-alkoxy ; d-C8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; d-C8-alkoxy-Ci-C8-alkyl ; substituted or non substituted Ci-C8-alkylsulfanyl ; Ci-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2- C8-alkynyloxy ; C2-C8-halogenoalkynyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl ; C3-C7- halogenocycloalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl-d-C8-alkyl ; substituted or non substituted C3-C7-cycloalkyl-C2-C8-alkenyl ; substituted or non substituted C3-C7- cycloalkyl-C2-C8-alkynyl ; substituted or non substituted C3-C7-cycloalkyl-C3-C7- cycloalkyl ; substituted or non substituted d-C8-alkyl-C3-C7-cycloalkyl ; formyl ; formyloxy ; formylamino ; carboxy ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ;
(hydroxyimino)-d-C8-alkyl ; substituted or non substituted Ci-C8-alkylcarbonyl ; Ci-C8- halogenoalkylcarbonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8-alkylcarbamoyl ; substituted or non substituted di-d-Cs-alkylcarbamoyl ; N-(substituted or non substituted Ci-C8- alkyloxy)carbamoyl ; substituted or non substituted Ci-C8-alkoxycarbamoyl ; N- (substituted or non substituted d-C8-alkyl)-(substituted or non substituted Ci-C8- alkoxy)-carbamoyl ; substituted or non substituted Ci-C8-alkoxycarbonyl ; Ci-C8- halogenoalkoxycarbonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-Cs-alkylaminocarbonyl ; di- substituted or non substituted Ci-Cs-alkylaminocarbonyl ; substituted or non substituted Ci-C8- alkylcarbonyloxy ; Ci-Cs-halogenoalkylcarbonyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8- alkylcarbonylamino ; Ci-Cs-halogenoalkylcarbonylamino comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8- alkylaminocarbonyloxy ; substituted or non substituted di-Ci-Cs-alkylaminocarbonyloxy ; substituted or non substituted Ci-Cs-alkyloxycarbonyloxy ; substituted or non substituted Ci-C8-alkylsulfinyl ; Ci-C8-halogenoalkylsulfinyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8-alkylsulfonyl ; Ci-C8- halogenoalkylsulfonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8-alkoxyimino ; (Ci-C8-alkoxyimino)-Ci-C8- alkyl ; substituted or non substituted (Ci-C8-alkenyloxyimino)-Ci-C8-alkyl ; (Ci-C8- alkynyloxyimino)-Ci-C8-alkyl ; a (benzyloxyimino)-Ci-C8-alkyl ; tri(substituted or non substituted Ci-C8-alkyl)silyl ; tri(substituted or non substituted Ci-C8-alkyl)silyl-Ci-C8- alkyl ; benzyloxy which can be substituted by up to 5 groups Q ; benzylsulfanyl which can be substituted by up to 5 groups Q ; benzylamino which can be substituted by up to 5 groups Q ; aryl which can be substituted by up to 7 groups Q ; aryloxy which can be substituted by up to 7 groups Q ; arylamino which can be substituted by up to 7 groups Q ; arylsulfanyl which can be substituted by up to 7 groups Q ; aryl-Ci-C8alkyl which can be substituted by up to 7 groups Q ; aryl-C2-C8-alkenyl which can be substituted by up to 7 groups Q ; aryl-C2-C8-alkynyl which can be substituted by up to 7 groups Q ; pyridinyl which can be substituted by up to 4 groups Q ; pyridinyloxy which can be substituted by up to 4 groups Q ; aryl-C3-C7-cycloalkyl which can be substituted by up to 7 groups Q ; or
Two vicinal substituents R together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5- or 6-membered, saturated, carbo- or hetero-cycle comprising up to 3 heteroatoms and the other substituents R are as herein-described; or R1 and Z3 together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5-, 6- or 7-membered, partly saturated, carbo- or hetero- cycle comprising up to 3 heteroatoms, and R2 to R5 are as herein-described; • Q, which can be the same or different, represents a halogen atom ; cyano ; nitro ; C1-
C8-alkyl ; C-ι-C8-alkoxy ; C-ι-C8-alkylsulfanyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; d-C8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; tri(Ci-C8)alkylsilyl or tri(Ci- C8)alkylsilyl-Ci-C8-alkyl ;
with the provisio that when Y represents N, and T represents O, and Z1 represents a cyclopropyl group, and R1 represents a chlorine atom, and R3 represents a trifluoromethyl group, and R2 and R4 represent a hydrogen atom, then a least one of the substituent Z2 or Z3 is not a hydrogen atom , as well as salts, N-oxydes, metallic complexes, metalloidic complexes and optically active or geometric isomers thereof.
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 ; nitro ; hydroxyl ; cyano ; isonitrile ; amino ; thio ; a pentafluoro-λ6-sulfanyl group ; formyl ; formyloxy ; formylamino ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)-C-ι-C6-alkyl ; d-C8-alkyl ; a tri(C-ι-C8-alkyl)silyl ; C3-C8-cycloalkyl ; C1-C8- halogenoalkyl having 1 to 5 halogen atoms ; a C3-C8-halogenocycloalkyl having 1 to 5 halogen atoms ; C2-C8-alkenyl ; C2-C8-alkynyl ; C2-C8-alkenyloxy ; C2-C8-alkynyloxy ; C1-C8- alkylamino ; di-C-ι-C8-alkylamino ; C-ι-C8-alkoxy ; C-ι-C8-halogenoalkoxy having 1 to 5 halogen atoms ; C-ι-C8-alkylsulfanyl ; C-i-C8-halogenoalkylsulfanyl having 1 to 5 halogen atoms ; C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy having 1 to 5 halogen atoms ; C3-C8- alkynyloxy ; C3-C8-halogenoalkynyloxy having 1 to 5 halogen atoms ; C-i-Cs-alkylcarbonyl ; C-i-Cs-halogenoalkylcarbonyl having 1 to 5 halogen atoms ; C-i-Cs-alkylcarbamoyl ; CIi-C1-C8- alkylcarbamoyl ; N-C-i-Cs-alkyloxycarbamoyl ; C-i-Cs-alkoxycarbamoyl ; N-C-i-Cs-alkyl-C-i-Cs- alkoxycarbamoyl ; C-i-Cs-alkoxycarbonyl ; C-i-Cs-halogenoalkoxycarbonyl having 1 to 5 halogen atoms ; C-i-Cs-alkylcarbonyloxy ; C-i-Cs-halogenoalkylcarbonyloxy having 1 to 5 halogen atoms ; C-i-Cs-alkylcarbonylamino ; C-i-Cs-halogenoalkylcarbonylamino having 1 to 5 halogen atoms ; C-i-Cs-alkylaminocarbonyloxy ; di-C-i-Cs-alkylaminocarbonyloxy ; C1-C8- alkyloxycarbonyloxy ; C-ι-C8-alkylsulfanyl ; C-ι-C8-halogenoalkylsulfanyl having 1 to 5 halogen atoms; C-ι-C8-alkylsulfinyl ; C-i-C8-halogenoalkylsulfinyl having 1 to 5 halogen atoms ; C-ι-C8-alkylsulphonyl ; C-i-Cs-halogenoalkylsulfonyl having 1 to 5 halogen atoms ; C-i-Cs-alkylaminosulfamoyl ; di-C-i-Cs-alkylaminosulfamoyl ; (C1-C6-BIkOXyImInO)-C1-C6- alkyl ; (C-i-Ce-alkenyloxyimino^C-i-Ce-alkyl ; (C-i-Ce-alkynyloxyimino^C-i-Ce-alkyl ; 2- oxopyrrolidin-1-yl ; (benzyloxyimino)-C-ι-C6-alkyl ; C-ι-C8-alkoxyalkyl ; C1-C8- halogenoalkoxyalkyl having 1 to 5 halogen atoms ; benzyloxy ; benzylsulfanyl ; benzylamino ; aryloxy ; arylsulfanyl or arylamino. 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 that are known per se by the man ordinary skilled in the art.
According to the invention, the following generic terms are generally used with the following meanings: • halogen means fluorine, chlorine, bromine or iodine ;
• heteroatom can be nitrogen, oxygen or sulphur ;
• any alkyl, alkenyl or alkynyl group can be linear or branched ;
• the term "aryl" means phenyl or naphthyl, optionally substituted ;
• In the case of an amino group or the amino moiety of any other amino-comprising group, substituted by two substituents that can be the same or different, the two substituents together with the nitrogen atom to which they are linked can form a heterocyclyl group, preferably a 5- to 7-membered heterocyclyl group, that can be substituted or that can include other hetero atoms, for example a morpholino or piperidinyl group.
Preferred compounds of formula (I) according to the invention are those wherein Y represents CR5.
Other preferred compounds of formula (I) according to the invention are those wherein Y represents N.
Other preferred compounds of formula (I) according to the invention are those wherein T represents O.
Other preferred compounds of formula (I) according to the invention are those wherein X1 represents a fluorine atom.
Other preferred compounds of formula (I) according to the invention are those wherein X2 represents a fluorine atom.
Other preferred compounds of formula (I) according to the invention are those wherein Z1 represents a non substituted cyclopropyl. Other preferred compounds of formula (I) according to the invention are those wherein Z2 and Z3 independently represent a hydrogen atom or a methyl.
More preferred compounds of formula (I) according to the invention are those wherein Z2 represents a hydrogen atom and Z3 represents a hydrogen atom or a methyl.
Other preferred compounds of formula (I) according to the invention are those wherein R1, R2, R3, R4 and R5, which can be the same or different, represent a hydrogen atom ; a halogen atom ; substituted or non substituted C-ι-C8-alkyl ; C-ι-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl ; tri(C-ι-C8-alkyl)silyl ; or substituted or non substituted C-ι-C8-alkylsulfanyl.
More preferred compounds of formula (I) according to the invention are those wherein the substituent R1 represents a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C3-C7-cycloalkyl ; tri(Ci-C8-alkyl)silyl or d- C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
Other more preferred compounds of formula (I) according to the invention are those wherein the substitutents R1 and R5, which can be the same or different, represent a halogen atom ; Ci-C8- alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C3-C7-cycloalkyl; tri(Ci-C8-alkyl)silyl or Ci-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
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, either individually, partially or entirely. 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 T with preferred features of one or more X1, X2, Y, Z1 to Z3, and R1 to R5; - preferred features of X1 with preferred features of one or more T, X2, Y, Z1 to Z3, and R1 to R5;
- preferred features of X2 with preferred features of one or more T, X1, Y, Z1 to Z3, and R1 to R5;
- preferred features of Y with preferred features of one or more T, X1, X2, Z1 to Z3, and R1 to R5;
- preferred features of Z1 with preferred features of one or more T, X1, X2, Y, Z2, Z3, and R1 to
R5; - preferred features of Z2 with preferred features of one or more T, X1, X2, Y, Z1, Z3, and R1 to
R5;
- preferred features of Z3 with preferred features of one or more T, X1, X2, Y, Z1, Z2, and R1 to
R5; - preferred features of R1 with preferred features of one or more T, X1, X2, Y, Z1 to Z3, and R2 to
R5;
- preferred features of R2 with preferred features of one or more T, X1, X2, Y, Z1 to Z3, R1, and R3 to R5; - preferred features of R3 with preferred features of one or more T, X1, X2, Y, Z1 to Z3, R1, R2, R4, and R5;
- preferred features of R with preferred features of one or more T, X , X , Y, Z to Z , R to R , and R5;
- preferred features of R5 with preferred features of one or more T, X1, X2, Y, Z1 to Z3, and R1 to R4;
In these combinations of preferred features of the substituents of the compounds according to the invention, the said preferred features can also be selected among the more preferred features of each of T, X1, X2, Y, Z1 to Z3, and R1 to R5; so as to form most preferred subclasses of compounds according to the invention.
The present invention also relates to a process for the preparation of compounds of formula (I). Thus according to a further aspect of the present invention there is provided a process P1 for the preparation of compound of formula (Ia) as herein-defined for which T represents a oxygen atom, as illustrated by the following reaction scheme :
Figure imgf000011_0001
(iig) (He) (in)
Process P1 wherein Z\ Z2, Z3, R1, R2 ,R3 ,R4, Y and X2 are as herein-defined ;
5-chloro-3-(difluoronnethyl)-1-nnethyl-1 H-pyrazole-4-carbaldehyde is known from WO- 2004/014138 (reference example 35)
N-Cyclopropylamines of formula are known (WO-2008/037789, WO-2007/087906, WO- 2006/120224 and WO-2009/016218) or can be prepared by known methods
Step 1 and 13 of process P1 is performed in the presence of an oxidant, and if appropriate in the presence of a solvent. Steps 2 and 9 of process P1 are performed in the presence of acid halide, and if appropriate in the presence of a solvent.
Steps 4, 7 and 10 of process P1 are performed in the presence of an acid binder, and if appropriate in the presence of a solvent.
Steps 3 and 8 of process P1 are performed in the presence of a condensing agent, and if appropriate in the presence of a solvent.
Step 5 and 12 of process P1 is performed in the presence of a fluorinating agent, and if appropriate in the presence of a solvent.
Step 11 of process P1 is performed in the presence of a chlorinating agent and a lewis acid, and if appropriate in the presence of a solvent.
According to a further aspect of the present invention there is provided a process P2 for the preparation of compound of formula (Ia) as herein-defined for which T represent a oxygen atom, as illustrated by the following reaction scheme :
Figure imgf000012_0001
Process P2 wherein
Z\ Z2, Z3, Y, R1, R2 ,R3 ,R4, X1 and X2 are as herein-defined ;
W1 represents a halogen atom or a hydroxyl ;
W2 represents a halogen or a leaving group such as tosylate, mesylate or triflate group.
Pyrazoles derivatives of formula (Mh) may be prepared according to process P1. N-cyclopropylamines of formula (IV) and methylene derivatives of formula (V) are known or may be prepared by known methods.
Step 1 of process P2 is performed in the presence of an acid binder or a condensing agent, and if appropriate in the presence of a solvent.
Step 2 of process P2 is performed in the presence of a solvent and if appropriate in the presence of an acid binder. According to a further aspect of the present invention there is provided a process P3 for the preparation of compound of formula (Ib) as herein-defined for which T represent a sulfur atom, as illustrated by the following reaction scheme :
Figure imgf000013_0001
Process P3 wherein
Z1, Z2, Z3, Y, R1, R2 ,R3 ,R4, X1 and X2 are as herein-defined ;
Step 1 of process P3 is performed in the presence of a thionating agent and if appropriate in the presence of an acid binder and if appropriate in the presence of solvent.
Suitable oxidants for carrying out step 1 or 13 of process P1 according to the invention are in each case all inorganic and organic oxidant which are customary for such reactions. Preference is given to using benzyltriethylammonium permanganate; bromine; chlorine; m- chloroperbenzoic acid; chromic acid; chromium (Vl) oxide; hydrogen peroxide; hydrogen peroxide-boron trifluoride; hydrogen peroxide-urea; 2-hydroxyperoxyhexafluoro-2-propanol; Iodine; oxygen-platinum catalyst, perbenzoic acid; peroxyacetyl nitrate; potassium permanganate; potassium ruthenate; pyridinium dichromate; ruthenium (VIII) oxide; silver (I) oxide; silver (II) oxide; silver nitrite; sodium chlorite; sodium hypochlorite; 2,2,6,6- tetramethylpiperidin-1-oxyl.
Suitable acid halides for carrying out steps 2 and 9 of process P1 according to the invention are in each case all organic or inorganic acid halides which are customary for such reactions. Preference is given to using notably phosgene, phosphorous trichloride, phosphorous pentachloride, phosphorous trichloride oxide; thionyl chloride; or carbon tetrachloride- triphenylphosphine.
Suitable acid binder for carrying out steps 4, 7 and 10 of process P1 , steps 1 and 2 of process P2 and process P3 according to the invention are in each case all 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 alkoxydes, 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, alkali metal or alkaline earth metal acetates, such as sodium acetate, potassium acetate, calcium acetate, and also ternary amines, such as trimethylamine, triethylamine, tributylamine, N,N-dimethylaniline, di-isopropyl-ethylamine, pyridine, methylethylpyridine, methylimidazole, N-methylpiperidine, N,N-dimethylanninopyridine, diazabicyclooctane (DABCO), diazabicyclononene (DBN) or diazabicycloundecene (DBU). It is also possible to work in the absence of an acid binder or to employ an excess of the amine component, so that it simultaneously acts as acid binder agent.
Suitable condensing agent for carrying out steps 3 and 8 of process P1 and step 1 of process P2 according to the invention are in each case all condensing agents which are customary for such reactions. Preference is given to using carbodiimides, such as N1N'- dicyclohexylcarbodiimide (DCC) or other customary condensing agents, notably phosphorous pentoxide, polyphosphoric acid, N,N'-carbonyldiimidazole, 2-ethoxy-N-ethoxycarbonyl-1 ,2- dihydroquinoline (EEDQ), triphenylphosphine/tetrachloromethane or bromo- tripyrrolidinophosphonium-hexafluorophosphate.
Suitable fluorinating agent for carrying out step 5 or 12 of process P1 according to the invention is in each case all fluorinating agents which are customary for such reactions. Preference is given to using cesium fluoride; potassium fluoride; potassium fluoride-calcium difluoride; tetrabutylammonium fluoride.
Suitable chlorination agent for carrying out step 1 1 of process P1 according to the invention is in each case all chlorination agents agents which are customary for such reactions (WO- 2007/062776). Preference is given to using tetrachlorosilane /aluminium trichloride, aluminium trichloride .
Suitable thionating agents for carrying out process P3 according to the invention can be sulphur (S), sulfhydric acid (H2S), sodium sulfide (Na2S), sodium hydrosulfide (NaHS), boron trisulfide (B2S3), bis (diethylaluminium) sulfide ((AIEt2)2S), ammonium sulfide ((NH4)2S), phosphorous pentasulfide (P2S5), Lawesson's reagent (2,4-bis(4-methoxyphenyl)-1 ,2,3,4-dithiadiphosphetane 2,4-disulfide) or a polymer-supported thionating reagent such as described in J.Chem.Soc. Perkin 1 , (2001 ), 358.
Suitable solvents for carrying out steps 1 to 13 of process P1 , steps 1 and 2 of process P2 and process P3 according to the invention are in each case all 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, cyclopentyl methylether, diisopropyl ether, methyl t-butyl ether, methyl t-amyl ether, dioxane, tetrahydrofuran, 2-methyl tetrahydrofuran, 1 ,2-dimethoxyethane, 1 ,2-diethoxyethane or anisole; nitriles, such as acetonitrile, propionitrile, n- or i-butyronitrile or benzonitrile; amides, such as N,N-dimethylfornnannide, N,N-dimethylacetannide, 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.
When carrying out steps 1 to 13 of process P1 and steps 1 and 2 of process P2 according to the invention, the reaction temperatures can independently be varied within a relatively wide range. Generally, processes according to the invention are carried out at temperatures between O0C and 16O0C, preferably between 1O0C and 12O0C. A way to control the temperature for the processes according to the invention is to use the micro-waves technology.
Steps 1 to 13 of process P1 and steps 1 and 2 of process P2 according to the invention are generally independently carried out under atmospheric pressure. However, in each case, it is also possible to operate under elevated or reduced pressure.
When carrying out step 1 or 13 of process P1 according to the invention, generally 1 mol or other an excess of the oxidant is employed per mole of aldehyde of formula (Ma) or (Ng). It is also possible to employ the reaction components in other ratios. When carrying out carrying out steps 2 and 9 of process P1 to the invention, generally 1 mol or other an excess of the acid halides is employed per mole of acid of formula (lib) or (Me). It is also possible to employ the reaction components in other ratios.
When carrying out steps 4, 7 and 10 of process P1 and step 1 and 2 of process P2 according to the invention generally 1 mol or other an excess of the acid binder is employed per mole of acid halides of formula (Mc), (Md) or (Mf). It is also possible to employ the reaction components in other ratios.
When carrying out process P3 according to the invention, generally 1 mol or other an excess of the acid binder is employed per mole of compound (Ia). It is also possible to employ the reaction components in other ratios. When carrying out steps 3 and 8 of process P1 and step 1 of process P2 according to the invention generally 1 mol or other an excess of the condensing agent is employed per mole of acid of formula (lib) and (Me). It is also possible to employ the reaction components in other ratios.
When carrying out step 5 or 12 of process P1 according to the invention, generally 2 moles or other an excess of the fluorinating agent is employed per mole of chlorinated compound of formula (Na) or (lie). It is also possible to employ the reaction components in other ratios. When carrying out step 11 of process P1 according to the invention, generally 0,2 - 0,3 mol of chlorinating agent is employed per mole of acid fluoride formula (Nd). It is also possible to employ the reaction components in other ratios.
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, recrystallization or distillation, from any impurities that may still be present.
Compounds according to the invention can be prepared according to the above described process. It will nevertheless be understood that, on the basis of his general knowledge and of available publications, the skilled worker will be able to adapt these processes according to the specifics of each of the compounds according to the invention that is desired to be synthesized.
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 (lib)
Figure imgf000016_0001
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom;
- compounds of formula (Mc')
Figure imgf000016_0002
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom and W3 represent a halogen atom preferably a chlorine atom;
- compounds of formula (Nd)
Figure imgf000017_0001
(Hd) wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom;
- compounds of formula (lie)
Figure imgf000017_0002
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
- compounds of formula (Mf)
Figure imgf000017_0003
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
- compounds of formula (Ng)
Figure imgf000017_0004
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
In a further aspect, the present invention also relates to a composition, particularly a fungicide 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 that is sufficient to control or destroy the fungi, and/or insects, and/or nematicides, and/or weeds present or liable to appear on or around the crops, and that does not entail any appreciable symptom of phytotoxicity for the said crops. Such an amount can vary within a wide range depending on the target, particularly fungus, to be controlled, the type of crop, the climatic conditions and the compounds included in the composition according to the invention. This amount can be determined by systematic field trials, that are within the capabilities of a person skilled in the art.
Thus, according to the invention, there is provided a composition, particularly a fungicide 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 that 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 comprising sulphate, sulphonate and phosphate functions. The presence of at least one surfactant is generally essential when the active compound and/or the inert support are water-insoluble and when 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, that 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 that 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 that 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 normally a broadened spectrum of activity. The mixtures with other fungicide compounds are particularly advantageous.
Examples of suitable fungicide mixing partners can be selected in the following lists:
(1 ) Inhibitors of the ergosterol biosynthesis, for example (1.1 ) aldimorph (1704-28-5), (1.2) azaconazole (60207-31-0), (1.3) bitertanol (55179-31-2), (1.4) bromuconazole (116255-48-2), (1.5) cyproconazole (113096-99-4), (1.6) diclobutrazole (75736-33-3), (1.7) difenoconazole (119446-68-3), (1.8) diniconazole (83657-24-3), (1.9) diniconazole-M (83657-18-5), (1.10) dodemorph (1593-77-7), (1.11 ) dodemorph acetate (31717-87-0), (1.12) epoxiconazole (106325-08-0), (1.13) etaconazole (60207-93-4), (1.14) fenarimol (60168-88-9), (1.15) fenbuconazole (114369-43-6), (1.16) fenhexamid (126833-17-8), (1.17) fenpropidin (67306-00- 7), (1.18) fenpropimorph (67306-03-0), (1.19) fluquinconazole (136426-54-5), (1.20) flurprimidol (56425-91-3), (1.21 ) flusilazole (85509-19-9), (1.22) flutriafol (76674-21-0), (1.23) furconazole (112839-33-5), (1.24) furconazole-cis (112839-32-4), (1.25) hexaconazole (79983-71-4), (1.26) imazalil (60534-80-7), (1.27) imazalil sulfate (58594-72-2), (1.28) imibenconazole (86598-92-7), (1.29) ipconazole (125225-28-7), (1.30) metconazole (125116-23-6), (1.31 ) myclobutanil (88671-89-0), (1.32) naftifine (65472-88-0), (1.33) nuarimol (63284-71-9), (1.34) oxpoconazole (174212-12-5), (1.35) paclobutrazol (76738-62-0), (1.36) pefurazoate (101903-30-4), (1.37) penconazole (66246-88-6), (1.38) piperalin (3478-94-2), (1.39) prochloraz (67747-09-5), (1.40) propiconazole (60207-90-1 ), (1.41 ) prothioconazole (178928-70-6), (1.42) pyributicarb (88678- 67-5), (1.43) pyrifenox (88283-41-4), (1.44) quinconazole (103970-75-8), (1.45) simeconazole (149508-90-7), (1.46) spiroxamine (118134-30-8), (1.47) tebuconazole (107534-96-3), (1.48) terbinafine (91 161-71-6), (1.49) tetraconazole (112281-77-3), (1.50) triadimefon (43121-43-3), (1.51 ) triadimenol (89482-17-7), (1.52) tridemorph (81412-43-3), (1.53) triflumizole (68694-11-1 ), (1.54) triforine (26644-46-2), (1.55) triticonazole (131983-72-7), (1.56) uniconazole (83657-22- 1 ), (1.57) uniconazole-p (83657-17-4), (1.58) viniconazole (77174-66-4), (1.59) voriconazole (137234-62-9), (1.60) i^-chlorophenyO^I H-i ^^-triazol-i-yOcycloheptanol (129586-32-9), (1.61 ) methyl 1-(2,2-dimethyl-2,3-dihydro-1 H-inden-1-yl)-1 H-imidazole-5-carboxylate (111323- 95-0), (1.62) N'-{5-(difluoromethyl)-2-methyl-4-[3-(trimethylsilyl)propoxy]phenyl}-N-ethyl-N- methylimidoformamide, (1.63) N-ethyl-N-methyl-N'-{2-methyl-5-(trifluoronnethyl)-4-[3- (trimethylsilyl)propoxy]phenyl}imidoformamide and (1.64) O-[1-(4-methoxyphenoxy)-3,3- dimethylbutan-2-yl] I H-imidazole-1-carbothioate (11 1226-71-2).
(2) inhibitors of the respiratory chain at complex I or II, for example (2.1 ) bixafen (581809-46-03), (2.2) boscalid (188425-85-6), (2.3) carboxin (5234-68-4), (2.4) diflumetorim (130339-07-0), (2.5) fenfuram (24691-80-3), (2.6) fluopyram (658066-35-4), (2.7) flutolanil (66332-96-5), (2.8) furametpyr (123572-88-3), (2.9) furmecyclox (60568-05-0), (2.10) isopyrazam (mixture of syn- epimeric racemate 1 RS,4SR,9RS and anti-epimeric racemate 1 RS, 4SR, 9SR) (881685-58-1 ), (2.1 1 ) isopyrazam (anti-epimeric racemate 1 RS, 4SR, 9SR), (2.12) isopyrazam (anti-epimeric enantiomer 1 R,4S,9S), (2.13) isopyrazam (anti-epimeric enantiomer 1S,4R,9R), (2.14) isopyrazam (syn epimeric racemate 1 RS,4SR,9RS), (2.15) isopyrazam (syn-epimeric enantiomer 1 R,4S,9R), (2.16) isopyrazam (syn-epimeric enantiomer 1S,4R,9S), (2.17) mepronil (55814-41-0), (2.18) oxycarboxin (5259-88-1 ), (2.19) penflufen (494793-67-8), (2.20) penthiopyrad (183675-82-3), (2.21 ) sedaxane (874967-67-6), (2.22) thifluzamide (130000-40-7), (2.23) 1-methyl-N-[2-(1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-3-(trifluoromethyl)-1 H-pyrazole-4- carboxamide, (2.24) fluxapyroxad (907204-31-3), (2.25) 3-(difluoromethyl)-1-methyl-N-[2- (1 ,1 ,2,2-tetrafluoroethoxy)phenyl]-1 H-pyrazole-4-carboxamide, (2.26) 3-(difluoromethyl)-N-[4- fluoro-2-(1 ,1 ,2,3,3,3-hexafluoropropoxy)phenyl]-1-methyl-1 H-pyrazole-4-carboxamide, (2.27) N- [1-(2,4-dichlorophenyl)-1-methoxypropan-2-yl]-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4- carboxamide , and salts thereof.
(3) inhibitors of the respiratory chain at complex III, for example (3.1 ) amisulbrom (348635-87-0), (3.2) azoxystrobin (131860-33-8), (3.3) cyazofamid (120116-88-3), (3.4) dimoxystrobin (141600- 52-4), (3.5) enestroburin (238410-11-2) (known from WO 2004/058723), (3.6) famoxadone (131807-57-3) (known from WO 2004/058723), (3.7) fenamidone (161326-34-7) (known from WO 2004/058723), (3.8) fluoxastrobin (361377-29-9) (known from WO 2004/058723), (3.9) kresoxim-methyl (143390-89-0) (known from WO 2004/058723), (3.10) metominostrobin (133408-50-1 ) (known from WO 2004/058723), (3.11 ) orysastrobin (189892-69-1 ) (known from WO 2004/058723), (3.12) picoxystrobin (117428-22-5) (known from WO 2004/058723), (3.13) pyraclostrobin (175013-18-0) (known from WO 2004/058723), (3.14) pyrametostrobin (915410- 70-7) (known from WO 2004/058723), (3.15) pyraoxystrobin (862588-11-2) (known from WO 2004/058723), (3.16) pyribencarb (799247-52-2) (known from WO 2004/058723), (3.17) trifloxystrobin (141517-21-7) (known from WO 2004/058723), (3.18) (2E)-2-(2-{[6-(3-chloro-2- methylphenoxy)-5-fluoropyrimidin-4-yl]oxy}phenyl)-2-(methoxyimino)-N-methylethanamide (known from WO 2004/058723), (3.19) (2E)-2-(methoxyimino)-N-methyl-2-(2-{[({(1 E)-1-[3- (trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)ethanamide (known from WO 2004/058723) and salts thereof., (3.20) (2E)-2-(methoxyimino)-N-methyl-2-{2-[(E)-({1-[3- (trifluoromethyl)phenyl]ethoxy}imino)methyl]phenyl}ethanamide (158169-73-4), (3.21 ) (2E)-2-{2- [({[(1 E)-1-(3-{[(E)-1-fluoro-2-phenylethenyl]oxy}phenyl)ethylidene]amino}oxy)methyl]phenyl}-2- (methoxyimino)-N-methylethanamide (326896-28-0), (3.22) (2E)-2-{2-[({[(2E,3E)-4-(2,6- dichlorophenyl)but-3-en-2-ylidene]amino}oxy)methyl]phenyl}-2-(methoxyimino)-N- methylethanamide, (3.23) 2-chloro-N-(1 ,1 ,3-trimethyl-2,3-dihydro-1 H-inden-4-yl)pyridine-3- carboxamide (119899-14-8), (3.24) 5-methoxy-2-methyl-4-(2-{[({(1 E)-1-[3-
(trifluoromethyl)phenyl]ethylidene}amino)oxy]methyl}phenyl)-2,4-dihydro-3H-1 ,2,4-triazol-3-one, (3.25) methyl (2E)-2-{2-[({cyclopropyl[(4-methoxyphenyl)imino]methyl}sulfanyl)methyl]phenyl}-3- methoxyprop-2-enoate (149601-03-6), (3.26) N-(3-ethyl-3,5,5-trimethylcyclohexyl)-3- (formylamino)-2-hydroxybenzamide (226551-21-9), (3.27) 2-{2-[(2,5- dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (173662-97-0), (3.28) (2R)-2- {2-[(2,5-dimethylphenoxy)methyl]phenyl}-2-methoxy-N-methylacetamide (394657-24-0) and salts thereof.
(4) Inhibitors of the mitosis and cell division, for example (4.1 ) benomyl (17804-35-2), (4.2) carbendazim (10605-21-7), (4.3) chlorfenazole (3574-96-7), (4.4) diethofencarb (87130-20-9), (4.5) ethaboxam (162650-77-3), (4.6) fluopicolide (239110-15-7), (4.7) fuberidazole (3878-19-1 ), (4.8) pencycuron (66063-05-6), (4.9) thiabendazole (148-79-8), (4.10) thiophanate-methyl (23564-05-8), (4.11 ) thiophanate (23564-06-9), (4.12) zoxamide (156052-68-5), (4.13) 5-chloro- 7-(4-methylpiperidin-1-yl)-6-(2,4,6-trifluorophenyl)[1 ,2,4]triazolo[1 ,5-a]pyrimidine (214706-53-3) and (4.14) S-chloro-S-^-chloropyridin-S-yO-θ-methyW-^AΘ-trifluorophenyOpyridazine (1002756-87-7) and salts thereof. (5) Compounds capable to have a multisite action, like for example (5.1 ) bordeaux mixture (8011-63-0), (5.2) captafol (2425-06-1 ), (5.3) captan (133-06-2) (known from WO 02/12172), (5.4) chlorothalonil (1897-45-6), (5.5) copper hydroxide (20427-59-2), (5.6) copper naphthenate (1338-02-9), (5.7) copper oxide (1317-39-1 ), (5.8) copper oxychloride (1332-40-7), (5.9) copper(2+) sulfate (7758-98-7), (5.10) dichlofluanid (1085-98-9), (5.11 ) dithianon (3347-22-6), (5.12) dodine (2439-10-3), (5.13) dodine free base, (5.14) ferbam (14484-64-1 ), (5.15) fluorofolpet (719-96-0), (5.16) folpet (133-07-3), (5.17) guazatine (108173-90-6), (5.18) guazatine acetate, (5.19) iminoctadine (13516-27-3), (5.20) iminoctadine albesilate (169202-06- 6), (5.21 ) iminoctadine triacetate (57520-17-9), (5.22) mancopper (53988-93-5), (5.23) mancozeb (2234562), (5.24) maneb (12427-38-2), (5.25) metiram (9006-42-2), (5.26) metiram zinc (9006-42-2), (5.27) oxine-copper (10380-28-6), (5.28) propamidine (104-32-5), (5.29) propineb (12071-83-9), (5.30) sulphur and sulphur preparations including calcium polysulphide (7704-34-9), (5.31 ) thiram (137-26-8), (5.32) tolylfluanid (731-27-1 ), (5.33) zineb (12122-67-7), (5.34) ziram (137-30-4) and salts thereof.
(6) Compounds capable to induce a host defence, like for example (6.1 ) acibenzolar-S-methyl (135158-54-2), (6.2) isotianil (224049-04-1 ), (6.3) probenazole (27605-76-1 ) and (6.4) tiadinil (223580-51-6).
(7) Inhibitors of the amino acid and/or protein biosynthesis, for example (7.1 ) andoprim (23951- 85-1 ), (7.2) blasticidin-S (2079-00-7), (7.3) cyprodinil (121552-61-2), (7.4) kasugamycin (6980- 18-3), (7.5) kasugamycin hydrochloride hydrate (19408-46-9), (7.6) mepanipyrim (110235-47-7) and (7.7) pyrimethanil (53112-28-0).
(8) Inhibitors of the ATP production, for example (8.1 ) fentin acetate (900-95-8), (8.2) fentin chloride (639-58-7), (8.3) fentin hydroxide (76-87-9) and (8.4) silthiofam (175217-20-6).
(9) Inhibitors of the cell wall synthesis, for example (9.1 ) benthiavalicarb (177406-68-7), (9.2) dimethomorph (110488-70-5), (9.3) flumorph (211867-47-9), (9.4) iprovalicarb (140923-17-7), (9.5) mandipropamid (374726-62-2), (9.6) polyoxins (1 1113-80-7), (9.7) polyoxorim (22976-86- 9), (9.8) validamycin A (37248-47-8) and (9.9) valifenalate (283159-94-4; 283159-90-0).
(10) Inhibitors of the lipid and membrane synthesis, for example (10.1 ) biphenyl (92-52-4), (10.2) chloroneb (2675-77-6), (10.3) dicloran (99-30-9), (10.4) edifenphos (17109-49-8), (10.5) etridiazole (2593-15-9), (10.6) iodocarb (55406-53-6), (10.7) iprobenfos (26087-47-8), (10.8) isoprothiolane (50512-35-1 ), (10.9) propamocarb (25606-41-1 ), (10.10) propamocarb hydrochloride (25606-41-1 ), (10.11 ) prothiocarb (19622-08-3), (10.12) pyrazophos (13457-18-6), (10.13) quintozene (82-68-8), (10.14) tecnazene (117-18-0) and (10.15) tolclofos-m ethyl (57018-04-9).
(11 ) Inhibitors of the melanine biosynthesis, for example (11.1 ) carpropamid (104030-54-8), (11.2) diclocymet (139920-32-4), (11.3) fenoxanil (115852-48-7), (1 1.4) phthalide (27355-22-2), (11.5) pyroquilon (57369-32-1 ) and (11.6) tricyclazole (41814-78-2).
(12) Inhibitors of the nucleic acid synthesis, for example (12.1 ) benalaxyl (71626-11-4), (12.2) benalaxyl-M (kiralaxyl) (98243-83-5), (12.3) bupirimate (41483-43-6), (12.4) clozylacon (67932-
85-8), (12.5) dimethirimol (5221-53-4), (12.6) ethirimol (23947-60-6), (12.7) furalaxyl (57646-30- 7), (12.8) hymexazol (10004-44-1 ), (12.9) metalaxyl (57837-19-1 ), (12.10) metalaxyl-M (mefenoxam) (70630-17-0), (12.11 ) ofurace (58810-48-3), (12.12) oxadixyl (77732-09-3) and (12.13) oxolinic acid (14698-29-4).
(13) Inhibitors of the signal transduction, for example (13.1 ) chlozolinate (84332-86-5), (13.2) fenpiclonil (74738-17-3), (13.3) fludioxonil (131341-86-1 ), (13.4) iprodione (36734-19-7), (13.5) procymidone (32809-16-8), (13.6) quinoxyfen (124495-18-7) and (13.7) vinclozolin (50471-44-8).
(14) Compounds capable to act as an uncoupler, like for example (14.1 ) binapacryl (485-31-4), (14.2) dinocap (131-72-6), (14.3) ferimzone (89269-64-7), (14.4) fluazinam (79622-59-6) and (14.5) meptyldinocap (131-72-6).
(15) Further compounds like for example (15.1 ) 1-(4-{4-[(5R)-5-(2,6-difluorophenyl)-4,5-dihydro- 1 ,2-oxazol-3-yl]-1 ,3-thiazol-2-yl}piperidin-1-yl)-2-[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1- yl]ethanone, (15.2) 1-(4-methoxyphenoxy)-3,3-dimethylbutan-2-yl 1 H-imidazole-1-carboxylate (111227-17-9), (15.3) 2,3,5,6-tetrachloro-4-(methylsulfonyl)pyridine (13108-52-6), (15.4) 2,3- dibutyl-6-chlorothieno[2,3-d]pyrimidin-4(3H)-one (221451-58-7), (15.5) 2-[5-methyl-3- (trifluoromethyl)-1 H-pyrazol-1-yl]-1-(4-{4-[(5R)-5-phenyl-4,5-dihydro-1 ,2-oxazol-3-yl]-1 ,3-thiazol- 2-yl}piperidin-1-yl)ethanone, (15.6) 2-butoxy-6-iodo-3-propyl-4H-chromen-4-one, (15.7) 2- phenylphenol and salts (90-43-7), (15.8) 3,4,5-trichloropyridine-2,6-dicarbonitrile (17824-85-0), (15.9) 3-[5-(4-chlorophenyl)-2,3-dimethyl-1 ,2-oxazolidin-3-yl]pyridine, (15.10) 3-chloro-5-(4- chlorophenyl)-4-(2,6-difluorophenyl)-6-methylpyridazine, (15.11 ) 4-(4-chlorophenyl)-5-(2,6- difluorophenyl)-3,6-dimethylpyridazine, (15.12) 5-amino-1 ,3,4-thiadiazole-2-thiol, (15.13) 5- chloro-N'-phenyl-N'-(prop-2-yn-1-yl)thiophene-2-sulfonohydrazide (134-31-6), (15.14) 5-methyl- 6-octyl[1 ,2,4]triazolo[1 ,5-a]pyrimidin-7-amine, (15.15) ametoctradin (865318-97-4), (15.16) benthiazole (21564-17-0), (15.17) bethoxazin (163269-30-5), (15.18) capsimycin (70694-08-5), (15.19) carvone (99-49-0), (15.20) chinomethionat (2439-01-2), (15.21 ) chlazafenone (688046- 61-9), (15.22) cufraneb (1 1096-18-7), (15.23) cyflufenamid (180409-60-3), (15.24) cymoxanil (57966-95-7), (15.25) cyprosulfamide (221667-31-8), (15.26) dazomet (533-74-4), (15.27) debacarb (62732-91-6), (15.28) dichlorophen (97-23-4), (15.29) diclomezine (62865-36-5), (15.30) difenzoquat (43222-48-6), (15.31 ) difenzoquat methylsulphate (43222-48-6), (15.32) diphenylamine (122-39-4), (15.33) ecomate, (15.34) ethyl (2Z)-3-amino-2-cyano-3-phenylprop- 2-enoate, (15.35) flumetover (154025-04-4), (15.36) fluoroimide (41205-21-4), (15.37) flusulfamide (106917-52-6), (15.38) flutianil (304900-25-2), (15.39) fosetyl-aluminium (39148- 24-8), (15.40) fosetyl-calcium, (15.41 ) fosetyl-sodium (39148-16-8), (15.42) hexachlorobenzene (118-74-1 ), (15.43) irumamycin (81604-73-1 ), (15.44) methasulfocarb (66952-49-6), (15.45) methyl isothiocyanate (556-61-6), (15.46) metrafenone (220899-03-6), (15.47) mildiomycin (67527-71-3), (15.48) N-(4-chlorobenzyl)-3-[3-methoxy-4-(prop-2-yn-1- yloxy)phenyl]propanamide, (15.49) N-[(4-chlorophenyl)(cyano)methyl]-3-[3-methoxy-4-(prop-2- yn-1-yloxy)phenyl]propanamide, (15.50) N-[(5-bromo-3-chloropyridin-2-yl)methyl]-2,4- dichloropyridine-3-carboxamide, (15.51 ) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2,4- dichloropyridine-3-carboxannide, (15.52) N-[1-(5-bromo-3-chloropyridin-2-yl)ethyl]-2-fluoro-4- iodopyridine-3-carboxamide, (15.53) N-{(E)-[(cyclopropylmethoxy)imino][6-(difluoromethoxy)- 2,3-difluorophenyl]methyl}-2-phenylacetamide, (15.54) N-{(Z)-[(cyclopropylmethoxy)innino][6- (difluoromethoxy)-2,3-difluorophenyl]methyl}-2-phenylacetamide (221201-92-9), (15.55) natamycin (7681-93-8), (15.56) nickel dimethyldithiocarbamate (15521-65-0), (15.57) nitrothal- isopropyl (10552-74-6), (15.58) N-methyl-2-(1-{[5-methyl-3-(trifluoromethyl)-1 H-pyrazol-1- yljacetylJpiperidin^-y^-N^I ^.S^-tetrahydronaphthalen-i-y^-I .S-thiazole^-carboxannide, (15.59) N-methyl^i-ltS-methyl-S-OrifluoromethyO-I H-pyrazol-i-yllacetylJpiperidin^-yO-N- [(1 R)-1 ,2,3,4-tetrahydronaphthalen-1-yl]-1 ,3-thiazole-4-carboxamide, (15.60) octhilinone (26530-20-1 ), (15.61 ) oxamocarb (917242-12-7), (15.62) oxyfenthiin (34407-87-9), (15.63) pentachlorophenol and salts (87-86-5), (15.64) pentyl {6-[({[( 1-m ethyl- 1 H-tetrazol-5- yl)(phenyl)methylidene]amino}oxy)methyl]pyridin-2-yl}carbamate, (15.65) phenazine-1- carboxylic acid, (15.66) phenothrin, (15.67) phosphorous acid and its salts (13598-36-2), (15.68) propamocarb-fosetylate, (15.69) propanosine-sodium (88498-02-6), (15.70) proquinazid (189278-12-4), (15.71 ) pyrrolnitrine (1018-71-9) (known from EP-A 1 559 320), (15.72) quinolin- 8-ol (134-31-6), (15.73) quinolin-8-ol sulfate (2:1 ) (134-31-6), (15.74) fenpyrazamine (473798- 59-3), (15.75) tebufloquin (376645-78-2), (15.76) tecloftalam (76280-91-6), (15.77) tolnifanide (304911-98-6), (15.78) triazoxide (72459-58-6), (15.79) trichlamide (70193-21-4), (15.80) zarilamid (84527-51-5) and salts thereof.
(16) Further compounds like for example (2.27) 1-methyl-3-(trifluoromethyl)-N-[2'-
(trifluoromethyl)biphenyl-2-yl]-1 H-pyrazole-4-carboxamide, (2.28) N-(4'-chlorobiphenyl-2-yl)-3- (difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxamide, (2.29) N-(2',4'-dichlorobiphenyl-2-yl)-3- (difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxamide, (2.30) 3-(difluoromethyl)-1-methyl-N-[4'- (trifluoromethyl)biphenyl-2-yl]-1 H-pyrazole-4-carboxannide, (2.31 ) N-(2',5'-difluorobiphenyl-2-yl)- 1-nnethyl-3-(trifluoronnethyl)-1 H-pyrazole-4-carboxannide, (2.32) 3-(difluoromethyl)-1-nnethyl-N- [4'-(prop-1-yn-1-yl)biphenyl-2-yl]-1 H-pyrazole-4-carboxamide (known from WO 2004/058723), (2.33) S-fluoro-i ^-dimethyl-N-^'^prop-i-yn-i-yObiphenyl^-yll-I H-pyrazole^-carboxannide (known from WO 2004/058723), (2.34) 2-chloro-N-[4'-(prop-1-yn-1-yl)biphenyl-2-yl]pyridine-3- carboxamide (known from WO 2004/058723), (2.35) 3-(difluoromethyl)-N-[4'-(3,3-dimethylbut-1- yn-1-yl)biphenyl-2-yl]-1-methyl-1 H-pyrazole-4-carboxamide (known from WO 2004/058723), (2.36) N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]-5-fluoro-1 ,3-dimethyl-1 H-pyrazole-4- carboxamide (known from WO 2004/058723), (2.37) 3-(difluoromethyl)-N-(4'-ethynylbiphenyl-2- yl)-1-methyl-1 H-pyrazole-4-carboxamide (known from WO 2004/058723), (2.38) N-(4'- ethynylbiphenyl-2-yl)-5-fluoro-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide (known from WO 2004/058723), (2.39) 2-chloro-N-(4'-ethynylbiphenyl-2-yl)pyridine-3-carboxamide (known from WO 2004/058723), (2.40) 2-chloro-N-[4'-(3,3-dimethylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3- carboxamide (known from WO 2004/058723), (2.41 ) 4-(difluoromethyl)-2-methyl-N-[4'- (trifluoromethyl)biphenyl-2-yl]-1 ,3-thiazole-5-carboxamide (known from WO 2004/058723),
(2.42) 5-fluoro-N-[4'-(3-hydroxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1 ,3-dimethyl-1 H-pyrazole- 4-carboxamide (known from WO 2004/058723), (2.43) 2-chloro-N-[4'-(3-hydroxy-3-methylbut-1- yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723), (2.44) 3- (difluoromethyl)-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]-1-methyl-1 H-pyrazole-4- carboxamide (known from WO 2004/058723), (2.45) 5-fluoro-N-[4'-(3-methoxy-3-methylbut-1- yn-1-yl)biphenyl-2-yl]-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide (known from WO 2004/058723), (2.46) 2-chloro-N-[4'-(3-methoxy-3-methylbut-1-yn-1-yl)biphenyl-2-yl]pyridine-3-carboxamide (known from WO 2004/058723) and salts thereof., (15.81 ) (5-bromo-2-methoxy-4-methylpyridin- 3-yl)(2,3,4-trimethoxy-6-methylphenyl)methanone (known from EP-A 1 559 320) and (9.10) N- [2-(4-{[3-(4-chlorophenyl)prop-2-yn-1-yl]oxy}-3-methoxyphenyl)ethyl]-N2- (methylsulfonyl)valinamide (220706-93-4).
The composition according to the invention comprising a mixture of a compound of formula (I) with a bactericide compound can also be particularly advantageous. Examples of suitable bactericide mixing partners can be selected in the following list: bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate, kasugamycin, octhilinone, furancarboxylic acid, oxytetracycline, probenazole, streptomycin, tecloftalam, copper sulphate and other copper preparations.
The compounds of formula (I) and the fungicide composition according to the invention can be used to curatively or preventively control the phytopathogenic fungi of plants or crops. Thus, according to a further aspect of the invention, there is provided a method for curatively or preventively controlling the phytopathogenic fungi of plants or crops characterised in that a compound of formula (I) or a fungicide composition according to the invention is applied to the seed, the plant or to the fruit of the plant or to the soil wherein the plant is growing or wherein it is desired to grow.
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 overground parts of the plant such as trunks, stems or stalks, leaves, flowers and fruit of the concerned plant.
Among the plants that may be protected by the method according to the invention, mention may 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, rye, 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), Elaeis sp. (for instance oil palm); horticultural and forest crops; as well as genetically modified homologues of these crops.
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 leucotricha ;
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 vastatrix ;
Phakopsora diseases caused for example by Phakopsora pachyrhizi and Phakopsora meibomiae ; Puccinia diseases caused for example by Puccinia recondita, Puccinia graminis or Puccinia striiformis ;
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 and Peronospora 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 and
Pseudoperonospora cubensis ;
Pythium diseases caused for example by Pythium ultimum ;
• Leaf spot, Leaf blotch and Leaf Blight Diseases such as Alternaria diseases caused for example by Alternaria solani ;
Cercospora diseases caused for example by Cercospora beticola ;
Cladiosporium diseases caused for example by Cladiosporium cucumerinum ;
Cochliobolus diseases caused for example by Cochliobolus sativus (Conidiaform:
Drechslera, Syn: Helminthosporium) or Cochliobolus miyabeanus ; Colletotrichum diseases caused for example by Colletotrichum lindemuthianum ;
Cycloconium diseases caused for example by Cycloconium oleaginum ;
Diaporthe diseases caused for example by Diaporthe citri ;
Elsinoe diseases caused for example by Elsinoe fawcettii ;
Gloeosporium diseases caused for example by Gloeosporium laeticolor ; Glomerella diseases caused for example by Glomerella cingulata ;
Guignardia diseases caused for example by Guignardia bidwellii ;
Leptosphaeria diseases caused for example by Leptosphaeria maculans and Leptosphaeria nodorum ;
Magnaporthe diseases caused for example by Magnaporthe grisea ; Mycosphaerella diseases caused for example by Mycosphaerella graminicola,
Mycosphaerella arachidicola and Mycosphaerella fijiensis ;
Phaeosphaeria diseases caused for example by Phaeosphaeria nodorum ;
Pyrenophora diseases caused for example by Pyrenophora teres or Pyrenophora tritici repentis ; Ramularia- diseases caused for example by Ramularia collo-cygni or Ramularia areola ;
Rhynchosporium diseases caused for example by Rhynchosporium secalis ;
Septoria diseases caused for example by Septoria apii and Septoria lycopersici ;
Typhula diseases caused for example by Thyphula incarnata ; Venturia diseases caused for example by Venturia inaequalis ;
• Root-, Sheath and Stem Diseases such as Corticium diseases caused for example by Corticium graminearum ; Fusarium diseases caused for example by Fusarium 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 ; Thielaviopsis 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 Cladiosporium cladosporioides ; 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 diseases caused for example by Botrytis cinerea ;
Penicillium diseases caused for example by Penicillium expansum and Penicillium purpurogenum ;
Rhizopus diseases caused by example by Rhizopus stolonifer Sclerotinia diseases caused for example by Sclerotinia sclerotiorum ;
Verticillium diseases caused for example by Verticillium alboatrum ;
• Seed- and Soilborne Decay, Mould, Wilt, Rot and Damping-off diseases 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 Fusarium culmorum ;
Gibberella diseases caused for example by Gibberella zeae ; Macrophomina diseases caused for example by Macrophomina phaseolina ;
Microdochium diseases caused for example by Microdochium nivale ;
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 ;
• Blight Diseases such as
Monilinia diseases caused for example by Monilinia laxa ; • Leaf Blister or Leaf Curl Diseases including deformation of blooms and fruit such as
Exobasidium diseases caused for example by Exobasidium vexans. Taphrina diseases caused for example by Taphrina deformans ;
• Decline Diseases of Wooden Plants such as Esca disease caused for example by Phaeomoniella clamydospora, Phaeoacremonium aleophilum and Fomitiporia mediterranea ; 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 Helminthosporium 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 campestris pv. oryzae; Pseudomonas species for example Pseudomonas syringae pv. lachrymans; Erwinia species for example Erwinia amylovora.
The fungicide 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.
The dose of active compound usually applied in the methods of treatment according to the invention is generally and advantageously from 10 to 800 g/ha, preferably from 50 to 300 g/ha for applications in foliar treatment. The dose of active substance applied is generally and advantageously from 2 to 200 g per 100 kg of seed, preferably from 3 to 15O g per 100 kg of seed in the case of seed treatment. It is clearly understood that the doses indicated herein are given as illustrative examples of the 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.
Furthermore combinations and compositions according to the invention may also be used to reduce the contents of mycotoxins in plants and the harvested plant material and therefore in foods and animal feed stuff made therefrom.
Especially but not exclusively the following mycotoxins can be specified:
Deoxynivalenole (DON), Nivalenole, 15-Ac-DON, 3-Ac-DON, T2- und HT2- Toxins,
Fumonisines, Zearalenone Moniliformine, Fusarine, Diaceotoxyscirpenole (DAS), Beauvericine, Enniatine, Fusaroproliferine, Fusarenole, Ochratoxines, Patuline, Ergotalkaloides und
Aflatoxines, which are caused for example by the following fungal diseases: Fusarium spec, like Fusarium acuminatum, F. avenaceum, F. crookwellense, F. culmorum, F. graminearum
(Gibberella zeae), F. equiseti, F. fujikoroi, F. musarum, F. oxysporum, F. proliferatum, F. poae,
F. pseudograminearum, F. sambucinum, F. scirpi, F. semitectum, F. solani, F. sporotrichoides, F. langsethiae, F. subglutinans, F. tricinctum, F. verticillioides and others but also by Aspergillus spec, Penicillium spec, Claviceps purpurea, Stachybotrys spec, and others.
The present invention therefore relates to the use of compounds of formula (I) as herein- described for the reduction of mycotoxins in plants and part of plants, and to methods of combating phytopathogenic and mycotoxin producing fungi characterized in that compounds of formula (I) as herein-described are applied to these fungi and/or their habitat.
The present invention therefore relates to the use of compounds of formula (I) as herein- described as insecticide, and/or nematicide.
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 in which a heterologous gene has been stably integrated into the genome. The expression "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, co suppression 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 transformation 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 phytopathogenic fungi and/ or microorganisms and/or viruses. This may, if appropriate, be one of the reasons of the enhanced activity of the combinations according to the invention, 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 phytopathogenic fungi and/ or microorganisms and/or viruses, the treated plants display a substantial degree of resistance to these unwanted phytopathogenic fungi and/ or microorganisms and/or viruses. In the present case, unwanted phytopathogenic fungi and/ or microorganisms and/or viruses are to be understood as meaning phytopathogenic 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, ozon 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. 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 stress factors. 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- 1992/005251 , WO-1995/009910, WO- 1998/27806, WO-2005/002324, WO-2006/021972 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-1989/10396 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-1991/002069).
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-tolerant 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., Science (1983), 221 , 370-371 ), the CP4 gene of the bacterium Agrobacterium sp. (Barry et al., Curr. Topics Plant Physiol. (1992), 7, 139-145), the genes encoding a Petunia EPSPS (Shah et al., Science (1986), 233, 478-481 ), a Tomato EPSPS (Gasser et al., J. Biol. Chem. (1988),263, 4280-4289), or an Eleusine EPSPS (WO-2001/66704). It can also be a mutated EPSPS as described in for example EP-A 0837944, WO-2000/066746, WO-2000/066747 or WO-2002/026995. Glyphosate-tolerant plants can also be obtained by expressing a gene that encodes a glyphosate oxido-reductase enzyme as described in US 5,776,760 and US 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- 2002/036782, WO-2003/092360, WO-2005/012515 and WO-2007/024782. 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-2001/024615 or WO-2003/013226. 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 US 5,561 ,236; US 5,648,477; US 5,646,024; US 5,273,894; US 5,637,489; US 5,276,268; US 5,739,082; US 5,908,810 and US 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- 1996/038567, WO- 1999/024585 and WO-1999/024586. 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-1999/034008 and WO-2002/36787. Tolerance of plants to HPPD inhibitors can also be improved by transforming plants with a gene encoding an enzyme prephenate dehydrogenase 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, pyrimidinyloxy(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, Weed Science (2002), 50, 700-712, but also, in US 5,605,011 , US 5,378,824, US 5,141 ,870, and US 5,013,659. The production of sulfo ny I urea- tolerant plants and imidazolinone-tolerant plants is described in US 5,605,011 ; US 5,013,659; US 5,141 ,870; US 5,767,361 ; US 5,731 ,180; US 5,304,732; US 4,761 ,373; US 5,331 ,107; US 5,928,937; and US 5,378,824; and international publication WO-1996/033270. 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-2007/024782. 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 US 5,084,082, for rice in WO-1997/41218, for sugar beet in US 5,773,702 and WO- 1999/057965 , for lettuce in US 5,198,599, or for sunflower in WO- 2001/065922.
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., Microbiology and Molecular Biology Reviews (1998), 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 F, Cry2Ab, Cry3Aa, or Cry3Bb or insecticidal portions thereof; 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., Nat. Biotechnol. (2001 ), 19, 668-72; Schnepf et al., Applied Environm. Microbiol. (2006), 71 , 1765-1774); 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 MON98034 (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; 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_Cricknnore/Bt/vip.htnnl, 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 β. cereus, such as the binary toxin made up of the VIP1A and VIP2A proteins (WO-1994/21795); 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 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 (while still encoding an insecticidal protein), such as the VIP3Aa protein in cotton event COT102.
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 8. In one embodiment, an insect-resistant plant contains more than one transgene encoding a protein of any one of the above classes 1 to 8, 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.
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:
a. 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-2000/004173 or WO2006/045633 or PCT/EP07/004142. b. 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.
c. plants which contain a stress tolerance enhancing transgene coding for a plant-functional enzyme of the nicotinamide adenine dinucleotide salvage synthesis pathway including nicotinamidase, nicotinate phosphoribosyltransferase, nicotinic acid mononucleotide adenyl transferase, nicotinamide adenine dinucleotide synthetase or nicotine amide phosphoribosyltransferase as described e.g. in WO2006/032469 or WO- 2006/133827 or PCT/EP07/002433.
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-chemical 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-1995/004826, EP 0719338, WO-1996/15248, WO-1996/19581 , WO-1996/27674, WO-1997/11188, WO- 1997/26362, WO-1997/32985, WO-1997/42328, WO-1997/44472, WO-1997/45545, WO-1998/27212, WO-1998/40503, WO99/58688, WO-1999/58690, WO-1999/58654,
WO-2000/008184, WO-2000/008185, WO-2000/008175, WO-2000/28052, WO- 2000/77229, WO-2001/12782, WO-2001/12826, WO-2002/101059, WO-2003/071860, 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-
2000/22140, WO-2006/063862, WO-2006/072603, WO-2002/034923, EP 06090134.5, EP 06090228.5, EP 06090227.7, EP 07090007.1 , EP 07090009.7, WO-2001/14569, WO-2002/79410, WO-2003/33540, WO-2004/078983, WO-2001/19975, WO- 1995/26407, WO-1996/34968, WO-1998/20145, WO-1999/12950, WO-1999/66050, WO-1999/53072, US 6,734,341 , WO-2000/11192, WO-1998/22604, WO-1998/32326,
WO-2001/98509, WO-2001/98509, WO-2005/002359, US 5,824,790, US 6,013,861 , WO- 1994/004693, WO- 1994/009144, WO-1994/1 1520, WO-1995/35026, WO- 1997/20936.
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- 1996/001904, WO-1996/021023, WO-1998/039460, and WO-1999/024593, plants producing alpha 1 ,4 glucans as disclosed in WO-1995/031553, US 2002/031826, US 6,284,479, US 5,712,107, WO-1997/047806, WO-1997/047807, WO-1997/047808 and WO-2000/014249, plants producing alpha-1 ,6 branched alpha-1 ,4-glucans, as disclosed in WO-2000/73422, plants producing alternan, as disclosed in WO- 2000/047727, 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 2006/304779, and WO-2005/012529.
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-1998/000549 b) Plants, such as cotton plants, containing an altered form of rsw2 or rsw3 homologous nucleic acids as described in WO2004/053219 c) Plants, such as cotton plants, with increased expression of sucrose phosphate synthase as described in WO-2001/017333 d) Plants, such as cotton plants, with increased expression of sucrose synthase as described in WO02/45485 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 fiberselective β 1 ,3-glucanase as described in WO2005/017157 f) Plants, such as cotton plants, having fibers with altered reactivity, e.g. through the expression of N-acteylglucosaminetransferase gene including nodC and chitinsynthase genes as described in WO2006/136351
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 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 6,270828, 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 5,434,283
Particularly useful transgenic plants which may be treated according to the invention are plants which comprise one or more genes which encode one or more toxins, such as the following which are sold under the trade names YIELD GARD® (for example maize, cotton, soya beans), KnockOut® (for example maize), BiteGard® (for example maize), Bt-Xtra® (for example maize), StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton), Nucotn 33B®(cotton), NatureGard® (for example maize), Protecta® and NewLeaf® (potato). Examples of herbicide- tolerant plants which may be mentioned are maize varieties, cotton varieties and soya bean varieties which are sold under the trade names Roundup Ready® (tolerance to glyphosate, for example maize, cotton, soya bean), Liberty Link® (tolerance to phosphinotricin, for example oilseed rape), IMI® (tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, for example maize). Herbicide-resistant plants (plants bred in a conventional manner for herbicide tolerance) which may be mentioned include the varieties sold under the name Clearfield® (for example maize).
Particularly useful transgenic plants which may be treated according to the invention are plants containing transformation events, or combination of transformation events, that are listed for example in the databases from various national or regional regulatory agencies (see for example http://gmoinfo.jrc.it/gmp_browse.aspx and http://www.agbios.com/dbase.php).
The compounds or mixtures 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 various aspects of the invention will now be illustrated with reference to the following table of compound examples and the following preparation or efficacy examples. Table 1 illustrates in a non-limiting manner examples of compounds of formula (I) according to the invention.
Figure imgf000040_0001
(i)
In table 1 , M+H (Apcl+) means the molecular ion peak plus 1 a.m.u. (atomic mass unit) as observed in mass spectroscopy via positive atmospheric pressure chemical ionisation. In table 1 , the logP values were determined in accordance with EEC Directive 79/831 Annex V.A8 by HPLC (High Performance Liquid Chromatography) on a reversed-phase column (C 18), using the method described below :
Temperature: 4O0C ; Mobile phases : 0.1 % aqueous formic acid and acetonitrile ; linear gradient from 10% acetonitrile to 90% acetonitrile.
Calibration was carried out using unbranched alkan-2-ones (comprising 3 to 16 carbon atoms) with known logP values (determination of the logP values by the retention times using linear interpolation between two successive alkanones). lambda-max-values were determined using UV-spectra from 200 nm to 400 nm and the peak values of the chromatographic signals.
Table 2 provides the NMR data (1H and/or 13C) of a selected number of compounds from table 1.
Figure imgf000041_0001
Figure imgf000042_0001
Figure imgf000043_0001
Figure imgf000044_0001
Figure imgf000045_0001
Figure imgf000046_0001
Figure imgf000047_0001
Figure imgf000048_0001
Figure imgf000049_0001
Figure imgf000050_0001
Figure imgf000051_0001
Ul
O
Figure imgf000052_0001
Figure imgf000053_0001
Ul K>
Figure imgf000054_0001
table 2
Figure imgf000055_0001
CL
I NMR
LJJ
13 1C NMR (400 MHz, DMSO-d6) δ ppm : 9.21 , 13.99, 22.58, 28.48, 31.17, 31.67, 33.18,
27 34.69, 107.33, 109.69, 112.05, 127.58, 128.11 , 128.79
13C NMR (400 MHz, DMSO-d6) δ ppm : 8.62, 9.17, 23.62, 28.33, 29.78, 30.32, 34.75, 45.79, 107.52, 109.89, 112.25, 127.10, 127.94, 128.50
13 J /C- NMR (400 MHz, DMSO-d6) δ ppm : 8.82, 34.73, 107.64, 110.00, 112.37, 128.33, 128.68, 131.87, 138.63
13C NMR (400 MHz, DMSO-d6) δ ppm : 9.15, 22.36, 28.47, 30.33, 34.70, 42.34, 44.62, Λ 107.34, 109.71 , 112.07, 127.73, 128.48, 129.14
13 6 /C- NMR (400 MHz, DMSO-d6) δ ppm : 8.96, 22.53, 29.70, 34.70, 41.79, 107.55, 109.92, 112.28, 126.12, 127.03, 127.89, 130.50
13C NMR (400 MHz, DMSO-d6) δ ppm : 23.72, 28.59, 36.91 , 1 10.27, 125.33, 125.73, ό 127.81 , 128.74
13 6 /C- NMR (400 MHz, DMSO-d6) δ ppm : 6.25, 8.79, 30.78, 36.94, 37.17, 55.89, 108.01 , 110.37, 112.72, 128.33, 128.49, 129.04, 139.55
13C NMR (400 MHz, DMSO-d6) δ ppm : 5.91 , 8.46, 30.89, 36.95, 46.94, 108.16, 110.51 , M 112.87, 127.31 , 127.47, 127.52, 128.26
13 6 /C- NMR (400 MHz, DMSO-d6) δ ppm : -0.00, 5.57, 8.21 , 30.63, 36.68, 50.76, 110.17, 125.13, 125.97, 129.31 , 134.32
1H NMR (250 MHz, DMSO-d6) δ ppm :0.37 (s, 9H), 0.54 - 0.74 (m, 4H), 3.11 (bs, 1 H), 3.83 (s, 3H), 5.41 (bs, 2H), 7.14 (t, J=54.40 Hz, 1 H), 7.04 - 7.51 (m, 4H)
13 6 /C- NMR (400 MHz, DMSO-d6) δ ppm : 0.01 , 10.10, 34.69, 34.99, 35.04, 58.78, 107.56, 109.93, 112.30, 127.24, 127.68, 127.76, 127.99, 128.71 , 128.91 CL
I NMR
LJJ
13 J /C- NMR (400 MHz, DMSO-d6) δ ppm : 7.30, 9.01 , 17.02, 27.64, 27.70, 34.70, 34.81 , 53.95, 110.16, 112.53, 125.52, 127.40
13C NMR (400 MHz, DMSO-d6) δ ppm : 7.27, 7.34, 9.09, 12.40, 34.76, 127.45, 127.51 , 127.83
13
1C NMR (400 MHz, DMSO-d6) δ ppm : 6.38, 9.65, 21.96, 22.05, 22.15, 22.51 , 23.39, 2 28.15, 29.97, 30.17, 34.67, 38.91 , 69.69, 69.97, 107.86, 110.22, 112.58, 113.96, 1 14.07, 114.19, 115.86, 127.64, 129.67
13C NMR (400 MHz, DMSO-d6) δ ppm : 7.81 , 8.71 , 18.51 , 22.67, 26.36, 27.40, 27.46, 29.20, 34.68, 35.79, 44.18, 52.33, 109.87, 125.14, 125.21 , 129.49
13 J /C- NMR (400 MHz, DMSO-d6) δ ppm : 7.11 , 8.73, 17.30, 21.41 , 27.39, 30.31 , 34.65, b 54.44, 107.77, 1 10.13, 112.49, 124.70, 128.69
13C NMR (400 MHz, DMSO-d6) δ ppm : 7.88, 8.72, 18.57, 22.83, 23.20, 25.36, 27.48, 27.54, 30.21 , 34.67, 52.31 , 107.50, 109.86, 112.22, 124.99, 125.22, 129.04
13 J /C- NMR (400 MHz, DMSO-d6) δ ppm : 8.75, 30.53, 34.77, 47.19, 107.72, 110.08, 112.45, 127.62, 127.67, 127.73, 127.79, 130.44, 131.21
13C NMR (400 MHz, DMSO-d6) δ ppm : 8.60, 9.03, 31.42, 36.96, 37.06, 45.71 , 50.78, 107.59, 109.94, 1 12.30, 134.02, 143.88
13C NMR (400 MHz, DMSO-d6) δ ppm : 6.94, 8.03, 8.45, 17.15, 27.56, 36.86, 108.19, 0 110.55, 112.90, 118.54, 118.91 , 123.31 , 128.48, 129.76
13C NMR (400 MHz, DMSO-d6) δ ppm : 8.17, 9.07, 11.13, 25.05, 28.79, 28.86, 34.62, 9 34.83, 60.09, 107.53, 108.88, 109.88, 112.24, 126.89, 129.62, 130.55
13 JC/- NMR (400 MHz, DMSO-d6) δ ppm : 8.16, 8.75, 18.18, 28.48, 28.55, 34.64, 53.99, 107.45, 109.82, 112.18, 126.88, 129.44, 130.23 CL
I NMR
LJJ
13
1C NMR (400 MHz, DMSO-d6) δ ppm : 4.80, 7.92, 8.91 , 17.35, 28.63, 28.70, 34.66,
72 52.64, 52.80, 107.55, 108.56, 109.90, 112.26, 122.21 , 122.73, 123.45, 124.01
13C NMR (400 MHz, DMSO-d6) δ ppm : 7.92, 8.40, 17.76, 27.38, 27.45, 27.77, 28.45,
73 28.82, 31.62, 31.65, 31.71 , 34.65, 34.82, 41.42, 41.56, 53.62, 107.49, 108.88, 109.86, 112.22
13
1C NMR (400 MHz, DMSO-d6) δ ppm : 6.42, 9.75, 19.69, 20.89, 21.01 , 22.38, 22.73,
74 26.52, 27.52, 28.24, 34.67, 56.32, 107.94, 110.30, 112.66, 124.34, 129.04
13C NMR (400 MHz, DMSO-d6) δ ppm : 1.03, 8.06, 8.53, 8.84, 18.56, 22.97, 25.17,
80 27.46, 27.53, 27.89, 34.65, 34.77, 45.72, 51.59, 107.50, 109.87, 112.23, 125.33, 125.58, 127.93, 128.19
13 JC/- NMR (400 MHz, DMSO-d6) δ ppm : 8.03, 8.82, 14.76, 18.50, 24.30, 27.42, 27.49, 29.71 , 34.64, 52.06, 107.53, 109.88, 112.24, 125.49, 127.84, 127.95, 128.19
13C NMR (400 MHz, DMSO-d6) δ ppm : 6.79, 9.11 , 25.72, 25.85, 34.45, 34.56, 34.73, 40.63, 58.46, 109.87, 112.24, 125.63, 126.14, 127.80, 128.64
1H NMR (300 MHz, CHCI3-d) δ ppm : 0.60-0.64 (m, 4H), 2.51 (bs, 1 H), 3.79 (s, 3H), 4.97 (s, 2H), 6.91 (t, J=54.4 Hz, 1 H), 7.27-7.33 (m, 1 H), 7.39-7.46 (m, 1 H), 7.52 (d, 1 H).
84 13C NMR (400 MHz, DMSO-d6) δ ppm : 8.99, 34.69, 109.64, 119.55, 119.79, 122.28, 129.53, 129.62
13 JC/- NMR (400 MHz, DMSO-d6) δ ppm : 9.14, 31.44, 34.75, 36.50, 102.00, 109.92, 125.63
13
89 1C NMR (400 MHz, DMSO-d6) δ ppm : 9.24, 34.74, 109.66, 125.55, 125.59
13C NMR (400 MHz, DMSO-d6) δ ppm : 8.63, 9.24, 9.44, 16.76, 27.55, 27.62, 34.69,
90 45.80, 55.51 , 109.68, 134.31 , 143.61 , 143.65
1H NMR (300 MHz, CHCI3-d): d 0.64 (d, 4H), 1.21 (t, 3H), 2.50 (bs, 1 H), 2.64 (q, 2H), 3.79 (s, 3H), 4.81 (s, 2H), 6.87 (t, J=54.4 Hz, 1 H), 6.96-7.09 (m, 2H). CL
L I NMR JJ
1H NMR (300 MHz, CHCI3-d): d 0.64 (d, 4H), 0.90 (d, 6H), 1.79-1.83 (m, 1 H), 2.55 (m,
1 12 3H), 3.79 (s, 3H), 4.79 (s, 2H), 6.87 (t, J=54.4 Hz, 1 H), 6.89-7.06 (m, 2H).
1H NMR (300 MHz, CHCI3-d): d 0.56-0.58 (m, 2H), 0.66-0.70 (m, 4H), 0.92-0.99 (m, 2H),
1 13 1.98-2.01 (m, 1 H), 2.39 (bs, 1 H), 3.79 (s, 3H), 5.12 (s, 2H), 6.93 (t, J=54.4 Hz, 1 H), 6.87- 7.23 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.65-0.66 (m, 4H), 1.21 (t, 3H), 2.62 (q, 2H), 2.64 (bs,
1 14 1 H), 3.81 (s, 3H), 4.71 (s, 2H), 6.86 (t, J=54.6 Hz, 1 H), 6.89-6.95 (m, 2H), 7.13-7.18 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.53-0.60 (m, 4H), 0.90 (t, 3H), 1.31-1.38 (m, 2H), 1.48-
1 15 1.57 (m, 2H), 2.37 (bs, 1 H), 2.69-2.74 (m, 2H), 3.79 (s, 3H), 4.90 (s, 2H), 6.93 (t, J=54.6 Hz, 1 H), 7.12-7.21 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.35 (s, 9H), 0.46 (m, 4H), 2.58 (bs, 1 H), 3.80 (s, 3H), 4.92 (s, 2H), 6.92 (t, J=54.7 Hz, 1 H), 7.10-7.43 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.62-0.70 (m, 4H), 2.89 (bs, 1 H), 3.83 (s, 3H), 4.92 (s, 2H), 6.84 (t, J=54.6 Hz, 1 H), 7.02-7.25 (m, 2H), 7.64-7.69 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.36 (s, 9H), 0.56-0.65 (m, 4H), 2.90 (bs, 1 H), 3.83 (s, 3H), 4.86 (s, 2H), 6.68-7.04 (m, 3H), 7.44-7.49 (m, 1 H).
1 18
13C NMR (400 MHz, DMSO-d6) δ ppm : -0.00, 8.64, 34.60, 50.68, 109.84, 112.13, 112.34, 112.89, 1 13.09, 136.43, 136.50
1H NMR (300 MHz, CHCI3-d): d 0.65-0.68 (m, 4H), 0.92 (t, 3H), 1.33-1.40 (m, 2H), 1.49-
1 19 1.54 (m, 2H), 2.60 (t, 2H), 2.65 (bs, 1 H), 3.81 (s, 3H), 4.71 (s, 2H), 6.85 (t, J=54.6 Hz, 1 H), 7.04-7.20 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.64-0.65 (m, 4H), 0.92 (d, 6H), 1.80-1.84 (m, 1 H), 2.50
120 (d, 2H), 2.74 (bs, 1 H), 3.81 (s, 3H), 4.71 (s, 2H), 6.85 (t, J=54.6 Hz, 1 H), 7.05-7.18 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.64-0.66 (m, 4H), 0.92 (t, 3H), 1.33-1.41 (m, 2H), 1.49-
121 1.54 (m, 2H), 2.60 (t, 2H), 2.74 (bs, 1 H), 3.81 (s, 3H), 4.71 (s, 2H), 6.86 (t, J=54.6 Hz, 1 H), 6.87-6.92 (m, 2H), 7.04-7.12 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.63-0.67 (m, 4H), 0.93 (d, 6H), 1.79-1.83 (m, 1 H), 2.50 (d, 2H), 2.76 (bs, 1 H), 3.81 (s, 3H), 4.71 (s, 2H), 6.67-7.07 (m, 4H). CL
L I NMR JJ
1H NMR (300 MHz, CHCI3-d): d 0.60-0.66 (m, 6H), 0.89-0.95 (m, 2H), 1.82-1.84 (m, 1 H), 2.73 (bs, 1 H), 3.81 (s, 3H), 4.89 (s, 2H), 6.68-6.99 (m, 4H).
1H NMR (300 MHz, CHCI3-d): d 0.52-0.62 (m, 4H), 1.21 (t, 3H), 2.37 (bs, 1 H), 2.75 (q, 2H), 3.79 (s, 3H), 4.93 (s, 2H), 6.93 (t, J=54.4 Hz, 1 H), 7.11-7.20 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.65-0.69 (m, 4H), 1.21 (t, 3H), 2.62-2.64 (m, 3H), 3.81 (s, 3H), 4.70 (s, 2H), 6.85 (t, J=54.6 Hz, 1 H), 7.04-7.22 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.65 (d, 4H), 0.88 (t, 3H), 1.29-1.37 (m, 2H), 1.46-1.54
126 (m, 2H), 2.51 (bs, 1 H), 2.63 (t, 2H), 3.79 (s, 3H), 4.80 (s, 2H), 6.88 (t, J=54.6 Hz, 1 H), 6.90-7.03 (m, 2H).
1H NMR (300 MHz, DMSO-d6): d 0.54-0.57 (m, 4H), 0.82 (d, 6H), 1.73-1.78 (m, 1 H),
127 2.33 (bs, 1 H), 2.54 (d, 2H), 3.75 (s, 3H), 4.68 (s, 2H), 6.76-7.12 (m, 3H), 7.23-7.30 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.55-0.62 (m, 4H), 0.89 (t, 3H), 1.25-1.42 (m, 2H), 1.49-
128 1.54 (m, 2H), 2.46 (bs, 1 H), 2.67 (t, 2H), 3.78 (s, 3H), 4.79 (s, 2H), 6.89 (t, J=54.5 Hz, 1 H), 6.88-7.07 (m, 2H), 7.17-7.22 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.60-0.64 (m, 4H), 1.20 (t, 3H), 2.50 (bs, 1 H), 2.68 (q, 2H), 3.78 (s, 3H), 4.80 (s, 2H), 6.71-7.07 (m, 3H), 7.22-7.23 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.59-0.61 (m, 2H), 0.65-0.70 (m, 4H), 0.91-0.97 (m, 2H),
130 1.96 (bs, 1 H), 2.44 (bs, 1 H), 3.79 (s, 3H), 4.96 (s, 2H), 6.89 (t, J=54.6 Hz, 1 H), 6.72-7.23 (m, 3H).
13 JC/- NMR (400 MHz, DMSO-d6) δ ppm : 10.41 , 23.67, 28.95, 34.71 , 34.99, 35.04, 56.09, 109.77, 112.14, 125.52, 125.79, 126.07, 128.12, 128.29, 128.46
1H NMR (300 MHz, CHCI3-d): d 0.65-0.69 (m, 4H), 1.22 (d, 6H), 2.69 (bs, 1 H), 3.10-3.14
135 (m, 1 H), 3.81 (s, 3H), 4.75 (s, 2H), 6.86 (t, J=54.6 Hz, 1 H), 6.88-6.93 (m, 2H), 7.23-7.28 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.66 (d, 4H), 1.19 (d, 6H), 2.47 (bs, 1 H), 3.12-3.19 (m, 1 H), 3.78 (s, 3H), 4.83 (s, 2H), 6.89 (t, J=54.6 Hz, 1 H), 7.03-7.13 (m, 2H). CL
Ξ cc NMR x
LJJ
1H NMR (300 MHz, CHCI3-d): d 0.59-0.62 (m, 4H), 1.56-1.63 (m, 2H), 1.65-1.75 (m, 2H),
137 1.76-1.82 (m, 2H), 1.95-2.02 (m, 2H), 2.41-2.44 (m, 1 H), 3.22-3.27 (m, 1 H), 3.79 (s, 3H), 4.84 (s, 2H), 6.89 (t, J=52.5 Hz, 1 H), 6.86-7.26 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.64-0.68 (m, 4H), 1.56-1.62 (m, 2H), 1.62-1.70 (m, 2H),
138 1.76-1.83 (m, 2H), 1.96-2.05 (m, 2H), 2.71 (bs, 1 H), 3.13-3.19 (m, 1 H), 3.81 (s, 3H), 4.76 (s, 2H), 6.86 (t, J=54.6 Hz, 1 H), 6.87-6.97 (m, 2H), 7.23-7.28 (m, 1 H).
1H NMR (300 MHz, CHCI3-d): d 0.62-0.64 (d, 4H), 1.56-1.61 (m, 2H), 1.62-1.68 (m, 2H),
139 1.70-1.83 (m, 2H), 1.94-2.04 (m, 2H), 2.47 (bs, 1 H), 3.17-3.23 (m, 1 H), 3.79 (s, 3H), 4.84 (s, 2H), 6.88 (t, J=54.6 Hz, 1 H), 7.04-7.11 (m, 2H).
1H NMR (300 MHz, CHCI3-d): d 0.65-0.69 (m, 4H), 1.56-1.62 (m, 2H), 1.66-1.73 (m, 2H),
140 1.78-1.83 (m, 2H), 1.96-2.03 (m, 2H), 2.70 (bs, 1 H), 3.14-3.19 (m, 1 H), 3.81 (s, 3H), 4.75 (s, 2H), 6.86 (t, J=54.6 Hz, 1 H), 7.18-7.23 (m, 3H).
1H NMR (300 MHz, CHCI3-d): d 0.56-0.58 (m, 4H), 1.56-1.63 (m, 2H), 1.65-1.72 (m, 2H),
141 1.78-1.81 (m, 2H), 2.00-2.02 (m, 2H), 2.39 (bs, 1 H), 3.28-3.33 (m, 1 H), 3.79 (s, 3H), 4.98 (s, 2H), 6.93 (t, J=54.4 Hz, 1 H), 7.12-7.26 (m, 3H).
1H NMR (300 MHz, DMSO-d6): δ 0.43 (q, 1 H), 0.68 (d, 3H), 0.60-0.80 (m, 1 H), 0.90-
142 1.00 (m, 1 H), 1.16 (t, 3H), 2.15-2.35 (m, 1 H), 2.62 (q, 2H), 3.80 (s, 3H), 4.51 (d, 1 H), 4.77 (d, 1 H), 6.98 (t, J=53.8 Hz, 1 H), 7.10-7.30 (m, 4H).
1H NMR (300 MHz, DMSO-d6): δ 0.35 (s, 9H), 0.35-0.45 (m, 1 H), 0.60-0.70 (m, 4H),
143 0.80-0.95 (m, 1 H), 3.83 (s, 3H), 4.61 (d, 1 H), 4.87 (d, 1 H), 6.99 (t, J=53.7 Hz, 1 H), 7.10 (d, 1 H) 7.25 (t, 1 H) 7.38 (t, 1 H) 7.49 (d, 1 H).
1H NMR (300 MHz, DMSO-d6): δ 0.31-0.33 (m, 1 H), 0.53 (d, 3H), 0.66-0.67 (m, 1 H),
144 0.80 (m, 1 H), 2.01 (bs, 1 H), 3.77 (s, 3H), 4.83-4.98 (m, 2H), 6.95 (t, J=53.8 Hz, 1 H), 7.59 (t, 1 H) 7.79-7.82 (m, 2H).
1H NMR (300 MHz, DMSO-d6): d 0.41-0.43 (m, 1 H), 0.65-0.67 (m, 3H), 0.74-0.78 (m,
157 1 H), 0.80-0.86 (m, 1 H), 1.14 (m, 6H), 2.14-2.16 (m, 1 H), 3.10 (bs, 1 H), 3.78 (s, 3H), 4.48- 4.81 (m, 2H), 6.96 (t, J=53.8 Hz, 1 H), 7.13-7.20 (m, 4H).
The following examples illustrate in a non limiting manner the preparation and efficacy of the compounds of formula (I) according to the invention.
Synthesis of δ-chloro-S-fdifluoromethvD-i-methyl-I H-pyrazole^-carboxylic acid (example Mb-D In a 500 ml flask, 6.0 g (31 mmol) of 5-chloro-3-(difluoromethyl)-1-nnethyl-1 H-pyrazole-4- carbaldehyde were added to 30 ml of toluene. A solution of 2.4 g (62 mmol) of sodium hydroxide in 6ml of water was added to the reaction mixture, followed by 103 ml of a 30% solution of hydrogen peroxide in water, whilst keeping the temperature below 370C. After the end of the addition, the reaction mixture was stirred at 5O0C for 7 hours. Once the reaction mixture was back to room temperature, the two phases were separated and the organic phase was extracted with 100 ml of water. The combined aqueous phases were acidified to pH 2 with aqueous hydrochloric acid. The resulting white precipitate was filtered, washed with 2*20 ml of water, and dried to yield 3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxylic acid as a white solid.
1H NMR (400 MHz, DMSO-c/6) δ ppm : 3.78 (s, 3H); 7.12 (t, 1 H, JHF= 53.60 Hz)13.19 (s, 1 H); IR (KBr) : 1688 cm"1 (C=O); 2200-3200 cm"1 broad (hydrogen bond);
Synthesis of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbonyl chloride (example lie-
11
3.2 g of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxylic acid and 44.3 ml of thionyl chloride were refluxed for 5 hours. After cooling down, the reaction mixture was evaporated under vacuum to yield 3.5 g of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4- carbonyl chloride as a yellow oil.
1H NMR (400 MHz, CHCI3-c/6) δ ppm : 3.97 (s, 3H); 7.00 (t, J = 52.01 Hz, 1 H); IR (TQ) : 1759 and 1725 cm"1 (C=O);
Synthesis of 3-(difluoromethyl)-5-fluoro-1-methyl-1 H-pyrazole-4-carbonyl fluoride (example Md-
I)
To a dried solution of 4.0 g (70 mmol) of potassium fluoride in 21 ml of tetrahydrothiophene-1 ,1- dioxide was added a solution of 5.0 g (22 mmol) of 5-chloro-3-(difluoromethyl)-1-methyl-1 H- pyrazole-4-carbonyl chloride in 15 ml of toluene at 1000C. The resulting reaction mixture was stirred at 190-2000C for 22 hours. Distillation under vacuum yielded 8 g of a solution (25% molar) of 3-(difluoromethyl)-5-fluoro-1-methyl-1 H-pyrazole-4-carbonyl fluoride in tetrahydro- thiophene-1 ,1 -dioxide.
1H NMR (250 MHz, CHCI3-c/6) δ ppm : 3.87 (s, 3H); 6.79 (t, J = 53.75 Hz, 1 H); 19F NMR (250 MHz, CHCI3-c/6) δ ppm : 45.37 (s, COF); -117.5 (d, J = 28.2 Hz); -131.6 (m); Synthesis of 5-fluoro-3-(difluoroπnethvπ-1-πnethyl-1 H-pyrazole-4-carboxylic acid (example Me-D To 400 ml of a 1 N sodium hydroxyde aqueous solution, was added dropwise 67.5 g of a solution (10% molar) of 3-(difluoromethyl)-5-fluoro-1-methyl-1 H-pyrazole-4-carbonyl fluoride in tetrahydrothiophene 1 ,1-dioxide. The temperature was kept below 2O0C during the addition. After 2 hours of stirring at room temperature, the reaction mixture was carefully acidified to pH 2 with concentrated aqueous hydrochloric acid. The resulting white precipitate was filtered, washed with water, and dried to yield 6 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4- carboxylic acid as a white solid.
1H NMR (400 MHz, DMSO-c/6) δ ppm: 3.90 (s, 3H); 7.22 (t, 1 H, JHF= 53.55Hz); 13.33 (s, 1 H);
Synthesis of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbonyl chloride (example Nf-
11 9.1 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carboxylic acid and 75.5 ml of thionyl chloride were refluxed for 1.5 hours. After cooling down, the reaction mixture was evaporated under vacuum to yield 10 g of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4- carbonyl chloride as a yellow oil.
GC-MS ; observed M/z :Molecular ion : (M+ ) = 212 ; fragments : (M+ -Cl) = 177 and (M+ -F) = 193;
Synthesis of δ-fluoro-S-fdifluoromethvD-i-methyl-I H-pyrazole^-carboxylic acid (Me-D
Step a : synthesis of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbaldehyde (example Ma-D
To 96.3 g (1660 mmol) of spray-dried potassium fluoride, was added a solution of 129.2 g (664mmol) of 5-chloro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbaldehyde in 1000 ml of dimethylformamide. The resulting reaction mixture was stirred at 15O0C for 3 hours. The reaction mixture was cooled to room temperature and to it was added 4L of water. The aqueous phase was extracted with ethyl acetate. The combined organic phase were washed with brine, dried over sodium sulphate and evaporated under vacuum to give the expected product. 1H NMR (CD3CN) δ ppm: 9.8 (1 H, s), 6,88 (1 H, t), 3,7 (3H, s ); 19F NMR (CD3CN) δ ppm: -114,75 (2F, t), -124,06 (1 F, s); Step b: synthesis of 5-fluoro-3-(difluoromethyl)-1-nnethyl-1 H-pyrazole-4-carboxylic acid A suspension of 79.7 g (350 mmol) of periodic acid in 640 ml absolute acetonitrile was stirred for 30 min. To this was added 56.6g (318 mmol) of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H- pyrazole-4-carbaldehyde at O0C and a solution of 1.4 g (6 mmol) of pyridinium chlorochromate in 130 ml dry acetonitrile. The reaction mixture was stirred for 2.5 hours at room temperature. 1600 ml of ethyl acetate was added to the reaction mixture and the separated organic phase was washed consecutively with brine/ water(1 :1 ), saturated sodium metabisulfite and brine. Then the organic phase was dried with sodium sulphate, and evaporated under vacuum to give the expected product as a pale yellow solid.
Synthesis of N-cvclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl1-1 H- pyrazole-4-carboxamide (example 3)
To 175 mg (0.80 mmol) of N-[2-(trimethylsilyl)benzyl]cyclopropanamine in 5 ml of dry tetrahydrofurane was added 0.234 ml (1.68 mmol) of triethylamine, followed by a solution of 187 mg (0.88 mmol) of 5-fluoro-3-(difluoromethyl)-1-methyl-1 H-pyrazole-4-carbonyl chloride in 3 ml of tetrahydrofurane. The reaction mixture was stirred under reflux for 3 hours. After cooling down, the reaction mixture was filtered, and the filtrate was evaporated under vacuum. The residue was dissolved in ethyl acetate / water. The aqueous phase was further extracted with ethyl acetate. The combined organic phase were dried and evaporated under vacuum to give 209 mg of the expected product.
1 H NMR (400 MHz, DMSO-d6) δ ppm : 0.36 (s, 9H), 0.53 (bs, 2H) 0.64 (d, 2H), 2.86 (bs, 1 H), 3.82 (bs, 3H), 4.77 (bs, 2H), 7.00 (t, J=54.06 Hz, 1 H), 7.11-7.49 (m, 4H);
Synthesis of N-cvclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl1-1 H- pyrazole-4-carbothioamide (example 38)
A solution of 140 mg (0.31 mmol) of phosphorus pentasulfide and 500 mg (1.26 mmol) of N- cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-N-[2-(trimethylsilyl)benzyl]-1 H-pyrazole-4- carboxamide in 20 ml of dioxane was heated at 1000C for 2.5 hours. 2 ml of water were then added and the reaction mixture was heated at 1000C for another 1 hour.
After cooling down, the reaction mixture was extracted with ethyl acetate. The combined organic phase were washed with an aqueous solution of sodium carbonate, dried and evaporated under vacuum. The resulting residue was purified on silica to yield 220 mg of the expected product. 1 H NMR (250 MHz, DMSO-d6) δ ppm :0.37 (s, 9H), 0.54 - 0.74 (m, 4H), 3.11 (bs, 1 H), 3.83 (s, 3H), 5.41 (bs, 2H), 7.14 (t, J=54.40 Hz, 1 H), 7.04 - 7.51 (m, 4H);
Example A : in vivo preventive test on Venturia inaegualis (apple scab) 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 preventive 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 untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 10 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 26, 28, 29, 30, 31 , 32, 33, 34, 38, 39, 40, 41 , 42, 43, 44, 44a, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 58, 61 , 62, 63, 64, 65, 66, 68, 69, 70, 71 , 72, 74, 75, 76, 77, 78, 80, 81 , 82, 83, 84, 85, 88, 92, 95, 96, 98, 99, 101 , 105, 107, 108, 109, 110, 131 , 132, 133, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 135, 136, 137, 138, 139, 140, 141 , 142, 143, 144 and 157 according to the invention whereas weak protection (less than 30% of disease control) to no protection at all is observed at a dose of 10 ppm of active ingredient with the compounds of examples 45 disclosed in international patent WO-2006/120224, and 397 disclosed in international patent WO-2007/087906.
Example B: in vivo preventive test on Botrytis cinerea (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 preventive 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 untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, high (at least 90% of disease control) to total protection (100% of disease control) is observed at a dose of 100 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 38, 40, 41 , 42, 44, 44a, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 61 , 63, 65, 68, 69, 71 , 73, 75, 76, 77, 78, 81 , 82, 83, 85, 88, 89, 92, 95, 96, 99, 101 , 105, 107, 108, 109, 110, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 132, 133, 135, 136, 139, 138, 140, 141 , 142 and 144 according to the invention whereas weak protection (less than 30% of disease control) to no protection at all is observed at a dose of 100 ppm of active ingredient with the compounds of examples 45 disclosed in international patent WO-2006/120224, and 414 disclosed in international patent WO- 2007/087906.
Example C: in vivo curative test on Puccinia thticina (wheat)
Solvent: 49 parts by weight of n,n-dimethylacetamid
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 active 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 curative activity, young plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabinet at approximately 2O0C and a relative atmospheric humidity of approximately 100%.
2 days later the plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application. The plants are placed in the greenhouse at a temperature of approximately 2O0C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, high (at least 95% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 8, 9, 11 , 13, 15, 21 , 23, 24, 25, 28, 29, 33, 36, 37, 38, 39, 41 , 42, 43, 45, 48, 49, 52, 53, 61 , 63, 83, 84, 90 and 105 according to the invention whereas weak protection (less than 70% of disease control) to no protection at all is observed at a dose of 500 ppm of active ingredient with the compounds of examples 45 and 54 disclosed in international patent WO-2006/120224, and 22 disclosed in international patent WO-2009/016218 and weaker protection (less than 85% of disease control) is observed at a dose of 500 ppm of active ingredient with the compound of example 89 disclosed in international patent WO-2009/016221.
Example D: in vivo curative test on Fusahum nivale (wheat)
Solvent: 49 parts by weight of n,n-dimethylacetamid
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 active 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 curative activity, young plants are sprayed with a spore suspension of Puccinia triticina. The plants remain for 48 hours in an incubation cabinet at approximately 2O0C and a relative atmospheric humidity of approximately 100%. 2 days later the plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
The plants are placed in the greenhouse at a temperature of approximately 2O0C and a relative atmospheric humidity of approximately 80%.
The test is evaluated 8 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 4, 5, 6, 8, 9, 10, 14, 15, 16, 17, 18,
20, 23, 24, 25, 28, 29, 30, 33, 36, 39, 40, 41 , 42, 43, 44, 45, 46, 48, 51 , 52, 53, 61 , 63, 64, 80, 81 , 84, 90 and 105 according to the invention whereas weak protection (less than 95% of disease control) is observed at a dose of 500 ppm of active ingredient with the compound of example 89 disclosed in international patent WO-2009/016221.
Example E: in vivo preventive test on Phakopsora pachyrhizi (soybean rust) 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.
Under these conditions, high (at least 90% of disease control) to total protection (100% of disease control) is observed at a dose of 50 ppm of active ingredient with the following compounds : 3, 11 , 12, 13, 16, 24, 25, 37, 38, 49 and 74 according to the invention whereas weak protection (less than 50% of disease control) to no protection at all is observed at a dose of 50 ppm of active ingredient with the compounds of examples 397 and 402 disclosed in international patent WO-2007/087906, 22 disclosed in international patent WO-2009/016218 and 89 disclosed in international patent WO-2009/016221 and weaker protection (less than 85% of disease control) is observed at a dose of 50 ppm of active ingredient with the compound of example 7 disclosed in international patent WO-2009/016220.
Example F: in vivo curative test on Blumeria graminis (wheat) Solvent: 49 parts by weight of n,n-dimethylacetamid 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 active 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 curative activity, young plants are dusted with spores of Blumeria graminis f.sp. tritici and placed then in a greenhouse at a temperature of approximately 180C and a relative atmospheric humidity of approximately 80%.
48 hours after inoculation, the plants are sprayed with the preparation of active compound or active compound combination at the stated rate of application.
After the spray coating has been dried, the plants are placed again in a greenhouse at a temperature of approximately 180C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
The plants are placed in the greenhouse at a temperature of approximately 180C and a relative atmospheric humidity of approximately 80% to promote the development of mildew pustules.
The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 80% of disease control) to total protection (100% of disease control) is observed at a dose of 250 ppm of active ingredient with the following compounds : 1 , 2, 3, 5, 6, 8, 9, 10, 11 , 12, 15, 29, 30, 33, 38, 39, 46, 47, 48, 50, 51 , 52, 53, 61 ,
68, 70 and 72 according to the invention whereas weak protection (less than 70% of disease control) to no protection at all is observed at a dose of 250 ppm of active ingredient with the compounds of examples 22 disclosed in international patent WO-2009/016218 and 89 disclosed in international patent WO-2009/016221.
Example G : in vivo preventive test on Sphaerotheca fuliginea (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. After the spray coating has dried on, the plants are inoculated with an aqueous spore suspension of Sphaerotheca fuliginea. The plants are then 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 untreated control, while an efficacy of 100% means that no disease is observed. Under these conditions, total protection (100% of disease control) is observed at a dose of 10 ppm of active ingredient with the following compounds : 1 , 2, 5, 6, 8, 10, 1 1 , 12, 13, 14, 15, 18, 22, 23, 24, 26, 27, 29, 32, 38, 41 , 44a, 47, 49, 50, 52, 54, 62, 68, 70, 72, 73, 80, 81 , 82, 83, 84, 99, 101 , 111 , 112, 113, 115, 116, 117, 118, 119, 120, 121 , 123, 124, 126, 127, 128, 130, 131 , 132, 135, 136, 137, 138, 139, 141 , and 157 according to the invention whereas weak protection (less than 85% of disease control) is observed at a dose of 10 ppm of active ingredient with the compounds of examples 45 disclosed in international patent WO-2006/120224 and 89 disclosed in international patent WO-2009/016221.
Example H : in vivo preventive test on Alternaha solani (tomato) 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 Alternaria solani. The plants remain for one day in an incubation cabinet at approximately 220C and a relative atmospheric humidity of 100%. Then the plants are placed in an incubation cabinet at approximately 2O0C and a relative atmospheric humidity of 96%.
The test is evaluated 7 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 21 , 22b, 23, 24, 25, 27, 28, 29, 30, 31 , 32, 32, 33, 34, 35, 36, 38, 39, 40, 40a, 40b, 41 , 42, 43, 44, 44a, 44b, 45, 46b, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 64, 65, 66, 67, 68, 69, 71 , 73, 74, 75, 76, 77, 78, 83, 85, 86, 87, 88, 89, 92, 93, 94, 95, 96, 97, 99, 100, 101 , 102, 103, 105, 106, 107, 108, 109, 110, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 131 , 132, 133, 136, 137, 138, 139, 140, 141 , 142, 143, 144 and 157.
Example I: in vivo preventive test on Leptosphaeria nodorum (wheat) Solvent: 49 parts by weight of n,n-dimethylacetamid 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 preventive activity, young plants are sprayed with a 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 Leptosphaeria nodorum. The plants remain for 48 hours in an incubation cabinet at 220C and a relative atmospheric humidity of 100%. Then the plants are placed in a greenhouse at a temperature of approximately 220C and a relative atmospheric humidity of approximately 90%.
The test is evaluated 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control, while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 22a, 22b, 23,
24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 38, 39, 40, 40a, 40b, 41 , 42, 43, 44, 44a, 44b, 45, 46,
46a, 46b, 54, 55, 57, 58, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78,
80, 81 , 82, 83, 84, 85, 87, 88, 89, 90, 91 , 92, 95, 96, 97, 98, 100, 101 , 102, 103, 104, 105, 106, 107, 108, 109, 110, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125,
126, 127, 128, 129, 130, 131 , 132, 133, 135, 136, 137, 138, 139, 140, 141 and 144.
Example J: in vivo preventive test on Puccinia recondita (wheat)
Solvent: 49 parts by weight of n,n-dimethylacetamid 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 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 Puccinia recondita. The plants remain for 48 hours in an incubation cabinet at 220C and a relative atmospheric humidity of 100%. Then 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 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 22a, 23, 24,
25, 26, 27, 28, 29, 30, 31 , 32, 32, 33, 34, 35, 36, 37, 38, 39, 40, 40b, 41 , 42, 43, 44, 44a, 45, 46,
46a, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 68, 69, 70, 71 , 72, 74, 75, 76, 77, 78, 80, 81 ,
82, 83, 84, 84, 85, 86, 87, 88, 89, 92, 94, 95, 97, 99, 100, 103, 104, 105, 106, 107, 108, 109, 110, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128,
129, 130, 131 , 132, 133, 135, 136, 137, 138, 139, 140, 141 , 142, 143, 144 and 157.
Example K: in vivo preventive test on Pyrenophora teres (barley)
Solvent: 49 parts by weight of n,n-dimethylacetamid 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 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 Pyrenophora teres. The plants remain for 48 hours in an incubation cabinet at 220C and a relative atmospheric humidity of 100%. Then 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 7-9 days after the inoculation. 0% means an efficacy which corresponds to that of the untreated control while an efficacy of 100% means that no disease is observed.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 9, 10, 11 , 12, 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 22a, 22b, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 32, 33, 34, 35, 36, 37, 38, 39, 40, 40a, 40b, 41 , 42, 43, 44, 44a, 44b, 45, 46, 46a, 46b, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 64, 65, 66, 67, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 105, 106, 107, 108, 109, 110, 111 , 112, 113, 114, 115, 116, 117, 118, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 135, 136, 137, 138, 139, 140, 141 , 142, 143, 144 and 157.
Example L : in vivo preventive test on Sphaerotheca fuliginea (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 untreated 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.
Under these conditions, good (at least 70% of disease control) to total protection (100% of disease control) is observed at a dose of 500 ppm of active ingredient with the following compounds : 1 , 2, 3, 4, 5, 6, 8, 9, 10, 11 , 12, 13, 14, 15, 16, 18, 19, 20, 21 , 22, 22a, 22b, 23, 24, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 34, 36, 38, 39, 40, 40a, 40b, 41 , 42, 43, 44, 44a, 45, 46, 46a, 46b, 54, 55, 56, 58, 61 , 62, 63, 64, 65, 66, 68, 69, 70, 71 , 72, 73, 74, 75, 76, 77, 78, 80, 81 , 82, 83, 84, 85, 86, 87, 88, 89, 90, 91 , 92, 93, 94, 95, 96, 97, 98, 99, 100, 101 , 102, 103, 104, 105, 106, 107, 108, 109, 110, 111 , 112, 113, 114, 1 15, 1 16, 1 17, 1 18, 119, 120, 121 , 122, 123, 124, 125, 126, 127, 128, 129, 130, 131 , 132, 133, 135, 136, 137, 138, 139, 140, 141 , 142, 143, 144 and 157.
Example M : inhibition of Fumonisin FB1 produced by Fusahum proliferatum
Compounds were tested in microtiter plates in fumonisin-inducing liquid media (0.5g malt extract, 1g yeast extract, 1g bacto peptone, 20 g Fructose, 1g KH2PO4, 0.3g MgSO4x7H2O, 0.3g KCI, 0.05g ZnSO4x7H2O and 0.01g CuSO4x5H2O per liter) containing 0.5% DMSO, inoculated with a concentrated spore suspension of Fusarium proliferatum to a final concentration of 2000 spores/ml. Plates were covered and incubated at high humidity at 20 0C for 5 days
At start and after 5 days OD measurement at OD620 multiple read per well (square: 3 x 3) was taken to calculate growth inhibition.
After 5 days samples of each culture medium were taken and diluted 1 :1000 in 50 % acetonitrile.
The amounts of fumonisin FB1 of the samples were analysed per HPLC-MS/MS and results were used to calculate inhibition of FB1 production in comparison to a control without compound.
HPLC-MS/MS was done with the following parameters:
Ionization mode: ESI positive lonspray voltage: 5500V
Spraygas Temperature: 5000C
Declustering potential: 1 14V
Collision energy: 51 eV
Collision gas: N2
MRM trace: 722,3 > 352,3; dwell time 100ms
HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fully endcapped)
Particle size: 3μm
Column size: 50x2 mm
Temperature: 4O0C
Solvent A: Water+0.1 % HCOOH (v/v)
Solvent B: Acetonitrile+0.1 % HCOOH (v/v)
Flow: 400μL/min
Injection volume: 5μL
Gradient:
Figure imgf000074_0001
Under these conditions, an activity of > 80 % of inhibition of Fumonisin FB1 production is observed at a dose of 50 μM of active ingredient with the following compounds : 2, 4, 6, 8, 9, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 23, 25, 26, 27, 28, 29, 30, 31 , 32, 33, 35, 36, 40, 41 , 42, 44, 45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 56, 58, 60, 61 , 62, 63, 65, 66 and 67 whereas weak activity (less than 55% of Fumonisin FB1 production inhibition) to no activity is observed at a dose of 50 μM of active ingredient with the compound of example 54 disclosed in international patent WO- 2006/120224. Growth inhibition of Fusarium proliferatum of these examples varied from 27 to 84 % at 50 μM of active ingredient.
Example N : inhibition of deoxynivalenol (DON) and acetyldeoxynivalenol (Acetyl-DON) produced by Fusarium graminearum
Compounds were tested in microtiter plates in DON-inducing liquid media (1g (NhU)2HPO4, 0.2g
MgSO4x7H2O, 3g KH2PO4, 1Og Glycerin, 5g NaCI and 4Og Sachharose per liter), supplemented with 10 % oat extract, containing 0.5% DMSO, inoculated with a concentrated spore suspension of Fusarium graminearum to a final concentration of 2000 spores/ml. The plate was covered and incubated at high humidity at 280C for 7 days.
At start and after 3 days OD measurement at OD620 multiple read per well (square: 3 x 3) was taken to calculate the growth inhibition.
After 7 days 1 volume of 84/16 acetonitrile/water was added to each well and a sample of the liquid medium was taken and diluted 1 :100 in 10 % acetonitrile. The amounts of DON and Acetyl-DON of the samples were analysed per HPLC-MS/MS and results were used to calculate inhibition of DON/AcDON production in comparison to a control without compound.
HPLC-MS/MS was done with the following parameters:
Ionization mode: ESI negative lonspray voltage: -4500V Spraygas Temperature: 5000C
Declustering potential: -40V
Collision energy: -22eV
Collision gas: N2
MRM trace: 355,0 > 264,9; dwell time 150ms HPLC column: Waters Atlantis T3 (trifunctional C18 bonding, fully endcapped)
Particle size: 3μm
Column size: 50x2 mm
Temperature: 4O0C
Solvent A: Water/2.5mM NH4OAc+0.05% CH3COOH (v/v) Solvent B: Methanol/2.5mM NH4OAc+0.05% CH3COOH (v/v)
Flow: 400μL/min
Injection volume: 11 μL
Gradient:
Figure imgf000075_0001
Figure imgf000076_0001
Under these conditions, an activity of > 80 % of inhibition of DON/Acetyl-DON production is observed at a dose of 50 μM of active ingredient with the following compounds : 18, 22, 26, 40,
44, 46, 47, 48, 50, 51 , 54, 58, 62, 63, 65 and 66. Growth inhibition of Fusarium graminearum of these examples varied from 14 to 100 % at 50 μM of active ingredient.
Example O : inhibition of aflatoxines produced by Aspergillus parasiticus
Compounds were tested in microtiter plates (96 well black flat and transparent bottom) in Aflatoxin-inducing liquid media (2Og sucrose, yeast extract 4g, KH2PO4 1g, and MgSO4 7H2O 0.5g per liter), supplemented with 2OmM of Cavasol (hydroxypropyl-beta-cyclodextrin) and containing 1 % of DMSO. The assay is started by inoculating the medium with a concentrated spore suspension of Aspergillus parasiticus at a final concentration of 1000 spores/ml. The plate was covered and incubated at 2O0C for 7 days. After 7 days of culture, OD measurement at OD620nm with multiple read per well (circle: 4 x 4) was taken with an Infinite 1000 (Tecan) to calculate the growth inhibition. In the same time bottom fluorescence measurement at Em360n,,, and Ex426nm with multiple read per well (square: 3 x 3) was taken to calculate inhibition of aflatoxin formation.
Under these conditions, an activity of > 80 % of inhibition of aflatoxines production is observed at a dose of 50 μM of active ingredient with the following compounds : 1 , 2, 3, 6, 8, 9, 11 , 13, 14, 15, 16, 17, 18, 19, 20, 21 , 22, 22, 25, 26, 27, 28, 29, 30, 31 , 33, 34, 35, 36, 38, 39, 40, 42, 43,
45, 46, 47, 48, 49, 50, 51 , 52, 53, 54, 55, 56, 57, 58, 59, 60, 61 , 62, 63, 65 and 66.
Growth inhibition of Fusarium graminearum of these examples was also > 80% at 50 μM of active ingredient.
Example P : injection test on Boophilus microplus 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 1 μl 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, the following compounds from the preparation examples showed good activity of > 80% at application rate of 20μg of active ingredient /animal: 4, 5, 6, 7, 12, 29 and 30.
Example Q : spray application test on Tetranychus urticae Solvent: 78.0 parts by weight acetone
1.5 parts by weight dimethylformamide Emulsifier: 0.5 parts by weight alkylarylpolyglcolether
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, the following compounds from the preparation examples showed good activity of > 80 % at application rate of 50Og of active ingredient /ha: 1 , 5, 6, 30 and 40.
Example R : test on Meloidogyne ingognita
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 salade 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, the following compound from the preparation examples showed good activity of > 80 % at application rate of 20 ppm of active ingredient: 6. Example 45 disclosed in international patent WO-2006/120224 correspond to N-{[3-chloro-5-
(trifluoronnethyOpyridin^-yllnnethylJ-N-cyclopropyl-S-fluoro-I .S-dinnethyl-I H-pyrazole^- carboxamide. Example 54 disclosed in international patent WO-2006/120224 correspond to N-{[3-chloro-5-
(trifluoromethyl)pyridin-2-yl]methyl}-N-cyclopropyl-3-(difluoromethyl)-5-fluoro-1-methyl-1 H- pyrazole-4-carboxamide.
Example 397 disclosed in international patent WO-2007/087906 corresponds to N-[2-chloro-6-
(trifluoromethy^benzyll-N-cyclopropyl-S-fluoro-I .S-dimethyl-I H-pyrazole^-carboxamide. Example 402 disclosed in international patent WO-2007/087906 corresponds to N-cyclopropyl-
5-fluoro-N-(2-iodobenzyl)-1 ,3-dimethyl-1 H-pyrazole-4-carboxamide.
Example 414 disclosed in international patent WO-2007/087906 corresponds to N-cyclopropyl-
N-II^S.S-dichloropheny^ethyll-δ-fluoro-I .S-dimethyl-i l-l-pyrazole^-carboxamide.
Example 89 disclosed in international patent WO-2009/016221 corresponds to N-cyclopropyl-3- (difluoromethy^-S-fluoro-i-methyl-N-II^I-naphthy^ethyll-I H-pyrazole^-carboxamide.
Example 22 disclosed in international patent WO-2009/016218 corresponds to N-cyclopropyl-5- fluoro-N-(6-isopropoxy-1 ,2,3,4-tetrahydronaphthalen-1-yl)-1 ,3-dimethyl-1 H-pyrazole-4- carboxamide.
Example 7 disclosed in international patent WO-2009/016220 corresponds to N-cyclopropyl-5- fluoro-1 ,3-dimethyl-N-[2-(trimethylsilyl)benzyl]-1 H-pyrazole-4-carbothioamide.
These results show that the compounds according to the invention have a much better biological activity than the structurally closest compounds disclosed in WO-2006/120224, WO- 2007/087906, WO-2009/016218, WO-2009/016220 and WO-2009/016221.

Claims

1. A compound of formula (I)
Figure imgf000079_0001
wherein
• Y represents CR5 or N;
• T represents S or O ;
• X1 and X2 which can be the same or different, represent a chlorine or a fluorine atom ;
• Z1 represents a non substituted cyclopropyl or a cyclopropyl substituted by up to 2 atoms or groups which can be the same or different and which can be selected in the list consisting of halogen atoms ; cyano ; Ci-C8-alkyl ; or Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ;
• Z2 and Z3, which can be the same or different, represent a hydrogen atom ; substituted or non substituted Ci-C8-alkyl ; substituted or non substituted C2-C8-alkenyl ; substituted or non substituted C2-C8-alkynyl ; cyano ; isonitrile ; nitro ; a halogen atom ; substituted or non substituted Ci-C8-alkoxy ; substituted or non substituted C2-C8-alkenyloxy ; substituted or non substituted C2-C8-alkynyloxy ; substituted or non substituted C3-C7- cycloalkyl ; substituted or non substituted d-C8-alkylsulfanyl ; substituted or non substituted C-ι-C8-alkylsulfonyl ; substituted or non substituted C-ι-C8-alkylsulfinyl ; amino ; substituted or non substituted d-C8-alkylamino ; substituted or non substituted di-d-C8-alkylamino ; substituted or non substituted d-C8-alkoxycarbonyl ; substituted or non substituted C-ι-C8-alkylcarbamoyl ; substituted or non substituted CIi-C1-C8- alkylcarbamoyl ; or substituted or non substituted N-C-ι-C8-alkyl-C-ι-C8- alkoxycarbamoyl ; or
Z3 and R1 together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5-, 6- or 7-mennbered, partly saturated, carbo- or hetero- cycle comprising up to 3 heteroatoms and Z2 is as herein described; or Z2 and Z3 together with the carbon atom to which they are linked form a substituted or non substituted C3-C7 cycloalkyl ;
R1, R2, R3, R4 and R5, which can be the same or different, represent a hydrogen atom; a halogen atom ; nitro ; cyano ; isonitrile ; hydroxyl ; sulfanyl ; amino ; pentafluoro-λ6- sulfanyl ; substituted or non substituted Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-Cs-alkylamino ; substituted or non substituted di-Ci-C8-alkylamino ; substituted or non substituted Ci-C8-alkoxy ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; Ci-C8-alkoxy-Ci-C8-alkyl ; substituted or non substituted Ci-C8-alkylsulfanyl ; Ci-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkenyl ; C2-C8-halogenoalkenyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkynyl ; C2-C8-halogenoalkynyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2-C8-alkenyloxy ; C2-C8-halogenoalkenyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C2- C8-alkynyloxy ; C2-C8-halogenoalkynyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl ; C3-C7- halogenocycloalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl-Ci-C8-alkyl ; substituted or non substituted C3-C7-cycloalkyl-C2-C8-alkenyl ; substituted or non substituted C3-C7- cycloalkyl-C2-C8-alkynyl ; substituted or non substituted C3-C7-cycloalkyl-C3-C7- cycloalkyl ; substituted or non substituted Ci-C8-alkyl-C3-C7-cycloalkyl ; formyl ; formyloxy ; formylamino ; carboxy ; carbamoyl ; N-hydroxycarbamoyl ; carbamate ; (hydroxyimino)-Ci-C8-alkyl ; substituted or non substituted Ci-C8-alkylcarbonyl ; C1-C8- halogenoalkylcarbonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted Ci-C8-alkylcarbamoyl ; substituted or non substituted di-C-ι-C8-alkylcarbamoyl ; N-(substituted or non substituted C1-C8- alkyloxy)carbamoyl ; substituted or non substituted d-C8-alkoxycarbamoyl ; N- (substituted or non substituted d-C8-alkyl)-(substituted or non substituted C1-C8- alkoxy)-carbamoyl ; substituted or non substituted C-ι-C8-alkoxycarbonyl ; C1-C8- halogenoalkoxycarbonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted d-Cs-alkylaminocarbonyl ; di- substituted or non substituted d-Cs-alkylaminocarbonyl ; substituted or non substituted C1-C8- alkylcarbonyloxy ; d-Cs-halogenoalkylcarbonyloxy comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C1-C8- alkylcarbonylamino ; d-Cs-halogenoalkylcarbonylannino comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C1-C8- alkylaminocarbonyloxy ; substituted or non substituted di-d-Cs-alkylaminocarbonyloxy ; substituted or non substituted d-Cs-alkyloxycarbonyloxy ; substituted or non substituted d-C8-alkylsulfinyl ; d-C8-halogenoalkylsulfinyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted d-C8-alkylsulfonyl ; C1-C8- halogenoalkylsulfonyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted d-C8-alkoxyimino ; (d-C8-alkoxyimino)-d-C8- alkyl ; substituted or non substituted (d-C8-alkenyloxyimino)-d-C8-alkyl ; (C1-C8- alkynyloxyimino)-d-C8-alkyl ; a (benzyloxyimino)-d-C8-alkyl ; tri(substituted or non substituted d-C8-alkyl)silyl ; tri(substituted or non substituted d-C8-alkyl)silyl-d-C8- alkyl ; benzyloxy which can be substituted by up to 5 groups Q ; benzylsulfanyl which can be substituted by up to 5 groups Q ; benzylamino which can be substituted by up to 5 groups Q ; aryl which can be substituted by up to 7 groups Q ; aryloxy which can be substituted by up to 7 groups Q ; arylamino which can be substituted by up to 7 groups Q ; arylsulfanyl which can be substituted by up to 7 groups Q ; aryl-d-C8alkyl which can be substituted by up to 7 groups Q ; aryl-C2-C8-alkenyl which can be substituted by up to 7 groups Q ; aryl-C2-C8-alkynyl which can be substituted by up to 7 groups Q ; pyridinyl which can be substituted by up to 4 groups Q ; pyridinyloxy which can be substituted by up to 4 groups Q ; aryl-C3-C7-cycloalkyl which can be substituted by up to 7 groups Q ; or
Two vicinal substituents R together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5- or 6-membered, saturated, carbo- or hetero-cycle comprising up to 3 heteroatoms and the other substituents R are as herein-described; or • R1 and Z3 together with the consecutive carbon atoms to which they are linked form a substituted or non substituted 5-, 6- or 7-membered, partly saturated, carbo- or hetero- cycle comprising up to 3 heteroatoms, and R2 to R5 are as herein-described;
• Q, which can be the same or different, represents a halogen atom ; cyano ; nitro ; C1- C8-alkyl ; d-C8-alkoxy ; d-C8-alkylsulfanyl ; d-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; Ci-C8-halogenoalkoxy comprising up to 9 halogen atoms which can be the same or different ; tri(d-C8)alkylsilyl or tri(Ci- C8)alkylsilyl-Ci-C8-alkyl ;
with the provisio that when Y represents N , and T represents O, and Z1 represents a cyclopropyl group, and R1 represents a chlorine atom, and R3 represents a trifluoromethyl group, and R2 and R4 represent a hydrogen atom, then a least one of the substituent Z2 or Z3 is not a hydrogen atom , as well as salts, N-oxydes, metallic complexes, metalloidic complexes and optically active or geometric isomers thereof.
2. A compound according to claim 1 wherein Y represents CR5
3. A compound according to claim 1 wherein Y represents N.
4. A compound according to any one of claims 1 to 3 wherein T represents O.
5. A compound according to any one of claims 1 to 4 wherein X1 represents a fluorine atom.
6. A compound according to any one of claims 1 to 5 wherein X2 represents a fluorine atom.
7. A compound according to any one of claims 1 to 6 wherein Z1 represents a non substituted cyclopropyl.
8. A compound according to any one of claims 1 to 7 wherein Z2 and Z3 independently represent a hydrogen atom or a methyl.
9. A compound according to any one of claims 1 to 8 wherein Z2 represents a hydrogen atom and Z3 represents a hydrogen atom or a methyl.
10. A compound according to any one of claims 1 to 9 wherein R1, R2, R3, R4 and R5, which can be the same or different, represent a hydrogen atom ; a halogen atom ; substituted or non substituted Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; substituted or non substituted C3-C7-cycloalkyl ; tri(Ci-C8-alkyl)silyl ; or substituted or non substituted Ci-C8-alkylsulfanyl.
11. A compound according to any one of claims 1 to 10 wherein the substituent R1 represents a halogen atom ; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C3-C7-cycloalkyl ; tri(d-C8-alkyl)silyl or Ci-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
12. A compound according to any one of claims 1 to 11 wherein the substitutents R1 and R5, which can be the same or different, represent a halogen atom; Ci-C8-alkyl ; Ci-C8-halogenoalkyl comprising up to 9 halogen atoms which can be the same or different ; C3-C7-cycloalkyl; tri(d- C8-alkyl)silyl or C-ι-C8-halogenoalkylsulfanyl comprising up to 9 halogen atoms which can be the same or different.
13. A compound of formula (lib)
Figure imgf000083_0001
wherein X represents a chlorine or a fluorine atom, preferably a fluorine atom;
14. A compound of formula (Mc')
Figure imgf000083_0002
IC)
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom; and W3 represent a halogen atom, preferably a chlorine atom.
15. A compound of formula (Nd)
Figure imgf000083_0003
(Nd) wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom;
16. A compound of formula (lie)
Figure imgf000084_0001
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
17. A compound of formula (Nf)
Figure imgf000084_0002
(Mf)
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
18. A compound of formula (Ng)
Figure imgf000084_0003
wherein X2 represents a chlorine or a fluorine atom, preferably a fluorine atom.
19. A composition, particularly a fungicide composition, comprising, as an active ingredient, an effective amount of a compound of formula (I) according to claims 1 to 12 and an agriculturally acceptable support, carrier or filler.
20. A process for the preparation of a compound of formula (I) according to claims 1 to 12 and of compounds according to claims 13 to 18, according to the following scheme :
Figure imgf000085_0001
(Mg) (He)
wherein
Z1, Z2, Z3, R1, R2 ,R3 ,R4, Y and X2 are as defined in claims 1 to 12.
21. A method for controlling phytopathogenic fungi of crops, characterized in that an agronomically effective and substantially non-phytotoxic quantity of a compound according to claims 1 to 12 or a composition according to claim 19 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.
22. Use of compounds of formula (I) according to claims 1 to 12 or a composition according to claim 19 for controlling phytopathogenic fungi of crops or/and for the reduction of mycotoxins in plants and part of plants and/or as insecticide, and/or as nematicide.
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Cited By (104)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2010534714A (en) * 2007-07-31 2010-11-11 バイエル・クロツプサイエンス・エス・アー Fungicides 2-pyridyl-methylene-thiocarboxamide or 2-pyridyl-methylene-N-substituted carboximido derivatives
WO2012052490A1 (en) * 2010-10-21 2012-04-26 Bayer Cropscience Ag N-benzyl heterocyclic carboxamides
WO2012059497A1 (en) 2010-11-02 2012-05-10 Bayer Cropscience Ag N-hetarylmethyl pyrazolylcarboxamides
WO2012093100A1 (en) 2011-01-05 2012-07-12 Syngenta Participations Ag Pyrazol-4-yl carboxamide derivatives as microbiocides
WO2012113696A1 (en) 2011-02-21 2012-08-30 Syngenta Participations Ag Novel carboxamide microbiocides
WO2012143127A1 (en) * 2011-04-22 2012-10-26 Bayer Cropsciences Ag Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
WO2012143125A1 (en) * 2011-04-22 2012-10-26 Bayer Cropscience Ag Active compound combinations comprising a (thio)carboxamide derivative and an insecticidal or acaricidal or nematicidal active compound
WO2013116251A2 (en) 2012-02-01 2013-08-08 E. I. Du Pont De Nemours And Company Fungicidal pyrazole mixtures
WO2013156559A1 (en) 2012-04-20 2013-10-24 Bayer Cropscience Ag N-cycloalkyl-n-[(heterocyclylphenyl)methylene]-(thio)carboxamide derivatives
WO2013156560A1 (en) 2012-04-20 2013-10-24 Bayer Cropscience Ag N-cycloalkyl-n-[(trisubstitutedsilylphenyl)methylene]-(thio)carboxamide derivatives
WO2013160387A1 (en) 2012-04-26 2013-10-31 Bayer Cropscience Ag Process for preparing n-(5-chloro-2-isopropylbenzyl)cyclopropanamine
WO2014060520A1 (en) 2012-10-19 2014-04-24 Bayer Cropscience Ag Method for treating plants against fungi resistant to fungicides using carboxamide or thiocarboxamide derivatives
WO2014060518A1 (en) 2012-10-19 2014-04-24 Bayer Cropscience Ag Method of plant growth promotion using carboxamide derivatives
WO2014060519A1 (en) 2012-10-19 2014-04-24 Bayer Cropscience Ag Method for enhancing tolerance to abiotic stress in plants using carboxamide or thiocarboxamide derivatives
WO2014060502A1 (en) 2012-10-19 2014-04-24 Bayer Cropscience Ag Active compound combinations comprising carboxamide derivatives
WO2014060521A1 (en) 2012-10-19 2014-04-24 Bayer Cropscience Ag Active compound combinations comprising carboxamide derivatives and a biological control agent
WO2014076007A1 (en) * 2012-11-13 2014-05-22 Bayer Cropscience Ag Method for producing carboxamides
WO2014111449A1 (en) * 2013-01-17 2014-07-24 Bayer Cropscience Ag Process for preparing 5-fluoro-1-methyl-3-difluoromethyl-1h-pyrazole-4-carbaldehyde
WO2014130409A2 (en) 2013-02-21 2014-08-28 E. I. Du Pont De Nemours And Company Fungicidal pyrazole mixtures
US8841331B2 (en) 2009-05-15 2014-09-23 Gilead Sciences, Inc. Inhibitors of human immunodeficiency virus replication
WO2014172191A1 (en) 2013-04-15 2014-10-23 E. I. Du Pont De Nemours And Company Fungicidal carboxamides
WO2014206954A1 (en) * 2013-06-26 2014-12-31 Bayer Cropscience Ag N-cycloalkyl-n-[(fusedphenyl)methylene]-(thio)carboxamide derivatives
WO2014206953A1 (en) 2013-06-26 2014-12-31 Bayer Cropscience Ag N-cycloalkyl-n-[(bicyclylphenyl)methylene]-(thio)carboxamide derivatives
WO2015032859A1 (en) * 2013-09-05 2015-03-12 Bayer Cropscience Ag Procedure for the synthesis of n-benzyl-n-cyclopropyl-1h-pyrazole-4-carboxamide derivatives
WO2015055707A1 (en) * 2013-10-16 2015-04-23 Bayer Cropscience Ag Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
WO2015082587A1 (en) 2013-12-05 2015-06-11 Bayer Cropscience Ag N-cycloalkyl-n-{[2-(1-substitutedcycloalkyl)phenyl]methylene}-(thio)carboxamide derivatives
WO2015082586A1 (en) 2013-12-05 2015-06-11 Bayer Cropscience Ag N-cycloalkyl-n-{[2-(1-substitutedcycloalkyl)phenyl]methylene}-(thio)carboxamide derivatives
WO2015157005A1 (en) 2014-04-10 2015-10-15 E I Du Pont De Nemours And Company Substituted tolyl fungicide mixtures
WO2016174121A1 (en) * 2015-04-29 2016-11-03 Bayer Cropscience Aktiengesellschaft Method for preparing 5-fluoro-1h-pyrazole-4-carbonyl fluorides
WO2016184941A1 (en) * 2015-05-21 2016-11-24 Bayer Cropscience Aktiengesellschaft Fungicidal n-cycloalkyl-n-{[ortho-(1-substituted-cycloalkyl)heteroaryl]methyl}pyrazole(thio)carboxamids
WO2016184942A1 (en) * 2015-05-21 2016-11-24 Bayer Cropscience Aktiengesellschaft Fungicidal n-cycloalkyl-n-{[ortho-(1-substituted-cycloalkyl)heteroaryl]methyl}(thio)carboxamides
WO2016184879A1 (en) 2015-05-19 2016-11-24 Bayer Cropscience Aktiengesellschaft Method for treating coffee rust, citrus black spot, citrus scab and banana black sigatoka diseases
US9540314B2 (en) 2012-03-26 2017-01-10 Bayer Intellectual Property Gmbh N-cycloalkyl-N-[(cycloalkenylphenyl)methylene]-(thio) carboxamide derivatives
US9617220B2 (en) 2012-08-07 2017-04-11 Bayer Cropscience Ag Method for the preparation of perfluoroalkyl containing pyrazoles carboxylates
WO2017063973A1 (en) 2015-10-14 2017-04-20 Syngenta Participations Ag Fungicidal compositions
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WO2019012003A1 (en) 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019053027A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053015A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053024A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053010A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053019A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053016A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053026A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019068809A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019068812A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019096709A1 (en) 2017-11-15 2019-05-23 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019097054A1 (en) 2017-11-20 2019-05-23 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2019121149A1 (en) 2017-12-19 2019-06-27 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019207062A1 (en) 2018-04-26 2019-10-31 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2020002331A1 (en) 2018-06-29 2020-01-02 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020007658A1 (en) 2018-07-02 2020-01-09 Syngenta Crop Protection Ag 3-(2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole derivatives as agrochemical fungicides
WO2020016180A1 (en) 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020022412A1 (en) 2018-07-25 2020-01-30 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide having this as active component
WO2020058207A1 (en) 2018-09-19 2020-03-26 Syngenta Crop Protection Ag Microbiocidal quinoline carboxamide derivatives
WO2020057939A1 (en) 2018-09-17 2020-03-26 Bayer Aktiengesellschaft Use of the fungicide isoflucypram for controlling claviceps purpurea and reducing sclerotia in cereals
WO2020064696A1 (en) 2018-09-26 2020-04-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2020070131A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020070132A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020084075A1 (en) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2020141135A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020141136A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3698634A1 (en) * 2019-02-25 2020-08-26 Basf Se Pesticidal mixtures
CN114747582A (en) * 2022-03-03 2022-07-15 青岛海利尔生物科技有限公司 Pesticide composition containing Isoflucypram and oxine-copper and application thereof
RU2812485C2 (en) * 2019-02-25 2024-01-30 Басф Се Pesticide mixtures

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AR076839A1 (en) * 2009-05-15 2011-07-13 Bayer Cropscience Ag FUNGICIDE DERIVATIVES OF PIRAZOL CARBOXAMIDAS
DK2560961T3 (en) * 2010-04-23 2017-02-20 Bayer Ip Gmbh METHOD FOR PREPARING 5-FLUORO-1-ALKYL-3-FLUORALKYL-1H-PYRAZOL-4-CARBOXYLYRIC CHLORIDE AND FLUORIDES
US8999956B2 (en) * 2010-06-03 2015-04-07 Bayer Intellectual Property Gmbh N-[(het)arylalkyl)] pyrazole(thio)carboxamides and their heterosubstituted analogues
EP2850065A1 (en) * 2012-05-09 2015-03-25 Bayer CropScience AG Pyrazole indanyl carboxamides
BR112016016397B1 (en) * 2014-01-24 2021-06-29 Bayer Cropscience Aktiengesellschaft PROCESS TO PREPARE 1-ALKYL-3-DIFLUOROMETHYL-5-FLUORO-1H-PYRAZOL-4-CARBALDEHYDES OR ITS ESTERS
MX359619B (en) 2014-07-14 2018-10-04 Adjuvants Plus Usa Inc Clonostachys rosea inoculated plant materials with fungicides and adjuvants.
MX2019006915A (en) * 2016-12-16 2019-09-02 Bayer Cropscience Ag Method for the control of plant bacterial diseases using carboxamide derivatives.
WO2019007887A1 (en) 2017-07-06 2019-01-10 Bayer Aktiengesellschaft Insecticide and fungicide active ingredient combinations
CN109187785A (en) * 2018-09-13 2019-01-11 张云 The quantitative detecting method of pesticide biphenyl pyrrole bacterium amine in a kind of lotus seeds
CN111943975B (en) * 2019-07-31 2023-04-07 华中师范大学 Pyrazole amide compound containing silicon atoms, preparation method and application thereof, and bactericide

Family Cites Families (180)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5331107A (en) 1984-03-06 1994-07-19 Mgi Pharma, Inc. Herbicide resistance in plants
US5304732A (en) 1984-03-06 1994-04-19 Mgi Pharma, Inc. Herbicide resistance in plants
US4761373A (en) 1984-03-06 1988-08-02 Molecular Genetics, Inc. Herbicide resistance in plants
DE3765449D1 (en) 1986-03-11 1990-11-15 Plant Genetic Systems Nv PLANT CELLS RESISTED BY GENE TECHNOLOGY AND RESISTANT TO GLUTAMINE SYNTHETASE INHIBITORS.
US5637489A (en) 1986-08-23 1997-06-10 Hoechst Aktiengesellschaft Phosphinothricin-resistance gene, and its use
US5276268A (en) 1986-08-23 1994-01-04 Hoechst Aktiengesellschaft Phosphinothricin-resistance gene, and its use
US5273894A (en) 1986-08-23 1993-12-28 Hoechst Aktiengesellschaft Phosphinothricin-resistance gene, and its use
US5378824A (en) 1986-08-26 1995-01-03 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
US5013659A (en) 1987-07-27 1991-05-07 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
US5605011A (en) 1986-08-26 1997-02-25 E. I. Du Pont De Nemours And Company Nucleic acid fragment encoding herbicide resistant plant acetolactate synthase
US5638637A (en) 1987-12-31 1997-06-17 Pioneer Hi-Bred International, Inc. Production of improved rapeseed exhibiting an enhanced oleic acid content
GB8810120D0 (en) 1988-04-28 1988-06-02 Plant Genetic Systems Nv Transgenic nuclear male sterile plants
US5084082A (en) 1988-09-22 1992-01-28 E. I. Du Pont De Nemours And Company Soybean plants with dominant selectable trait for herbicide resistance
US6013861A (en) 1989-05-26 2000-01-11 Zeneca Limited Plants and processes for obtaining them
DE69033764T2 (en) 1989-08-10 2002-05-23 Aventis Cropscience N.V., Gent Plants with modified flowers
US5739082A (en) 1990-02-02 1998-04-14 Hoechst Schering Agrevo Gmbh Method of improving the yield of herbicide-resistant crop plants
US5908810A (en) 1990-02-02 1999-06-01 Hoechst Schering Agrevo Gmbh Method of improving the growth of crop plants which are resistant to glutamine synthetase inhibitors
EP0476093B1 (en) 1990-04-04 1997-05-07 Pioneer Hi-Bred International, Inc. Production of improved rapeseed exhibiting a reduced saturated fatty acid content
US5198599A (en) 1990-06-05 1993-03-30 Idaho Resarch Foundation, Inc. Sulfonylurea herbicide resistance in plants
ATE213774T1 (en) 1990-06-25 2002-03-15 Monsanto Technology Llc GLYPHOSATE TOLERANT PLANTS
FR2667078B1 (en) 1990-09-21 1994-09-16 Agronomique Inst Nat Rech DNA SEQUENCE GIVING MALE CYTOPLASMIC STERILITY, MITOCHONDRIAL, MITOCHONDRIA AND PLANT CONTAINING THE SAME, AND PROCESS FOR THE PREPARATION OF HYBRIDS.
DE4104782B4 (en) 1991-02-13 2006-05-11 Bayer Cropscience Gmbh Novel plasmids containing DNA sequences that cause changes in carbohydrate concentration and carbohydrate composition in plants, as well as plants and plant cells containing these plasmids
US5731180A (en) 1991-07-31 1998-03-24 American Cyanamid Company Imidazolinone resistant AHAS mutants
US6270828B1 (en) 1993-11-12 2001-08-07 Cargrill Incorporated Canola variety producing a seed with reduced glucosinolates and linolenic acid yielding an oil with low sulfur, improved sensory characteristics and increased oxidative stability
US5223526A (en) 1991-12-06 1993-06-29 Monsanto Company Pyrazole carboxanilide fungicides and use
DE4227061A1 (en) 1992-08-12 1994-02-17 Inst Genbiologische Forschung A polyfructane sucrase DNA sequence from Erwinia Amylovora
GB9218185D0 (en) 1992-08-26 1992-10-14 Ici Plc Novel plants and processes for obtaining them
CA2146998A1 (en) 1992-10-14 1994-04-28 Colin Roger Bird Novel plants and processes for obtaining them
GB9223454D0 (en) 1992-11-09 1992-12-23 Ici Plc Novel plants and processes for obtaining them
UA52579C2 (en) 1993-03-25 2003-01-15 Новартіс Аг Fragment of dna, having nucleotide sequence encoding vegetative insecticidal protein, an expression cassette, a vector molecule, an agrobacterium strain (variants), a bacillus strain, vegetative insecticidal protein, pesticidal composition, a method of plant treatment, a method of obtaining vegetative incsecticidal protein, a method of obtaining a transgenic host microorganism
JP3527242B2 (en) 1993-04-27 2004-05-17 カージル，インコーポレーテッド Edible non-hydrogenated canola oil
WO1995004826A1 (en) 1993-08-09 1995-02-16 Institut Für Genbiologische Forschung Berlin Gmbh Debranching enzymes and dna sequences coding them, suitable for changing the degree of branching of amylopectin starch in plants
DE4330960C2 (en) 1993-09-09 2002-06-20 Aventis Cropscience Gmbh Combination of DNA sequences that enable the formation of highly amylose-containing starch in plant cells and plants, processes for producing these plants and the modified starch that can be obtained therefrom
CA2150667C (en) 1993-10-01 2007-01-09 Mari Iwabuchi A gene which determines cytoplasmic sterility and a method of producing hybrid plants using said gene
AU692791B2 (en) 1993-10-12 1998-06-18 Agrigenetics, Inc. Brassica napus variety AG019
JPH09505467A (en) 1993-11-09 1997-06-03 イー・アイ・デユポン・ドウ・ヌムール・アンド・カンパニー Transgenic fructan accumulation crop and its production method
AU688006B2 (en) 1994-03-25 1998-03-05 Brunob Ii B.V. Method for producing altered starch from potato plants
IL113776A (en) 1994-05-18 2008-12-29 Bayer Bioscience Gmbh Dna sequences coding for enzymes which catalyze the synthesis of linear alpha 1,4 - glucans in plants, fungi and microorganisms
US5824790A (en) 1994-06-21 1998-10-20 Zeneca Limited Modification of starch synthesis in plants
AU706849B2 (en) 1994-06-21 1999-06-24 Cerestar Usa, Inc. Novel plants and processes for obtaining them
NL1000064C1 (en) 1994-07-08 1996-01-08 Stichting Scheikundig Onderzoe Production of oligosaccharides in transgenic plants.
DE4441408A1 (en) 1994-11-10 1996-05-15 Inst Genbiologische Forschung DNA sequences from Solanum tuberosum encoding enzymes involved in starch synthesis, plasmids, bacteria, plant cells and transgenic plants containing these sequences
DE4447387A1 (en) 1994-12-22 1996-06-27 Inst Genbiologische Forschung Debranching enzymes from plants and DNA sequences encoding these enzymes
EP0795018B1 (en) 1995-01-06 2007-09-12 Plant Research International B.V. Dna sequences encoding carbohydrate polymer synthesizing enzymes and method for producing transgenic plants
DE19509695A1 (en) 1995-03-08 1996-09-12 Inst Genbiologische Forschung Process for the preparation of a modified starch in plants, and the modified starch isolatable from the plants
EP0821729B1 (en) 1995-04-20 2006-10-18 Basf Aktiengesellschaft Structure-based designed herbicide resistant products
US5853973A (en) 1995-04-20 1998-12-29 American Cyanamid Company Structure based designed herbicide resistant products
DK0826061T3 (en) 1995-05-05 2007-09-24 Nat Starch Chem Invest Enhancements to or related to plant starch compositions
FR2734842B1 (en) 1995-06-02 1998-02-27 Rhone Poulenc Agrochimie DNA SEQUENCE OF A HYDROXY-PHENYL PYRUVATE DIOXYGENASE GENE AND OBTAINING PLANTS CONTAINING A HYDROXY-PHENYL PYRUVATE DIOXYGENASE GENE, TOLERANT TO CERTAIN HERBICIDES
US5712107A (en) 1995-06-07 1998-01-27 Pioneer Hi-Bred International, Inc. Substitutes for modified starch and latexes in paper manufacture
US6284479B1 (en) 1995-06-07 2001-09-04 Pioneer Hi-Bred International, Inc. Substitutes for modified starch and latexes in paper manufacture
GB9513881D0 (en) 1995-07-07 1995-09-06 Zeneca Ltd Improved plants
FR2736926B1 (en) 1995-07-19 1997-08-22 Rhone Poulenc Agrochimie 5-ENOL PYRUVYLSHIKIMATE-3-PHOSPHATE SYNTHASE MUTEE, CODING GENE FOR THIS PROTEIN AND PROCESSED PLANTS CONTAINING THIS GENE
PT1435205E (en) 1995-09-19 2010-02-04 Bayer Bioscience Gmbh Process for the production of a modified starch
DE19544800A1 (en) 1995-12-01 1997-06-05 Bayer Ag Process for the preparation of 1,3-dimethyl-5-fluoro-pyrazole-4-carboxanilides
GB9524938D0 (en) 1995-12-06 1996-02-07 Zeneca Ltd Modification of starch synthesis in plants
DE19601365A1 (en) 1996-01-16 1997-07-17 Planttec Biotechnologie Gmbh Nucleic acid molecules from plants encoding enzymes involved in starch synthesis
DE19608918A1 (en) 1996-03-07 1997-09-11 Planttec Biotechnologie Gmbh Nucleic Acid Molecules Encoding New Debranching Enzymes from Maize
US5773704A (en) 1996-04-29 1998-06-30 Board Of Supervisors Of Louisiana State University And Agricultural And Mechanical College Herbicide resistant rice
DE19618125A1 (en) 1996-05-06 1997-11-13 Planttec Biotechnologie Gmbh Nucleic acid molecules that encode new potato debranching enzymes
DE19619918A1 (en) 1996-05-17 1997-11-20 Planttec Biotechnologie Gmbh Nucleic acid molecules encoding soluble starch synthases from maize
CA2256461C (en) 1996-05-29 2012-07-24 Hoechst Schering Agrevo Gmbh Nucleic acid molecules encoding enzymes from wheat which are involved in starch synthesis
WO1997047806A1 (en) 1996-06-12 1997-12-18 Pioneer Hi-Bred International, Inc. Substitutes for modified starch in paper manufacture
EP0904453B1 (en) 1996-06-12 2001-12-19 Pioneer Hi-Bred International, Inc. Substitutes for modified starch in paper manufacture
AU729286B2 (en) 1996-06-12 2001-02-01 Pioneer Hi-Bred International, Inc. Substitutes for modified starch in paper manufacture
AUPO069996A0 (en) 1996-06-27 1996-07-18 Australian National University, The Manipulation of plant cellulose
US5850026A (en) 1996-07-03 1998-12-15 Cargill, Incorporated Canola oil having increased oleic acid and decreased linolenic acid content
US5773702A (en) 1996-07-17 1998-06-30 Board Of Trustees Operating Michigan State University Imidazolinone herbicide resistant sugar beet plants
GB9623095D0 (en) 1996-11-05 1997-01-08 Nat Starch Chem Invest Improvements in or relating to starch content of plants
US6232529B1 (en) 1996-11-20 2001-05-15 Pioneer Hi-Bred International, Inc. Methods of producing high-oil seed by modification of starch levels
DE19653176A1 (en) 1996-12-19 1998-06-25 Planttec Biotechnologie Gmbh New maize nucleic acid molecules and their use to produce a modified starch
CA2193938A1 (en) 1996-12-24 1998-06-24 David G. Charne Oilseed brassica containing an improved fertility restorer gene for ogura cytoplasmic male sterility
US5981840A (en) 1997-01-24 1999-11-09 Pioneer Hi-Bred International, Inc. Methods for agrobacterium-mediated transformation
DE19708774A1 (en) 1997-03-04 1998-09-17 Max Planck Gesellschaft Enzymes encoding nucleic acid molecules which have fructosyl polymerase activity
DE19709775A1 (en) 1997-03-10 1998-09-17 Planttec Biotechnologie Gmbh Nucleic acid molecules encoding corn starch phosphorylase
GB9718863D0 (en) 1997-09-06 1997-11-12 Nat Starch Chem Invest Improvements in or relating to stability of plant starches
DE19749122A1 (en) 1997-11-06 1999-06-10 Max Planck Gesellschaft Enzymes encoding nucleic acid molecules that have fructosyl transferase activity
FR2770854B1 (en) 1997-11-07 2001-11-30 Rhone Poulenc Agrochimie DNA SEQUENCE OF A GENE OF HYDROXY-PHENYL PYRUVATE DIOXYGENASE AND PRODUCTION OF PLANTS CONTAINING SUCH A GENE, HERBICIDE TOLERANT
FR2772789B1 (en) 1997-12-24 2000-11-24 Rhone Poulenc Agrochimie PROCESS FOR THE ENZYMATIC PREPARATION OF HOMOGENTISATE
AU3478499A (en) 1998-04-09 1999-11-01 E.I. Du Pont De Nemours And Company Starch r1 phosphorylation protein homologs
DE19820607A1 (en) 1998-05-08 1999-11-11 Hoechst Schering Agrevo Gmbh New enzyme with starch synthase activity, useful for producing starch for foods and packaging materials
DE19820608A1 (en) 1998-05-08 1999-11-11 Hoechst Schering Agrevo Gmbh New nucleic acid encoding isoamylase from wheat and related transgenic plants producing starch with altered properties
JP4494634B2 (en) 1998-05-13 2010-06-30 バイエル バイオサイエンス ゲーエムベーハー Transgenic plant with modified activity of plastid ADP / ATP transposable element
DE19821614A1 (en) 1998-05-14 1999-11-18 Hoechst Schering Agrevo Gmbh Sugar beet mutants which are tolerant to sulfonylurea herbicides
JP2002518015A (en) 1998-06-15 2002-06-25 ナショナル スターチ アンド ケミカル インベストメント ホールディング コーポレイション Improvement of or related to plants and plant products
US6693185B2 (en) 1998-07-17 2004-02-17 Bayer Bioscience N.V. Methods and means to modulate programmed cell death in eukaryotic cells
DE19836097A1 (en) 1998-07-31 2000-02-03 Hoechst Schering Agrevo Gmbh Nucleic acid molecules coding for an alpha-glucosidase, plants that synthesize a modified starch, process for producing the plants, their use and the modified starch
DE19836098A1 (en) 1998-07-31 2000-02-03 Hoechst Schering Agrevo Gmbh Plants that synthesize a modified starch, process for producing the plants, their use and the modified starch
DE19836099A1 (en) 1998-07-31 2000-02-03 Hoechst Schering Agrevo Gmbh Nucleic acid molecules coding for a β-amylase, plants which synthesize a modified starch, process for the preparation of the plants, their use and the modified starch
EP1108040A2 (en) 1998-08-25 2001-06-20 Pioneer Hi-Bred International, Inc. Plant glutamine: fructose-6-phosphate amidotransferase nucleic acids
CA2342124A1 (en) 1998-09-02 2000-03-16 Planttec Biotechnologie Gmbh Nucleic acid molecules encoding an amylosucrase
DE59915126D1 (en) 1998-10-09 2010-03-04 Bayer Bioscience Gmbh NUCLEIC ACID MOLECULES COPYING A BRANCHING BRANCH OF BACTERIA OF THE GENUS NEISSERIA AND PROCESS FOR PREPARING ALPHA-1,6-BRANCHED ALPHA-1,4-GLUCANES
DE19924342A1 (en) 1999-05-27 2000-11-30 Planttec Biotechnologie Gmbh Genetically modified plant cells and plants with increased activity of an amylosucrase protein and a branching enzyme
WO2000028052A2 (en) 1998-11-09 2000-05-18 Planttec Biotechnologie Gmbh Nucleic acid molecules from rice encoding an r1 protein and their use for the production of modified starch
US6531648B1 (en) 1998-12-17 2003-03-11 Syngenta Participations Ag Grain processing method and transgenic plants useful therein
DE19905069A1 (en) 1999-02-08 2000-08-10 Planttec Biotechnologie Gmbh Alternansucrase encoding nucleic acid molecules
US6323392B1 (en) 1999-03-01 2001-11-27 Pioneer Hi-Bred International, Inc. Formation of brassica napus F1 hybrid seeds which exhibit a highly elevated oleic acid content and a reduced linolenic acid content in the endogenously formed oil of the seeds
CZ20013859A3 (en) 1999-04-29 2002-04-17 Syngenta Ltd. Plants resistant to herbicides
MXPA01010922A (en) 1999-04-29 2003-06-24 Syngenta Ltd Herbicide resistant plants.
DE19926771A1 (en) 1999-06-11 2000-12-14 Aventis Cropscience Gmbh Nucleic acid molecules from wheat, transgenic plant cells and plants and their use for the production of modified starch
DE19937348A1 (en) 1999-08-11 2001-02-22 Aventis Cropscience Gmbh Nucleic acid molecules from plants encoding enzymes involved in starch synthesis
DE19937643A1 (en) 1999-08-12 2001-02-22 Aventis Cropscience Gmbh Transgenic cells and plants with altered activity of the GBSSI and BE proteins
AU7647000A (en) 1999-08-20 2001-03-19 Basf Plant Science Gmbh Increasing the polysaccharide content in plants
US6423886B1 (en) 1999-09-02 2002-07-23 Pioneer Hi-Bred International, Inc. Starch synthase polynucleotides and their use in the production of new starches
US6472588B1 (en) 1999-09-10 2002-10-29 Texas Tech University Transgenic cotton plants with altered fiber characteristics transformed with a sucrose phosphate synthase nucleic acid
GB9921830D0 (en) 1999-09-15 1999-11-17 Nat Starch Chem Invest Plants having reduced activity in two or more starch-modifying enzymes
AR025996A1 (en) 1999-10-07 2002-12-26 Valigen Us Inc NON-TRANSGENIC PLANTS RESISTANT TO HERBICIDES.
BR0109118A (en) 2000-03-09 2002-11-26 Monsanto Technology Llc Methods for producing glyphosate tolerant plants and compositions thereof
HU230370B1 (en) 2000-03-09 2016-03-29 E.I. Du Pont De Nemours And Co Sulfonylurea-tolerant sunflower plants
US6303818B1 (en) 2000-08-08 2001-10-16 Dow Agrosciences Llc Unsaturated oxime ethers and their use as fungicides
BR0114322A (en) 2000-09-29 2004-06-15 Syngenta Ltd Glyphosate-resistant epsps enzyme, isolated polynucleotide, vector, plant material, fertile, morphologically normal whole plants, soybean, canola, brassica, cotton, sugar beet, sunflower, peas, potatoes and weeds, methods for selectively controlling weeds in a field, and to produce plants that are substantially tolerant or substantially resistant to glyphosate herbicide, use of polynucleotide, methods for selecting transformed biological material to express a gene of interest, and for regenerating a transformed fertile plant to contain a foreign one. and diagnostic kit
US6734340B2 (en) 2000-10-23 2004-05-11 Bayer Cropscience Gmbh Monocotyledon plant cells and plants which synthesise modified starch
FR2815969B1 (en) 2000-10-30 2004-12-10 Aventis Cropscience Sa TOLERANT PLANTS WITH HERBICIDES BY METABOLIC BYPASS
US20030083480A1 (en) 2000-10-30 2003-05-01 Maxygen, Inc. Novel glyphosate N-acetyl transferase (GAT) genes
AU2036302A (en) 2000-12-08 2002-06-18 Commw Scient Ind Res Org Modification of sucrose synthase gene expression in plant tissue and uses therefor
WO2002079410A2 (en) 2001-03-30 2002-10-10 Basf Plant Science Gmbh Glucan chain length domains
ES2305257T3 (en) 2001-06-12 2008-11-01 Bayer Cropscience Ag TRANSGENIC PLANTS THAT SYNTHEIZE ALMIDON RICH IN AMILOSA.
US20030084473A1 (en) 2001-08-09 2003-05-01 Valigen Non-transgenic herbicide resistant plants
WO2003033540A2 (en) 2001-10-17 2003-04-24 Basf Plant Science Gmbh Starch
DE10208132A1 (en) 2002-02-26 2003-09-11 Planttec Biotechnologie Gmbh Process for the production of maize plants with an increased leaf starch content and their use for the production of maize silage
WO2003092360A2 (en) 2002-04-30 2003-11-13 Verdia, Inc. Novel glyphosate-n-acetyltransferase (gat) genes
UA78071C2 (en) 2002-08-07 2007-02-15 Kumiai Chemical Industry Co Herbicidal composition
FR2844142B1 (en) 2002-09-11 2007-08-17 Bayer Cropscience Sa TRANSFORMED PLANTS WITH ENHANCED PRENYLQUINON BIOSYNTHESIS
AU2003275859A1 (en) 2002-10-29 2004-05-25 Basf Plant Science Gmbh Compositions and methods for identifying plants having increased tolerance to imidazolinone herbicides
AU2003275716A1 (en) 2002-10-31 2004-05-25 Ishihara Sangyo Kaisha, Ltd. 3-benzoyl-2,4,5-substituted pyridine derivatives or salts thereof and bactericides containing the same
US20040110443A1 (en) 2002-12-05 2004-06-10 Pelham Matthew C. Abrasive webs and methods of making the same
AU2003293991B2 (en) 2002-12-19 2009-01-22 Bayer Intellectual Property Gmbh Plant cells and plants which synthesize a starch with an increased final viscosity
GB0230155D0 (en) 2002-12-24 2003-02-05 Syngenta Participations Ag Chemical compounds
US20060162021A1 (en) 2003-03-07 2006-07-20 Basf Plant Science Gmbh Enhanced amylose production in plants
WO2004090140A2 (en) 2003-04-09 2004-10-21 Bayer Bioscience N.V. Methods and means for increasing the tolerance of plants to stress conditions
EP1620557A2 (en) 2003-04-29 2006-02-01 Pioneer Hi-Bred International, Inc. Novel glyphosate-n-acetyltransferase (gat) genes
WO2005002359A2 (en) 2003-05-22 2005-01-13 Syngenta Participations Ag Modified starch, uses, methods for production thereof
UA92716C2 (en) 2003-05-28 2010-12-10 Басф Акциенгезелльшафт Wheat plants with increased tolerance towards imidazolinone herbicides
EP1493328A1 (en) 2003-07-04 2005-01-05 Institut National De La Recherche Agronomique Method of producing double low restorer lines of brassica napus having a good agronomic value
BRPI0412582A (en) 2003-07-31 2006-09-19 Toyo Boseki hyaluronic acid producing plants
ATE553200T1 (en) 2003-08-15 2012-04-15 Commw Scient Ind Res Org METHOD AND MEANS FOR MODIFYING THE FIBER PROPERTIES IN FIBER PRODUCING PLANTS
EP2294913B1 (en) 2003-08-29 2015-05-27 Instituto Nacional de Tecnologia Agropecuaria Rice plants having increased tolerance to imidazolinone herbicides
US20070011777A1 (en) 2003-09-30 2007-01-11 Claus Frohberg Plants with increased activity of a class 3 branching enzyme
WO2005030942A1 (en) 2003-09-30 2005-04-07 Bayer Cropscience Gmbh Plants with reduced activity of a class 3 branching enzyme
AR048025A1 (en) 2004-03-05 2006-03-22 Bayer Cropscience Gmbh PLANTS WITH INCREASED ACTIVITY OF AN ALMIDON FOSFORILING ENZYME
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AR048026A1 (en) 2004-03-05 2006-03-22 Bayer Cropscience Gmbh PROCEDURES FOR THE IDENTIFICATION OF PROTEINS WITH ENZYMATIC ACTIVITY FOSFORILADORA DE ALMIDON
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US7432082B2 (en) 2004-03-22 2008-10-07 Basf Ag Methods and compositions for analyzing AHASL genes
RU2007101383A (en) 2004-06-16 2008-07-27 БАСФ ПЛАНТ САЙЕНС ГмбХ (DE) Polynucleotides Encoding Mature AHASL Proteins To Create Imidazolin Resistant Plants
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CN101035900A (en) 2004-08-04 2007-09-12 巴斯福植物科学有限公司 Monocot AHASS sequences and methods of use
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CA2578187C (en) 2004-08-26 2015-08-04 Dhara Vegetable Oil And Foods Company Limited A novel cytoplasmic male sterility system for brassica species and its use for hybrid seed production in indian oilseed mustard brassica juncea
ES2327944T3 (en) 2004-09-23 2009-11-05 Bayer Cropscience Ag METHODS AND MEANS TO PRODUCE HIALURONAN.
AU2005287499B2 (en) 2004-09-24 2010-09-23 Bayer Cropscience Nv. Stress resistant plants
MX2007005166A (en) 2004-10-29 2007-06-26 Bayer Bioscience Nv Stress tolerant cotton plants.
AR051690A1 (en) 2004-12-01 2007-01-31 Basf Agrochemical Products Bv MUTATION INVOLVED IN THE INCREASE OF TOLERANCE TO IMIDAZOLINONE HERBICIDES IN PLANTS
EP1672075A1 (en) 2004-12-17 2006-06-21 Bayer CropScience GmbH Transformed plant expressing a dextransucrase and synthesizing a modified starch
EP1679374A1 (en) 2005-01-10 2006-07-12 Bayer CropScience GmbH Transformed plant expressing a mutansucrase and synthesizing a modified starch
JP2006304779A (en) 2005-03-30 2006-11-09 Toyobo Co Ltd Plant producing hexosamine in high productivity
EP1707632A1 (en) 2005-04-01 2006-10-04 Bayer CropScience GmbH Phosphorylated waxy potato starch
EP1710315A1 (en) 2005-04-08 2006-10-11 Bayer CropScience GmbH High phosphate starch
CN101175750B (en) * 2005-05-13 2011-09-07 拜尔农科股份公司 Fungicide 2-pyridyl-methylene-carboxamide derivatives
DE602006008459D1 (en) 2005-06-15 2009-09-24 Bayer Bioscience Nv PLANTS AGAINST HYPOXIC CONDITIONS
BRPI0613153A2 (en) 2005-06-24 2010-12-21 Bayer Bioscience Nv methods for altering plant cell wall reactivity
AR054174A1 (en) 2005-07-22 2007-06-06 Bayer Cropscience Gmbh OVERPRINTING OF ALMIDON SYNTHEASE IN VEGETABLES
WO2007024782A2 (en) 2005-08-24 2007-03-01 Pioneer Hi-Bred International, Inc. Compositions providing tolerance to multiple herbicides and methods of use thereof
BRPI0615657B8 (en) 2005-08-31 2019-12-24 Monsanto Technology Llc recombinant polynucleotide, protein and insecticidal composition, expression cassette and vector, as well as methods to control infestation by lepidopteran insects in plants and to protect harvest in field from infestation by lepidopteran insects
DE102005044451A1 (en) * 2005-09-17 2007-03-22 Bayer Cropscience Gmbh A process for producing 5-fluoro-1,3-dialkyl-1H-pyrazole-4-carboxylic acid fluorides
BRPI0616844A2 (en) 2005-10-05 2011-07-05 Bayer Cropscience Ag genetically modified plant cell, use thereof, plant, production process, plant reproductive material, harvestable plant parts, hyaluronan production process, composition as well as its production process
WO2007039314A2 (en) 2005-10-05 2007-04-12 Bayer Cropscience Ag Plants with increased hyaluronan production
AU2006298963A1 (en) 2005-10-05 2007-04-12 Bayer Cropscience Ag Improved methods and means for producings hyaluronan
DE102005057180A1 (en) 2005-12-01 2007-06-06 Bayer Cropscience Ag A process for producing 5-fluoro-1,3-dialkyl-1H-pyrazole-4-carboxylic acid fluorides
AR056882A1 (en) * 2006-02-01 2007-10-31 Bayer Cropscience Sa DERIVATIVES OF THE FUNGICIDE N- CICLOALQUIL- BENCIL- AMIDA
CL2007002787A1 (en) 2006-09-29 2008-05-30 Bayer Cropscience Sa COMPOUNDS DERIVED FROM N-CICLOALQUIL-CARBOXAMIDA, N-CICLOALQUIL-TIOCARBOXAMIDA AND N-CICLOALQUIL-CARBOXAMIDAMIDA N-SUBSTITUTED; FUNGICIDE COMPOSITION THAT INCLUDES SUCH COMPOUNDS; AND METHOD TO COMBAT FITOPATOGEN CULTURE FUNGIANS THAT YOU UNDERSTAND
WO2009016220A1 (en) * 2007-07-31 2009-02-05 Bayer Cropscience Sa Fungicidal n-cycloalkyl-benzyl-thiocarboxamides or n-cycloalkyl-benzyl-n' -substituted-amidine derivatives
CL2008002242A1 (en) * 2007-07-31 2009-08-21 Bayer Cropscience Ag N-cycloalkyl-n-carboxamide, thiocarboxamide, bicyclic derivatives or n-substituted carboximidamide derivatives; fungicidal composition; and method to control phytopathogenic fungi in crops.
KR101316247B1 (en) 2007-07-31 2013-10-08 엘지전자 주식회사 2 stage rotary compressor
AR067744A1 (en) 2007-07-31 2009-10-21 Bayer Cropscience Sa FUNGICIDE DERIVATIVES OF (HETERO) ARIL- METILEN -N- CONCENSED CARBOXAMIDE CYCLEALKYL OF 6 ELEMENTS WITH N
JP5319674B2 (en) * 2007-07-31 2013-10-16 バイエル・クロップサイエンス・アーゲー Fungicides 2-pyridyl-methylene-thiocarboxamide or 2-pyridyl-methylene-N-substituted carboximido derivatives
AR076839A1 (en) * 2009-05-15 2011-07-13 Bayer Cropscience Ag FUNGICIDE DERIVATIVES OF PIRAZOL CARBOXAMIDAS
EP2325173A1 (en) 2009-11-19 2011-05-25 Bayer CropScience AG Method for producing 5-fluor-1-alkyl-3-fluoralkyl-1H-pyrazol-4-carboxylic acid chlorides
DK2560961T3 (en) * 2010-04-23 2017-02-20 Bayer Ip Gmbh METHOD FOR PREPARING 5-FLUORO-1-ALKYL-3-FLUORALKYL-1H-PYRAZOL-4-CARBOXYLYRIC CHLORIDE AND FLUORIDES

Non-Patent Citations (9)

* Cited by examiner, † Cited by third party
Title
BARRY ET AL., CURR. TOPICS PLANT PHYSIOL., vol. 7, 1992, pages 139 - 145
COMAI ET AL., SCIENCE, vol. 221, 1983, pages 370 - 371
CRICKMORE ET AL., BACILLUS THURINGIENSIS TOXIN NOMENCLATURE, 2005, Retrieved from the Internet <URL:www.lifesci.sussex.ac.uk/Home/Neil-Crickmore/Bt>
CRICKMORE ET AL., MICROBIOLOGY AND MOLECULAR BIOLOGY REVIEWS, vol. 62, 1998, pages 807 - 813
GASSER ET AL., J. BIOL. CHEM., vol. 263, 1988, pages 4280 - 4289
MOELLENBECK ET AL., NAT. BIOTECHNOL., vol. 19, 2001, pages 668 - 72
SCHNEPF ET AL., APPLIED ENVIRONM. MICROBIOL., vol. 71, 2006, pages 1765 - 1774
SHAH ET AL., SCIENCE, vol. 233, 1986, pages 478 - 481
TRANEL; WRIGHT, WEED SCIENCE, vol. 50, 2002, pages 700 - 712

Cited By (178)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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US8841331B2 (en) 2009-05-15 2014-09-23 Gilead Sciences, Inc. Inhibitors of human immunodeficiency virus replication
WO2012052490A1 (en) * 2010-10-21 2012-04-26 Bayer Cropscience Ag N-benzyl heterocyclic carboxamides
US9084424B2 (en) 2010-10-21 2015-07-21 Bayer Intellectual Property Gmbh N-benzyl heterocyclic carboxamides
US9320276B2 (en) 2010-11-02 2016-04-26 Bayer Intellectual Property Gmbh N-hetarylmethyl pyrazolylcarboxamides
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US8653003B2 (en) 2011-01-05 2014-02-18 Syngenta Participations Ag Pyrazol-4-yl carboxamide derivatives as microbiocides
WO2012093100A1 (en) 2011-01-05 2012-07-12 Syngenta Participations Ag Pyrazol-4-yl carboxamide derivatives as microbiocides
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WO2012113696A1 (en) 2011-02-21 2012-08-30 Syngenta Participations Ag Novel carboxamide microbiocides
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US8822523B2 (en) 2011-02-21 2014-09-02 Syngenta Participations Ag Carboxamide microbiocides
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TWI705055B (en) * 2015-04-29 2020-09-21 德商拜耳作物科學公司 Method for preparing 5-fluoro-1h-pyrazole-4-carbonyl fluorides
WO2016184879A1 (en) 2015-05-19 2016-11-24 Bayer Cropscience Aktiengesellschaft Method for treating coffee rust, citrus black spot, citrus scab and banana black sigatoka diseases
US10244756B2 (en) 2015-05-21 2019-04-02 Bayer Cropscience Aktiengesellschaft Fungicidal N-cycloalkyl-N-{[ortho-(1-substituted-cycloalkyl)heteroaryl]methyl}(thio)carboxamides
WO2016184941A1 (en) * 2015-05-21 2016-11-24 Bayer Cropscience Aktiengesellschaft Fungicidal n-cycloalkyl-n-{[ortho-(1-substituted-cycloalkyl)heteroaryl]methyl}pyrazole(thio)carboxamids
WO2016184942A1 (en) * 2015-05-21 2016-11-24 Bayer Cropscience Aktiengesellschaft Fungicidal n-cycloalkyl-n-{[ortho-(1-substituted-cycloalkyl)heteroaryl]methyl}(thio)carboxamides
WO2017063973A1 (en) 2015-10-14 2017-04-20 Syngenta Participations Ag Fungicidal compositions
WO2017072166A1 (en) 2015-10-27 2017-05-04 Bayer Cropscience Aktiengesellschaft Active compound combinations comprising a (thio)carboxamide derivative and a fungicidal compound
WO2017178549A1 (en) 2016-04-12 2017-10-19 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017207757A1 (en) 2016-06-03 2017-12-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2017220485A1 (en) 2016-06-21 2017-12-28 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015449A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015458A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018015447A1 (en) 2016-07-22 2018-01-25 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018029242A1 (en) 2016-08-11 2018-02-15 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018055135A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018055133A1 (en) 2016-09-23 2018-03-29 Syngenta Participations Ag Microbiocidal tetrazolone derivatives
WO2018065414A1 (en) 2016-10-06 2018-04-12 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018109062A1 (en) 2016-12-16 2018-06-21 Bayer Cropscience Aktiengesellschaft Method for the control of plant bacterial diseases using carboxamide derivatives
WO2018139560A1 (en) 2017-01-26 2018-08-02 三井化学アグロ株式会社 Pyridone compound and bactericide for agricultural and horticultural use, which uses said compound as active ingredient
WO2018158365A1 (en) 2017-03-03 2018-09-07 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018162643A1 (en) 2017-03-10 2018-09-13 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018177894A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018177880A1 (en) 2017-03-31 2018-10-04 Syngenta Participations Ag Fungicidal compositions
WO2018185013A1 (en) 2017-04-03 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184984A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184986A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184988A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184985A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184982A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018184987A1 (en) 2017-04-05 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018185211A1 (en) 2017-04-06 2018-10-11 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018190350A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190351A1 (en) 2017-04-10 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018190352A1 (en) 2017-04-11 2018-10-18 三井化学アグロ株式会社 Pyridone compound, and agricultural and horticultural fungicide having this as active component
WO2018219825A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2018219773A1 (en) 2017-06-02 2018-12-06 Syngenta Participations Ag Fungicidal compositions
WO2018225829A1 (en) 2017-06-08 2018-12-13 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide
WO2018228896A1 (en) 2017-06-14 2018-12-20 Syngenta Participations Ag Fungicidal compositions
WO2019002151A1 (en) 2017-06-28 2019-01-03 Syngenta Participations Ag Fungicidal compositions
WO2019011928A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011929A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011926A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019011923A1 (en) 2017-07-11 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012001A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012011A1 (en) 2017-07-12 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019012003A1 (en) 2017-07-13 2019-01-17 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019053015A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053024A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053027A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053026A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053016A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053010A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019053019A1 (en) 2017-09-13 2019-03-21 Syngenta Participations Ag Microbiocidal quinoline (thio)carboxamide derivatives
WO2019068809A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019068812A1 (en) 2017-10-05 2019-04-11 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019096709A1 (en) 2017-11-15 2019-05-23 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019097054A1 (en) 2017-11-20 2019-05-23 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2019105933A1 (en) 2017-11-29 2019-06-06 Syngenta Participations Ag Microbiocidal thiazole derivatives
WO2019121149A1 (en) 2017-12-19 2019-06-27 Syngenta Participations Ag Microbiocidal picolinamide derivatives
WO2019207062A1 (en) 2018-04-26 2019-10-31 Syngenta Participations Ag Microbiocidal oxadiazole derivatives
WO2020002331A1 (en) 2018-06-29 2020-01-02 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020007658A1 (en) 2018-07-02 2020-01-09 Syngenta Crop Protection Ag 3-(2-thienyl)-5-(trifluoromethyl)-1,2,4-oxadiazole derivatives as agrochemical fungicides
WO2020016180A1 (en) 2018-07-16 2020-01-23 Syngenta Crop Protection Ag Microbiocidal oxadiazole derivatives
WO2020022412A1 (en) 2018-07-25 2020-01-30 三井化学アグロ株式会社 Pyridone compound and agricultural and horticultural fungicide having this as active component
WO2020057939A1 (en) 2018-09-17 2020-03-26 Bayer Aktiengesellschaft Use of the fungicide isoflucypram for controlling claviceps purpurea and reducing sclerotia in cereals
WO2020058207A1 (en) 2018-09-19 2020-03-26 Syngenta Crop Protection Ag Microbiocidal quinoline carboxamide derivatives
WO2020064696A1 (en) 2018-09-26 2020-04-02 Syngenta Crop Protection Ag Fungicidal compositions
WO2020070132A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020070131A1 (en) 2018-10-06 2020-04-09 Syngenta Participations Ag Microbiocidal quinoline dihydro-(thiazine)oxazine derivatives
WO2020084075A1 (en) 2018-10-24 2020-04-30 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfoximine containing substituents
WO2020141136A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
WO2020141135A1 (en) 2018-12-31 2020-07-09 Syngenta Crop Protection Ag Pesticidally active heterocyclic derivatives with sulfur containing substituents
EP3698634A1 (en) * 2019-02-25 2020-08-26 Basf Se Pesticidal mixtures
WO2020173706A1 (en) * 2019-02-25 2020-09-03 Basf Se Pesticidal mixtures
RU2812485C2 (en) * 2019-02-25 2024-01-30 Басф Се Pesticide mixtures
CN114747582A (en) * 2022-03-03 2022-07-15 青岛海利尔生物科技有限公司 Pesticide composition containing Isoflucypram and oxine-copper and application thereof

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